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    • 专利摘要:
    The present invention refers to a new formulation based on two components, which, added to articles made with unsaturated polyester resin or epoxy vinyl ester, contributes to the same unsightly characteristics and/or dissipation of electric charges, maintaining its mechanical characteristics and the possibility of to color the material in all possible color ranges. The formulation consists of a first component that is an active substance that is an ionic salt that will allow the mobility of ions, the cation being a compound based on the species (r4) n, n, N-trialkyl-alkyl-ol- ammonium as such or derivatized in the oh and a system that supports said active substance. This additive or formulation added to unsaturated polyester or epoxy vinyl ester resin can be used in the manufacture of agglomerated stone, gel coat, sheet molding composite or bulk molding composite. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2563903A1
    申请号:ES201500656
    申请日:2015-08-31
    公开日:2016-03-16
    发明作者:Julio Gómez Cordón；Luis OTAÑO JIMÉNEZ；Javier PÉREZ MARTÍNEZ
    申请人:Avanzare Innovacion Tecnologica S L；Avanzare Innovacion Tecnologica Sl；
    IPC主号:
    专利说明:

    DESCRIPTION
    BICOMPONENT ANTISTATIC FORMULATION FOR RESATS OF INSATURED POLYESTER AND EPOXIVINILESTER
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    TECHNICAL SECTOR
    The present invention relates to a new formulation and its manufacturing process, which added to articles made of unsaturated polyester resin or epoxy vinyl ester 10 provides these articles with anti-static characteristics and / or dissipation of electric charges, maintaining their mechanical characteristics and the possibility of coloring the material in all possible ranges of color.
    BACKGROUND OF THE INVENTION
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    Traditionally, articles made of unsaturated polyester and epoxy vinyl ester have problems of static charge accumulation on their surface, due to the great surface resistance and mass resistance they present, with resistivity values at 20 ° C that exceed 1012 Qm. The accumulation of charges produces 20 harmful effects such as electric shocks on people, materials, fuels and electronic systems, among others. Generally the accumulation of electric charges occurs in these materials when they are subjected to friction, for example by the passage of people or even by the action of the wind that contains particles of dust or sand. This effect limits the uses of the materials manufactured in the thermosetting resins indicated above.
    The solutions proposed to avoid this effect of accumulation of charges are classified into three groups:
    Addition of molecules to the resin that become part of the polymer, giving greater electrical conductivity to products manufactured with it. Patent 30 JPH02281071A proposes the use of a maleimide containing an amine group
    quaternary and an anion associated with said chemical group. This type of solution has the disadvantage that the mechanical characteristics of the material get worse compared to the composites to which no additives have been added to the polymer to achieve greater electrical conductivity since the polymerization of the antistatic additive, 35 derived from the maleimide, is different from that of the reactive solvent used
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    typically in unsaturated polyester and epoxy vinyl ester resins.
    It is well known in the scientific literature that the electrical conductivity in ionic conductors depends on the concentration and mobility of the cation and the anion. In this case, the cation derived from maleimide loses its mobility due to the polymerization reaction, decreases its effectiveness as an antistatic (see for example Specialty Polymers: Materials and Applications. 2007. Chapter 13 Conductive Polymers. A. Kumar, D. Salkia and Molecular mobility and Li + conduction in polyester copolymer ionomers based on polyethylene oxide D. Fragiadakis, Sh. Dou, RH Colby, J. Runt The journal of chemical physics, 2009, 130, 064907).
    The GB1127925 patent proposes the use of sulfonation reactions of the surface of textile fibers of unsaturated polyester with sulphurous derivatives. This type of materials has a weak antistatic effect due to the low reactivity of sulfur derivatives with unsaturated polyester and its stability over time is very short because the effect only occurs on the surface of textile fibers and is quickly lost. .
    Patent JPS63110242A proposes the use of quaternary ammonium salts of the type R1R2R3R4N + and an anion type R5S03 'being R1, R2, R3 and R4 hydrogen or a saturated alkyl group of 1 to 24 carbons. This type of salts causes only small increases in electrical conductivity in the material, but above all they produce a great deterioration of the mechanical characteristics of the pieces that contain them.
    These salts alone, among others, have a recognized effect of increasing viscosity when added to unsaturated polyester or epoxy vinyl ester resins as indicated in US4425287, US3538188.
    It is also known that quaternary ammonium salts produce modifications in the polymerization of unsaturated polyester systems, since they affect the activators. (Unsaturated Polyester Technology. 1976. Ed P. F. Bruins)
    The direct addition of ionic, organic and inorganic salts on the resin also produces the accumulation of this at points of the final finished piece because these salts are not completely soluble in the resins and these points in turn generate areas of worse mechanical characteristics and colored areas in different ways that make the manufactured parts invalid for the intended uses.
    Addition of carbon-based conductive solids, for example carbon black or acetylene blacks, as described in applications WO 2006/072553 A1, GB771559 (A), JPS552148587, CN1876714 A or CN1803918 A. These solutions
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    They have two disadvantages: Because carbon-derived materials act as free radical scavengers, mechanical properties are lost during the polymerization reaction of thermosetting resins. And mainly, because carbon-based materials are black, this limits the chromatic possibilities of manufactured items.
    Addition of conductive solids based on metals, conductive metal oxides or silicon carbide in the form of powder or granules as described in patents ES2320839 and US4853155A or in the form of metallic fibers or threads as described in US3996167A and W02013120719A1. These solutions again have a disadvantage: Due to the large size of the solids added, it is necessary to add large amounts thereof to the final material in order to reduce the electrical resistance. In turn, this high need for solid conductors significantly modifies the final properties of the product obtained and significantly limits its chromatic possibilities as they are visible.
    Therefore, there is still a need in the state of the art to provide a formulation or additive that allows obtaining anti-static objects and materials and / or dissipators of electric charges accumulated in unsaturated polyester resins and vinyl ester epoxy resins that have no loss of properties mechanical or chromatic possibilities.
    EXPLANATION OF THE INVENTION
    The object of the present invention is the manufacture of an additive or formulation based on two components, an ionic salt of specific characteristics and an encapsulant / dispersant of said ionic salt. The use of this second compound is intended to prevent the loss of mechanical properties and chromatic possibilities and improve the dispersion of ionic salt.
    The additive or formulation, once prepared, is added on unsaturated polyester or epoxy vinyl ester resins during its manufacturing processes and gives these antistatic and dissipation characteristics of electric charges for manufactured objects that contain this formulation.
    The additive or formulation can be used in manufacturing processes such as chipboard, sheet molding composite (SMC), mass molding composite (BMC) and / or gel coat, allowing the obtaining of panels, blocks, tiles, pianos or structures of this type, colorizable in any range of colors,
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    with optimal mechanical performance. The manufactured parts can be used in construction, decoration, furniture and construction of transport equipment.
    description
    Unsaturated polyester resins are polymeric with respect to which there is extensive knowledge about the state of the art. They consist of polyester chains formed by glycols and / or polyols esterified with dicarboxylic or polycarboxylic acids or anhydrides.
    The preferred glycol is propylene glycol, but others such as ethylene glycol, diethylene glycol, neopentyl glycol and other diols or polyols known in the state of the art can also be employed.
    The unsaturated polycarboxylic acids may be maleic acid, smoking acid, maleic anhydride or others and mixtures of these compounds.
    In addition to the production of unsaturated polyester resins, other polycarboxylic acids are added, such as phthalic anhydride, isophthalic acid, itaconic acid, dicarboxylic cyclohexane acid, terephthalic acid, adipic acid, sebacic acid, azelaic acid and any other glutaric acid, The state of the art.
    The total amount of acid or anhydride varies depending on the characteristics required of the unsaturated polyester formed.
    To the resins can be added dicyclopentadiene. The P.L. Smith et al. "The Use of Dicyclopentadiene in Polyesters" Proceedings of the 2nd Annual Technical Conference. Society of Plastics Industry, Division of Reinforced Plastics, Washington, DC (1967) describes the modification of polyester with dicyclopentadiene. Once the resin is formed, it is diluted in a reactive diluent in proportions ranging from 20 to 60% and may be: styrene, methyl methacrylate, butyl methacrylate, other methacrylates, acrylates, vinyl toluene, para-methyl styrene, divinylbenzene, diallyl phthalate, vinyl derivatives including mixtures thereof and other diluents known in the state of the art.
    In addition other additives such as suitable curing agents, low profile additives, accelerating agents, and the like are incorporated.
    Normally, for final use, reinforcing agents such as fiberglass and inert additives such as quartz, cristobalite, aluminum trihydroxide, glass, metal fillers, wood fillers, calcium carbonate, sand or clay, among others, are added. When necessary, desirable or convenient, pigments, mold release agents, plasticizers and the like are also conventionally used. The way to make these polyester resin compositions is well known in the art.
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    Vinyl ester epoxy resins are polymers for which there is extensive knowledge about the state of the art.
    They can be different types of polymer chains such as epoxy bisphenol A, epoxy bisphenol F or novolacs. All or some of the epoxy groups of the polymer are reacted with an agent that introduces an ester group and an unsaturation at least at each end of the chain, with methacrylic acid being preferred for this function and other monocarboxylic unsaturated acids may be used as acid Acrylic and crotonic acid.
    Once the resin is formed, it is diluted in a reactive diluent in proportions that can range between 20 and 60% and can be: styrene, methyl methacrylate, butyl methacrylate, other methacrylates, acrylates, vinyl toluene, para- methyl styrene, divinylbenzene, diallyl phthalate, vinyl derivatives including mixtures thereof and other diluents known in the state of the art.
    In addition other additives such as suitable curing agents, low profile additives, accelerating agents, and the like are incorporated.
    Normally, for final use, reinforcing agents such as fiberglass and inert additives and fillers such as quartz, cristobalite, aluminum trihydroxide, glass, metal fillers, wood fillers and inorganic fillers such as calcium carbonate, sand or clay, among others are added. . When necessary, desirable or convenient, pigments, mold release agents, plasticizers and the like are also conventionally used.
    This invention can also be applied to resins of the above modified types, for example with isocyanates or mixtures thereof perfectly known in the state of the art.
    The mixtures obtained based on unsaturated polyester or epoxy vinyl ester or its modifications are worked in several ways:
    Agglomerated stone, which allows the manufacture of panels, blocks or tiles, are the composite materials formed by resins and additives to which mineral fillers are added.
    The inorganic load used can comprise, for example, a mixture of crushed granulometry ranging from several centimeters to very few microns and may consist of one or more materials. The materials can be among others, quartz, marble, dolomite, silica, glass, mirror, cristobalite, granite, feldspar, basalt, glass, various sands and mixtures. Inorganic loading is obtained either commercially or by selecting and crushing inorganic starting materials
    to the desired granulometry and mixing them in the appropriate proportions to obtain an optimal packing of the material and a final appearance appropriate to the use that is required.
    The resin formulated with its components and previously homogenized additives is mixed with the mineral filler.
    The mass formed is treated by the processes applied in the state of the art and is deposited in open molds on two sides.
    Vibro-compaction under vacuum is performed on the mixture.
    The materials formed pass to a thermal heating phase in specific homos.
    Once the dough has hardened through the application of heat, the article obtained is subjected to a series of processes that include cooling the product obtained and performing mechanical treatments such as calibrating, polishing and cutting according to the desired final dimensions for the parts to be used. . The forms are mainly 15 pianos but other more complex forms can be obtained.
    Laminates made of composite material of sheet molding composite material of sheet molding "Sheet Molding Composite" (SMC) or bulk molding composite material "Bulk Molding Composite" (BMC) which are materials obtained from unsaturated polyester resins or epoxy vinyl ester described above and 20 which are manufactured by homogeneous mixing of fiberglass, mineral fillers and thermosetting resin of unsaturated polyester or epoxy vinyl ester, with the addition of coupling agents, crosslinking activators, pigments and high pressure fabrication pressure, heating and demoulding.
    Various mineral fillers are added to the resins in the form of fine granulometry powder such as aluminum trihydroxide, quartz, silica, pigments and mixed. Subsequently mainly cut fiberglass is added.
    For sheet molding composite materials (SMC) the material is laminated between plastic sheets. Once formed the sheets can be stored for later use.
    For mass molding composites (BMC) the material is introduced into the mold from a dough.
    To obtain the final materials, the sheets or dough are introduced into a press that works at high pressure and subject the material to heating. The mold can have different shapes.
    35 The resin polymerizes and hardens due to temperature and the pieces are obtained
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    of SMC or BMC composite materials.
    Gel coats are obtained by the homogeneous mixture of mineral fillers, and thermosetting resin of unsaturated polyester or epoxy vinyl ester, with the addition of coupling agents, polymerization activators, pigments, thickener and others and manufactured by mold deposition. They are 0.1 to 1 mm thick coatings of unsaturated polyester resin or vinyl ester epoxy that are applied in one or several layers on the surface of a mold and that serve as a surface protective surface of the main body of the piece being manufactured mainly again in unsaturated polyester or vinyl ester epoxy applied by casting on the gel coat layer.
    The gel coat is deposited on the mold by brush, roller or spray gun, among others.
    A gel coat contains base resin, preferably of good performance to resist the use that will be given to the piece in different types of environments, a reactive diluent mainly styrene, silica fume, precipitated silica or a mixture of both to adapt the product rheology and pigments when the product surface is required to be colored. The gelcoat is polymerized by a system consisting of peroxides and accelerators of cobalt or amines.
    In addition, the gel coat usually contains inorganic fillers. The most commonly used fillers are precipitated calcium carbonate and micronized talc. The self-extinguishing gel coat can be prepared with trihydrated alumina.
    To facilitate handling the gel coat is used mixed with solvents that are classified into two categories:
    The first includes non-copolymerizable viscosity reducers, which serve to reduce the viscosity of the gel coat for spray application. They should have as their main characteristic an extremely rapid degree of evaporation, preferably that they evaporate completely before the gel coat reaches the surface of the mold. Acetone is generally used for that purpose. Approximately 3 to 5% acetone reduces the viscosity of the gel coat to give values compatible with the spray gun application.
    The second category includes copolymerizable solvents, which are an integral part of the cured gel coat.
    Other components of the gel coat are polymerization inhibitors that generally contain the resin to facilitate its preservation before use and active substances, such as UV protectors.
    The formulation presented can also be used in other manufacturing methods
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    Applicable for polyester and epoxy vinyl ester resins, such as mass deposition on mold, contact molding, simultaneous projection molding, watt molding, compression molding, filament winding, pultrusion and their various modifications that are widely known in the state of the art All these different materials so manufactured are very bad electrical conductors and when they are subjected to friction by different materials (shoe soles, dust present in the wind ...) they have a strong tendency to charge electrically resulting in the production of electric discharges on materials and people originating from unpleasant effects to accidents related to fires and explosions. This effect limits or precludes the use of these materials on floors, facades or panels in transport equipment, etc.
    In the present invention a free formulation of conductive polymers, metals, carbon-based conductive materials such as carbon black, carbon fibers, graphite, graphene or carbon nanotubes is obtained, which provides antistatic effect and / or electric charge dissipator. in its application in thermostable resins of unsaturated polyester or in thermostable resins epoxy vinyl ester and in which the presence of two components is necessary so that the first component can be dispersed in the polymer matrix avoiding the loss of mechanical and aesthetic properties, also avoiding the formation of agglomerates or that reacts with the resin components, whose purpose is to increase the electrical conductivity of the materials described above and avoid the accumulation of electrical charges on its surface without losing the mechanical properties and chromatic possibilities.
    The formulation of the present invention consists of two components that are:
    The active substance, which will allow the mobility of ions through the surface and / or the interior of the material and therefore the mobility of electric charges giving rise to the conductive and dissipative effect of electric charges.
    A system that supports said active substance and allows the addition to the previously described composites, so that it maintains the presence of this active substance and its long-term effect, prevents the thickening effect and that the active substance interferes with the reactions of polymerization during the manufacture of the pieces. It also avoids the loss of mechanical properties and the loss of chromatic possibilities, as it is not a black or colored additive and does not generate spots and accumulations due to the low solubility of the ionic salt in the polymer matrix.
    The active substance, the first component, is a salt formed by a cation and an anion.
    The cation is a compound based on the cation as such N, N, N-trialkyl-alkyl-ol-
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    ammonium or derivatized in the OH group, as expressed in the following chemical formula:
    R1
    I +
    R2 - N - (CH2) n -OR4 R3
    R1, R2 and R3 can be -CH3, -CH2CH3, -CH2CH2CH3 or -CH2CH2CH2CH3 n can be 1, 2 or 3
    and OR4 can be hydroxyl or an organic acid derivative. The most common derivatives may be formyl, acetyl, propanoyl, butanoyl, hexanoyl, octanoyl, 2-ethylhexanoyl, decanoyl, dodecanoyl, tetradecanoyl, hexadecanoyl, stearoyl, oleoyl or benzoyl.
    The anion of said salt is inorganic or organic, being it possible to be: chloride, fluoride, bromide, iodide, perchlorate, sulfate, hydrogen sulfate, nitrate, nitrite, dihydrogen phosphate, hydrogen phosphate, phosphate, borate, carbonate, hydrogen carbonate, sulfocyanide, tetrafluroborate, hexafluorophosphate , sulfamate, acetate, propionate, butanoate, formate, oxalate, lactate, glycolate, benzoate, salicylate, citrate, tartrate, p-toluenesulfonate, xylenesulfonate, 2-ethylhexylsulfate, octanosulfonate, methanesulfonate, ethanesulfonate, propanosulfonate, methosulfate (methosulfate) ethyl sulfate), alkyl phosphates, aryl phosphates or saccharinate.
    These active salts are known in the scientific literature and can be obtained commercially or prepared as for example using the following methods:
    In the case of acid derivatives by reaction of cations whose -OR4 is -OH with acid anhydrides for example as indicated by US1957443A or other methods as indicated in US2731493A.
    In turn, the different anions can be introduced into the salt starting from a salt given with chloride anion with a silver derivative of the anion to be obtained in an appropriate solvent Renshaw, R.R .; Atkins, K.N. (1910) Preparation of choline and some of its salts Journal of the American Chemical Society Vol. 32 Issue 1, pp. 128-130 or US7320803B2. Similarly, starting from the initial salt with chloride anion, this can be treated by an alkaline hydroxide in an alcohol solvent and to the result add the acid of the new anion that is intended to be obtained in the final salt, as indicated in US2589707A
    You can also prepare different salts with different anions by reaction
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    of the cation hydroxide obtained by reacting the ethylene oxide with trimethylamine, triethylamine, tributylamine or other amines in water or aqueous solvents and subsequently neutralizing with the acid corresponding to the anion that is intended to be obtained in the final salt, for example as indicated in GB379260A, US2774759 A or US2870198A.
    As already mentioned, the direct addition of salt on the resin also produces thickening, negative modifications in the polymerization reaction, poor dispersion and appearance of agglomerates, which leads to the loss of mechanical properties, appearance of stains and loss of chromatic possibilities
    To avoid the thickening effect of the resin, achieve a homogeneous distribution of the manufactured part and avoid the loss of mechanical and decorative properties, it is necessary to encapsulate or predispers the salt before adding it to the resin.
    The second component is a support with a high surface that encapsulates, absorbs, adsorbs and / or protects the previous anion cation (salt) set, including the following: sodium aluminosilicate, precipitated silica, silicon smoke, sepiolite, attapulgite, estevensite- kerolite, bentonite, ball clay, kaolinite, caolln, metacaolm, haloista, zeolites, Ti02, alumina (Al203), bohemite, aluminum trihydroxide, magnesium hydroxide, magnesium oxide, calcium carbonate, magnesium carbonate, calcium carbonate and magnesium and / or mixtures thereof.
    Preferably, the support that encapsulates, absorbs, adsorbs and / or protects, has to have the following characteristics and is comprised between: precipitated silica with specific surface area (BET) between 30 and 250 m2 / gr, silica smoke 200-300 m2 / gr, sodium aluminosilicate (10 to 200 m2 / gr), sepiolite 0.01-100 pm, attapulgite 0.01-100 pm, estevensite-kerolite 0.01-100 pm, bentonites 0.01-100 pm, clay ball, kaolinite 0.01-100 pm, kaolin 0.01-100 pm, metacaolm 0.1-100 pm, haloist, zeolite 0.01-100 pm, Ti02 0.01-100 pm, alumina 0.01- 100 pm, bohemite 0.01-100pm, aluminum trihydroxide 0.01-100 pm, magnesium hydroxide 0.01-100 pm, magnesium oxide 0.01-100 pm, calcium carbonate 0.01-100 pm, 0.01-100 pm magnesium carbonate, 0.01-100 pm calcium and magnesium carbonate and / or mixtures thereof.
    The process of support and interaction between the two components is carried out in a dry environment, by means of a minimum homogenization of the salt used and the encapsulant due to mechanical action. The encapsulating effect is achieved when the active salt is distributed homogeneously on the surface of the encapsulant or inside, being adsorbed by the material. To that end, among other ways, it can be achieved by interacting the components in a fast mixer.
    Alternatively, the encapsulation can be carried out by: a) simultaneous grinding of the salt and the encapsulate agent, b) by dissolving the salt in an appropriate solvent, depositing it on the encapsulate and finally eliminating the solvent by distillation, evaporation, filtration or by other methods whose final result is a homogeneous distribution of the salt by the surface and / or the interior of the encapsulate.
    The encapsulate provides its effect when the ionic compound is supported by it and the preferable amount of compound is 1% to 40% by mass. Depending on the type of encapsulate used, the pernicious effects on chromatic characteristics, appearance and mechanical properties of the final material appear as the proportion of ionic compound on encapsulate increases. More preferably the proportion of ionic compound in the formulation is between 5 and 25% and even more preferably between 10 and 20%.
    The formulation formed by two components is added to the composite material by the same means, systems and at the same time in which any other filler or pigment is added. It can also be mixed with any inorganic charge that is previously added to the material. If necessary, the formulation can be added to the mixture of liquid resin components.
    The formulation ratios based on the 2 compounds to be added over the unsaturated polyester or the vinyl ester epoxy are preferably set in proportion to the amount of liquid resin employed and range between 1% and 19%, preferably between 2 and 15 % and more preferably between 5 and 10% formulation per unit of resin. This proportion depends on the level of electrical conductivity that is intended to be obtained in the final material.
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    EXAMPLE 1
    Preparation of encapsulation of a salt of (R4) N, NlN-trialkyl-alkyl-ol-ammonium in which R1, R2, R3 are CH3; n = 2 and OR4 is OH and the anion is 5% chloride (choline chloride) in 95% precipitated sodium aluminosilicate.
    Starting from 950 gr of sodium aluminosilicate should preferably have a composition 10 to 14.5 (Si02) 0.5 to 1.5 (Al203) 0.5 to 2 (Na20) and BET surface 50 to 90 m2 / gr, For this example we use 14.5 (Si02) AI203-1.4 (Na20) BET 60 m2 / gr fine powder obtained by precipitation. 50 g of the salt, choline chloride, powder are added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 2
    Preparation as in example 1, in which the ratio is 10% -90%.
    It is based on 900 g of sodium aluminosilicate 14.5 (Si02) AI203-1.4 (Na20) BET 60 m2 / gr fine powder obtained by precipitation. 100 g of choline chloride powder are added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 3
    Preparation as in example 1, in which the ratio is 15% -85%.
    It starts from 850 g of sodium aluminosilicate 14.5 (Si02) AI203-1.4 (Na20) BET 60 m2 / gr fine powder obtained by precipitation. 150 g of choline chloride powder are added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 4
    Preparation of (R4) N, N, N-trialkyl-alkyl-ol-ammonium encapsulation in which R1, R2, R3 are CH3; n = 2 and OR4 is OH and the anion is 10% bromide (choline bromide) in sepiolite.
    It starts from 900 gr of sepiolite BET 320 m2 / gr fine powder obtained by grinding in a humid medium. 100 g of choline bromide powder are added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 5
    Preparation of encapsulation (R4) N, N, N-trialkyl-alkyl-ol-ammonium in which R1, R2, R3
    they are CH3; n = 2 and OR4 is OH and the anion is 10% chloride (choline chloride) in attapulgite.
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    It starts from 970 gr of attapulgite BET 200 m2 / gr fine powder obtained by grinding in dry medium. 30 g of choline chloride powder are added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 6
    Preparation of encapsulation (R4) N, N, N-trialkyl-alkyl-ol-ammonium in which R1, R2, R3 are CH3; n = 2 and OR4 is OH and the anion is 10% chloride (choline chloride) in haloisite. It starts from 900 gr of haloetite BET 200 m2 / gr fine powder obtained by grinding in dry medium. 100 g of choline chloride powder are added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 7
    Preparation of encapsulation (R4) N, N, N-trialkyl-alkyl-ol-ammonium in which R1, R2, R3 are CH3; n = 2 and OR4 is OH and the anion is formate (choline formate) 10% in estevensite-kerolite.
    It starts from 900 gr of estevensite-kerolite BET 200 m2 / gr fine powder obtained by grinding in a dry environment. 100 g of choline formate powder are added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 8
    Preparation of encapsulation (R4) N, N, N-trialkyl-alkyl-ol-ammonium in which R1, R2, R3 are CH3; n = 2 and OR4 is OH and the anion is 10% acetate (choline acetate) in activated sodium bentonite.
    It starts from 900 g of fine powder activated sodium bentonite obtained by activation in liquid medium, drying and grinding in dry medium. 100 g of powdered choline acetate are added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 9
    Preparation of encapsulation (R4) N, N, N-trialkyl-alkyl-ol-ammonium in which R1, R2, R3 are CH3; n = 2 and OR4 is OH and the anion is 10% acetate (choline acetate) in calcium bentonite.
    It starts from 900 grams of fine powder calcium bentonite obtained by grinding in a dry environment. 100 g of powdered choline acetate are added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 10
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    Preparation of encapsulation (R4) N, N, N-trialkyl-alkyl-ol-ammonium in which R1, R2, R3 are CH3; n = 2 and OR4 is OH and the anion is methanesulfonate (choline methanesulfonate) 10% in ball clay.
    It starts from 900 gr fine dust ball clay obtained by grinding in dry medium. 100 g of choline methanesulfonate powder are added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 11
    Preparation of encapsulation (R4) N, N1N-trialkyl-alkyl-ol-ammonium in which R1, R2, R3 are CH3; n = 2 and OR4 is OH and the anion is 10% chloride (choline chloride) in kaolin.
    It starts from 950 gr of fine powder micronized kaolin obtained by grinding in dry medium. 50 g of choline chloride powder are added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 12
    Preparation of encapsulation (R4) N, N, N-trialkyl-alkyl-ol-ammonium in which R1, R2, R3 are CH3; n = 2 and OR4 is OH and the anion is 10% chloride (choline chloride) in metacaolln.
    It starts from 900 gr of fine powder micronized metacaolln obtained by heat treatment of kaolin and grinding in a dry environment. 100 g of choline chloride powder are added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 13
    Preparation of encapsulation (R4) N, N, N-trialkyl-alkyl-ol-ammonium in which R1, R2, R3 are CH3; n = 2 and OR4 is OH and the anion is 10% chloride (choline chloride) in zeolite A. It starts from 900 gr of zeolite A micronized fine powder obtained by precipitation and grinding in dry medium. 100 g of choline chloride powder are added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 14
    Preparation of encapsulation (R4) N1N, N-trialkyl-alkyl-ol-ammonium in which R1, R2, R3 are CH3; n = 2 and OR4 is OH and the anion is 10% chloride (choline chloride) in aluminum oxide (alumina).
    It starts from 900 g of aluminum oxide (alumina) fine powder less than 20 pm obtained by grinding in dry medium. 100 g choline chloride powder is added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
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    EXAMPLE 15
    Preparation of encapsulation (R4) NfN, N-trialkyl-alkyl-ol-ammonium in which R1, R2, R3 are CH3; n = 2 and OR4 is OH and the anion is 10% chloride (choline chloride) in bohemite. It starts from 900 g of bohemite fine powder less than 30 obtained by grinding in dry medium. 100 g choline chloride powder is added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes. EXAMPLE 16
    Preparation of encapsulation (R4) N, N, N-trialkyl-alkyl-ol-ammonium in which R1, R2, R3 are CH3; n = 2 and OR4 is OH and the anion is 10% chloride (choline chloride) in aluminum trihydroxide.
    It starts from 900 gr of fine aluminum powder trihydroxide less than 30 jim obtained by grinding in dry medium. 100 g choline chloride powder is added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 17
    Preparation of N, N, N-trialkyl-alkyl-stearoyl-ammonium encapsulation in which R1, R2, R3 are CH3; n = 2 and OR4 according to the general formula of the compounds of the present invention is stearoyl and the anion is 10% chloride (stearoylcholine chloride) in calcium carbonate.
    It starts from 900 g of calcium carbonate fine powder less than 5 fim obtained by grinding. 100 gr stearoylcholine chloride powder is added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 18
    Preparation of encapsulation (R4) N, N, N-trialkyl-alkyl-ol-ammonium in which R1, R2, R3 are CH3; n = 2 and OR4 is OH and the anion is 10% bromide (choline bromide) in sodium aluminiosilicate and haloisite.
    It starts from 500 gr of sodium aluminosilicate BET 60 m2 / gr. 400 gr of fine powder haloisite is added. 100 g choline bromide powder is added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 19
    Preparation of encapsulation (R4) N, N, N-trialkyl-alkyl-ol-ammonium in which R1, R2, R3 are CH3; n = 2 and OR4 is OH and the anion is chloride (choline chloride) 10% in precipitated silica 100 BET m2 / gr.
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    It starts from 900 gr of precipitated silica BET 100 m2 / gr. 100 g choline chloride powder is added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 20
    Preparation of encapsulation (R4) N, N> N-trialkyl-alkyl-ol-ammonium in which R1, R2, R3 are CH3; n = 2 and OR4 is OH and the anion is 10% chloride (choline chloride) in titanium dioxide (Ti02).
    It starts from 900 g of titanium dioxide (Ti02) smaller than 5 pm. 100 g choline chloride powder is added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 21
    Preparation of encapsulation (R4) N, N, N-trialkyl-alkyl-ol-ammonium in which R1, R2, R3 are CH3; n = 2 and OR4 is OH and the anion is 10% chloride (choline chloride) in magnesium hydroxide (Mg (OH) 2) of 5 pm of average particle size.
    It starts from 900 g of magnesium hydroxide (Mg (OH) 2) of 5 pm. 100 g choline chloride powder is added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 22
    Preparation of encapsulation (R4) N, N, N-trialkyl-alkyl-ol-ammonium in which R1, R2, R3 are CH3; n = 2 and OR4 is OH and the anion is 10% bromide (choline bromide) in magnesium hydroxide.
    It starts from 900 gr of magnesium hydroxide. 100 g of choline bromide powder are added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 23
    Preparation of encapsulation (R4) N, N, N-trialkyl-alkyl-ol-ammonium in which R1, R2, R3 are CH3; n = 2 and OR4 is OH and the anion is ethylsulfate (choline ethylsulfate) 10% in magnesium hydroxide.
    It starts from 900 gr of magnesium hydroxide. 100 g of powdered choline ethyl sulfate are added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 24
    Preparation of encapsulation (R4) N, N, N-trialkyl-alkyl-ol-ammonium in which R1, R2, R3 are CH3; n = 2 and OR4 is OH and the anion is methylsulfate (choline methylsulfate) 10% in Zeolite A.
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    It starts from 900 grams of Zeolite A. 100 grams of powdered choline ethylsulfate are added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 25
    Preparation of encapsulation (R4) N, N, N-trialkyl-alkyl-ol-ammonium in which R1, R2, R3 are CH3; n = 2 and OR4 is OH and the anion is tetrafluroborate (choline tetrafluoroborate) 10% calcium carbonate.
    It starts from 900 g of calcium carbonate. 100 g of choline tetrafluroborate powder are added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 26
    Preparation of encapsulation (R4) N, N, N-trialkyl-alkyl-ol-ammonium in which R1, R2, R3 are CH3; n = 2 and OR4 is OH and the anion is 10% acetate (choline acetate) in calcium carbonate.
    It starts from 900 gr of calcium carbonate. 100 g of powdered choline acetate are added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 27
    Preparation of encapsulation (R4) N, NIN-trialkyl-alkyl-ol-ammonium in which R1, R2, R3 are CH3; n = 2 and OR4 is OH and the anion is 10% lactate (choline lactate) in precipitated silica.
    It starts from 900 gr of precipitated silica. 100 g of powdered choline lactate are added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 28
    Preparation of encapsulation (R4) N, N, N-trialkyl-alkyl-ol-ammonium in which R1, R2, R3 are CH3; n = 2 and OR4 is OH and the anion is 2H-1A6,2-benzothiazoM, 1,3-thionate (choline saccharinate) 15% in precipitated silica.
    It starts from 900 gr of precipitated silica. 100 gr of choline saccharinate powder are added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 29
    Preparation of N, N, N-trialkyl-alkylacetylammonium encapsulation in which R1, R2, R3 are CH3; n = 2 and OR4 according to the general formula of the compounds of the present invention is OC (= 0) CH3 and the anion is 10% chloride (acetylcholine chloride) in precipitated silica.
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    It starts from 900 grams of precipitated silica. 100 g of powdered acetylcholine chloride are added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 30
    Preparation of encapsulation (R4) N, N, N-trialkyl-alkyl (n) -ol-ammonium in which R1, R2, R3 are CH2CH3; n = 2 and OR4 is OH and the anion is 10% chloride in precipitated sodium aluminosilicate.
    It starts from 900 g of sodium aluminosilicate 14.5 (Si02) AI203-1.4 (Na20) BET 60 m2 / gr fine powder obtained by precipitation. Add 100 gr of the salt powder. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 31
    Preparation of encapsulation (R4) N, NIN-trialkyl-alkyl-ol-ammonium in which R1, R2, R3 are CH2CH2CH3; n = 2 and OR4 is OH and the anion is 10% chloride in precipitated sodium aluminosilicate.
    It starts from 900 g of sodium aluminosilicate 14.5 (Si02) AI203-1.4 (Na20) BET 60 m2 / gr fine powder obtained by precipitation. Add 100 gr of the salt powder. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 32
    Preparation of encapsulation (R4) N, N, N-trialkyl-alkyl-ol-ammonium in which R1, R2, R3 are CH3; n = 2 and OR4 is OH and the anion is 10% bromide (choline bromide) in precipitated silica.
    It starts from 900 gr of precipitated silica. 100 g of choline bromide powder are added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 33
    Preparation of N, N, N-trialkylacetylalkyl-ammonium encapsulation in which R1, R2, R3 are CH3; n = 2 and OR4 according to the general formula of the compounds of the present invention is OC (= 0) CH3 and the anion is ethyl sulfate (acetylcholine ethyl sulfate) 10% in haloisite.
    It starts from 900 gr of haloisite. 100 g of powdered acetylcholine ethyl sulfate are added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 34
    Preparation of N, N, N-trialkyl 2-ethyl-hexanoyl alkylammonium encapsulation in which R 1,
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    R2, R3 are CH3; n = 2 and OR4 according to the general formula of the compounds of the present invention is 2-ethyl-hexanoyl and the anion is ethyl sulfate (2-ethyl-hexanoylcholine ethyl sulfate) 10% in precipitated silica.
    It starts from 900 gr of precipitated silica. 100 g of powdered 2-ethylhexanoylcholine ethyl sulfate are added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 35
    Preparation of encapsulation (R4) N, N, N-trialkyl-alkyl (n) -ol-ammonium in which R1, R2, R3 are CH3; n = 2 and OR4 is OH and the anion is 10% chloride (choline chloride) in precipitated silica.
    It starts from 900 gr of precipitated silica. 100 g of choline chloride powder are added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE 36
    Preparation of encapsulation (R4) N, N, N-trialkyl-alkyl (n) -ol-ammonium in which R1, R2, R3 are CH3; n = 2 and OR4 is OH and the anion is ethyl sulfate (choline ethyl sulfate) 10% in haloisite.
    It starts from 900 gr of haloisite. 100 g of powdered choline ethyl sulfate are added. It is encapsulated by mixing at high revolutions in a fast turbomixer at 2500 rpm for 10 minutes.
    EXAMPLE A
    Material type agglomerated stone, without antistatic additive, example that we take as a comparative reference 1.
    Homogeneous mass manufactured from 3 kg of materials with the following composition expressed in percentage by weight:
    Load formed by: 24% micronized cristobalite, 64% crushed quartz and 2% titanium dioxide pigment.
    Binder resin 10% formed by unsaturated polyester orthophthalic resin with: trimethoxysilylpropylmethacrylate (2% with respect to the resin), cumyl hydroperoxide (2% with respect to the resin)
    Additives are added to the resin and mixed and dispersed therein. The charges are mixed. The resin with its additives is added to the mixture of charges and homogenized in a planetary mixer. The dough is arranged on a mold in whose bottom kraft paper has been placed. It is pressed by vibrocompaction and empty for 2 minutes. The mold is snowed at a homo at 120 ° C temperature 40
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    minutes until the resin polymerizes. It is allowed to cool to room temperature and two days later it is demoulded, cut, polished and the thickness is calibrated.
    Electrical conductivity and flexural strength tests are performed with the following result:
     Example  Surface electrical resistance Flexural strength Appearance
     A Comparative reference 1  > 1000 GOhm 63 MPa Glossy surface
    EXAMPLE AO
    Material agglomerated stone, with antistatic additive tetramethylammonium methylsulfate (ACROS Organics), example that we take as reference JPS63110242A
    Homogeneous mass manufactured from 3 kg of materials with the following composition expressed in percentage by weight:
    Load formed by: 23.85% micronized cristobalite, 64% crushed quartz and 2% titanium dioxide pigment.
    0.15% antistatic additive with respect to the total and equivalent to 1.5% with respect to the binder, this tetramethylammonium methylsulfate being.
    Binder 10% formed by unsaturated polyester orthophthalic resin with: trimethoxysilylpropylmethacrylate (2% with respect to the resin), cumyl hydroperoxide (2% with respect to the resin)
    Additives are added to the resin and mixed and dispersed therein. The charges and the antistatic additive are mixed. The resin with its additives is added to the mixture of fillers and antistatic additive and homogenized in a planetary mixer. The dough is arranged on a mold in whose bottom kraft paper has been placed. It is pressed by vibrocompaction and empty for 2 minutes. The mold is brought to a homo at 120 ° C temperature 40 minutes until the resin is polymerized. It is allowed to cool to room temperature and two days later it is demoulded, cut, polished and the thickness is calibrated.
    Electrical conductivity and flexural strength tests are performed with the following result:
     Example  Surface electrical resistance Flexural strength Appearance
     A0 Comparative reference 2  489 GOhm 23 MPa Dark oily stains on
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     surface
    Only slight anti-static effect is produced, resistance to bending is lost, which makes the material invalid for use as tiles, countertops, tables and other construction materials, surface stains appearing that make the chromatic possibilities of the material useless.
    EXAMPLE B
    Material type agglomerated stone, with antistatic additive chloride choline, example that we take as a comparative reference.
    Homogeneous mass manufactured from 3 kg of materials with the following composition expressed in percentage by weight:
    Load formed by: 23.85% micronized cristobalite, 64% crushed quartz and 2% titanium dioxide pigment.
    0.15% antistatic additive with respect to the total and equivalent to 1.5% with respect to the binder, this choline chloride being pure.
    Binder 10% formed by unsaturated polyester orthophthalic resin with: trimethoxysilylpropylmethacrylate (2% with respect to the resin), cumyl hydroperoxide (2% with respect to the resin)
    Additives are added to the resin and mixed and dispersed therein. The charges and the antistatic additive are mixed. The resin with its additives is added to the mixture of fillers and antistatic additive and homogenized in a planetary mixer. The dough is arranged on a mold in whose bottom kraft paper has been placed. It is pressed by vibrocompaction and empty for 2 minutes. The mold is snowed at a homo at 120 ° C temperature 40 minutes until the resin is polymerized. It is allowed to cool to room temperature and two days later it is demoulded, cut, polished and the thickness is calibrated.
    Electrical conductivity and flexural strength tests are performed with the following result:
     Example  Surface electrical resistance Flexural strength Appearance
     B Comparative reference 3  15 MOhm 22 MPa Oily dark spots on surface
    Electrical conductivity useful for the application of the material on floors or walls is achieved but the mechanical characteristics and chromatic possibilities are lost.
    EXAMPLE C
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    Material type agglomerated stone, with antistatic additive choline bromide, example that we take as a comparative reference.
    Homogeneous mass manufactured from 3 kg of materials with the following composition expressed in percentage by weight:
    Load formed by: 23.95% micronized cristobalite, 64% crushed quartz and 2% titanium dioxide pigment.
    0.05% antistatic additive with respect to the total and equivalent to 0.5% with respect to the binder, this choline bromide being pure.
    Binder 10% formed by unsaturated polyester orthophthalic resin with: trimethoxysilylpropylmethacrylate (2% with respect to the resin), cumyl hydroperoxide (2% with respect to the resin)
    Additives are added to the resin and mixed and dispersed therein. The charges and the antistatic additive are mixed. The resin with its additives is added to the mixture of fillers and antistatic additive and homogenized in a planetary mixer. The dough is arranged on a mold in whose bottom kraft paper has been placed. It is pressed by vibrocompaction and empty for 2 minutes. The mold is snowed at a homo at 120 ° C temperature 40 minutes until the resin is polymerized. It is allowed to cool to room temperature and two days later it is demoulded, cut, polished and the thickness is calibrated.
    Electrical conductivity and flexural strength tests are performed with the following result:
     Example  Electrical resistance Flexural strength Appearance
     C Comparative reference 4  8 GOhm 24 MPa Oily dark spots on surface
    The electrical conductivity is limited and the mechanical properties and chromatic possibilities are lost, so that the material loses its possibilities of use. EXAMPLE D
    Material agglomerated stone, with antistatic additive choline chloride encapsulated in sodium aluminosilicate according to EXAMPLE 1.
    Homogeneous mass manufactured from 3 kg of materials with the following composition expressed in percentage by weight:
    Load formed by: 23% micronized cristobalite, 64% crushed quartz and 2% titanium dioxide pigment.
    1% antistatic additive with respect to the total and equivalent to 10% with respect to the
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    binder, this encapsulation of 5% choline chloride in 95% sodium aluminosilicate according to EXAMPLE 1.
    Binder 10% formed by unsaturated polyester orthophthalic resin with: trimethoxysilylpropylmethacrylate (2% with respect to the resin), cumyl hydroperoxide (2% with respect to the resin)
    Additives are added to the resin and mixed and dispersed therein. The charges and the antistatic additive are mixed. The resin with its additives is added to the mixture of fillers and antistatic additive and homogenized in a planetary mixer. The dough is arranged on a mold in whose bottom kraft paper has been placed. It is pressed by vibrocompaction and empty for 2 minutes. The mold is snowed at a homo at 120 ° C temperature 40 minutes until the resin is polymerized. It is allowed to cool to room temperature and two days later it is demoulded, cut, polished and the thickness is calibrated.
    Electrical conductivity and flexural strength tests are performed with the following result:
     Example  Electrical resistance Flexural strength Appearance
     D  14 GOhm 44 MPa Correct
    EXAMPLE E
    Material agglomerated stone, with antistatic additive choline chloride encapsulated in sodium aluminosilicate according to EXAMPLE 2.
    Homogeneous mass manufactured from 3 kg of materials with the following composition expressed in percentage by weight:
    Load formed by: 23% micronized cristobalite, 64% crushed quartz and 2% titanium dioxide pigment.
    Antistatic additive 1% with respect to the total and equivalent to 10% with respect to the binder, this choline chloride encapsulated 10% in sodium aluminosilicate 90% according to EXAMPLE 2.
    Binder 10% formed by unsaturated polyester orthophthalic resin with: trimethoxysilylpropylmethacrylate (2% with respect to the resin), cumyl hydroperoxide (2% with respect to the resin)
    Additives are added to the resin and mixed and dispersed therein. The charges and the antistatic additive are mixed. The resin with its additives is added to the mixture of fillers and antistatic additive and homogenized in a planetary mixer. The dough is arranged on a mold in whose bottom kraft paper has been placed. Be
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    Press by vibrocompaction and vacuum for 2 minutes. The mold is brought to a homo at 120 ° C temperature 40 minutes until the resin is polymerized. It is allowed to cool to room temperature and two days later it is demoulded, cut, polished and the thickness is calibrated.
    Electrical conductivity and flexural strength tests are performed with the following result:
     Example  Electrical resistance Flexural strength Appearance
     AND  500 MOhm 41 MPa Correct
    EXAMPLE F
    Material agglomerated stone, with antistatic additive choline chloride encapsulated in sodium aluminosilicate according to EXAMPLE 3.
    Homogeneous mass manufactured from 3 kg of materials with the following composition expressed in percentage by weight:
    Load formed by: 23% micronized cristobalite, 64% crushed quartz and 2% titanium dioxide pigment.
    Antistatic additive 1% with respect to the total and equivalent to 10% with respect to the binder, this choline chloride encapsulated 15% in sodium aluminosilicate 85% according to EXAMPLE 3.
    Binder 10% formed by unsaturated polyester orthophthalic resin with: trimethoxysilylpropylmethacrylate (2% with respect to the resin), cumyl hydroperoxide (2% with respect to the resin)
    Additives are added to the resin and mixed and dispersed therein. The charges and the antistatic additive are mixed. The resin with its additives is added to the mixture of fillers and antistatic additive and homogenized in a planetary mixer. The dough is arranged on a mold in whose bottom kraft paper has been placed. It is pressed by vibrocompaction and empty for 2 minutes. The mold is brought to a homo at 120 ° C temperature 40 minutes until the resin is polymerized. It is allowed to cool to room temperature and two days later it is demoulded, cut, polished and the thickness is calibrated.
    Electrical conductivity and flexural strength tests are performed with the following result:
     Example  Electrical resistance Flexural strength Appearance
     F  80 MOhm 41 MPa Correct
    Material agglomerated stone, with antistatic additive choline bromide encapsulated in sepiolite according to EXAMPLE 4.
    Homogeneous mass manufactured from 3 kg of materials with the following 5 composition expressed in percentage by weight:
    Load formed by: 23% micronized cristobalite, 64% crushed quartz and 2% titanium dioxide pigment.
    Antistatic additive 1% with respect to the total and equivalent to 10% with respect to the binder, this choline bromide encapsulated 10% in sepiolite 90% 10 according to EXAMPLE 4.
    Binder 10% formed by unsaturated polyester orthophthalic resin with: trimethoxysilylpropylmethacrylate (2% with respect to the resin), cumyl hydroperoxide (2% with respect to the resin)
    Additives are added to the resin and mixed and dispersed therein. The charges and the antistatic additive are mixed. The resin with its additives is added to the mixture of fillers and antistatic additive and homogenized in a planetary mixer. The dough is arranged on a mold in whose bottom kraft paper has been placed. It is pressed by vibrocompaction and empty for 2 minutes. The mold is snowed at a homo at 120 ° C temperature 40 minutes until the resin is polymerized. It is allowed to cool to room temperature and two days later it is demoulded, cut, polished and
    Calibrate the thickness.
    Electrical conductivity and flexural strength tests are performed with the following result:
     Example  Electrical resistance Flexural strength Appearance
     G  680 MOhm 32 MPa Correct
    25 Several comparative examples are made with additions of 1% antistatic additive with respect to the total mass and equivalent to 10% with respect to the binder, prepared in different encapsulants in relation to 10% the indicated salt and 90% encapsulant.
    The form of preparation is identical to the one described above in example F and the 30 results are set out below:
     AHEM  SALT ADDITIVE 10% ENCAPSULA RESIST RESIST APPEAR
     PLO  ANTIEST Penthouse  NTE90% ENCIA SUPERF ICIAL ENCIA LA FLEXIO CIA SUPERFI CIAL
     H  Example 5 Atapulgite Chloride 384 MOhm 29 Correct
     one  Example 6 Haloisite Chloride 291 MOhm 34 Correct
     J  Example 7 Hill formate Estevensita- Kerolita 895 MOhm 27 Light lost brightness
     K  Example 8 Acetate Choline Bentonite Na activated 889 MOhm 26 Slight lost brightness
     L  Example 9 Acetate Choline Bentonite Calcium 982 MOhm 28 Slight lost brightness
     M  Example 10 Methanesulfon ato hill Ball clay 352 MOhm 29 Light lost gloss
     N  Example 11 Micronized Choline Choline Chloride 258 MOhm 26 Light lost gloss
     0  Example 12 Choline Chloride Metacaolin 267 MOhm 28 Light lost gloss
     p  Example 13 Zeolite Chloride A 689 MOhm 33 Correct
     Q  Example 14 Choline Chloride Alumina 572 MOhm 26 Slight lost brightness
     R  Example 15 Chloride Choline Bohemite 567 MOhm 26 Slight lost brightness
     s  Example 16 Choline chloride Aluminum trihydroxide 421 MOhm 29 Light lost gloss
     T  Example 17 Stearoylcholine Chloride Calcium Carbonate 745 MOhm 24 Light lost gloss
     OR  Example 18 Sodium Aluminosilicate bromide and Haloisite 623 MOhm 38 Correct
     V  Example 19 Precipitated Chloride Silica Chloride 496 MOhm 26 Slight lost brightness
     w  Example 20 Choline chloride Titanium dioxide 569 MOhm 28 Slight lost gloss
     X  Example 21 Choline Chloride Magnesium Hydroxide 556 MOhm 29 Slight lost gloss
     Y  Example 22 Choline bromide Magnesium hydroxide 731 MOhm 24 Correct
     z  Example Ethyl Sulfate 477 39 Hydroxide Light
     23 mg magnesium hill   lost brightness
     AA  Example 24 Zeolite Methylsulfate A 372 MOhm 36 Slight lost gloss
     AB  Example 25 Tetrafluorobor ato choline Calcium carbonate 450 MOhm 37 Light lost gloss
     AC  Example 26 Choline acetate Calcium carbonate 931 MOhm 37 Slight lost brightness
     AD  Example 27 Lactate Hill Silica precipitated 898 MOhm 35 Slight lost brightness
     AE  Example 28 Choline Saccharinate Silica precipitated 746 MOhm 39 Slight lost brightness
     AF  Example 29 Acetylcholine Chloride Silica precipitated 3 GOhm 38 Slight lost brightness
    EXAMPLE AG
    Material agglomerated stone, with antistatic additive choline bromide encapsulated in precipitated silica according to EXAMPLE 32.
    Homogeneous mass manufactured from 3 kg of materials with the following composition expressed in percentage by weight:
    Load formed by: 20% ground quartz, 64% crushed quartz and 5% titanium dioxide pigment.
    Antistatic additive 1% with respect to the total and equivalent to 10% with respect to the binder, this choline bromide encapsulation being 10% in precipitated silica 90% according to EXAMPLE 32.
    Binder 10% formed by unsaturated polyester orthophthalic resin with: trimethoxysilylpropylmethacrylate (2% with respect to the resin), cumyl hydroperoxide (2% with respect to the resin)
    Additives are added to the resin and mixed and dispersed therein. The charges and the antistatic additive are mixed. The resin with its additives is added to the mixture of fillers and antistatic additive and homogenized in a planetary mixer. The dough is arranged on a mold in whose bottom kraft paper has been placed. It is pressed by vibrocompaction and empty for 2 minutes. The mold is brought to a homo at 120 ° C temperature 40 minutes until the resin is polymerized. It is allowed to cool to room temperature and two days later it is demoulded, cut, polished and the thickness is calibrated.
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    Electrical conductivity and flexural strength tests are performed with the
    following result:
     Example  Electrical resistance Flexural strength Appearance
     AG  992 MOhm 44 MPa Correct
    EXAMPLE AH
    Material agglomerated stone, with antistatic additive choline chloride encapsulated in sodium aluminosilicate according to EXAMPLE 3.
    Homogeneous mass manufactured from 3 kg of materials with the following composition expressed in percentage by weight:
    Load formed by: 23% ground quartz, 64% crushed quartz and 2% titanium dioxide pigment over the total.
    Antistatic additive 1% with respect to the total and equivalent to 10% with respect to the binder, this choline chloride encapsulated 15% in sodium aluminosilicate 85% according to EXAMPLE 3.
    Binder 10% of the total, formed by unsaturated polyester orthophthalic resin with: trimethoxysilylpropylacrylate (2% with respect to the resin), cumyl hydroperoxide (2% with respect to the resin)
    Additives are added to the resin and mixed and dispersed therein. The charges and the antistatic additive are mixed. The resin with its additives is added to the mixture of fillers and antistatic additive and homogenized in a planetary mixer. The dough is arranged on a mold in whose bottom kraft paper has been placed. It is pressed by vibrocompaction and vacuum for 2 minutes. The mold is snowed at a homo at 120 ° C temperature 40 minutes until the resin is polymerized. It is allowed to cool to room temperature and two days later it is demoulded, cut, polished and the thickness is calibrated.
    Electrical conductivity and flexural strength tests are performed with the following result:
     Example  Electrical resistance Flexural strength Appearance
     AH  170 MOhm 55 MPa Correct
    EXAMPLE Al
    Agglomerated stone type material, with antistatic additive acetylcholine ethyl sulfate encapsulated in haloisite according to EXAMPLE 33.
    Homogeneous mass manufactured from 3 kg of materials with the following
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    composition expressed in percentage by weight:
    Load formed by: 23% ground quartz, 64% crushed quartz and 2% titanium dioxide pigment.
    Antistatic additive 1% with respect to the total and equivalent to 10% with respect to the binder, this encapsulation of acetylcholine ethyl sulfate 10% in haloisite 90% according to EXAMPLE 33.
    Binder 10% of the total, formed by epoxy vinyl ester resin with: trimethoxysilylpropylmethacrylate (2% with respect to the resin), cumyl hydroperoxide (2% with respect to the resin)
    Additives are added to the resin and mixed and dispersed therein to form the binder. The charges and the antistatic additive are mixed. The resin with its additives is added to the mixture of fillers and antistatic additive and homogenized in a planetary mixer. The dough is arranged on a mold in whose bottom kraft paper has been placed. It is pressed by vibrocompaction and empty for 2 minutes. The mold is snowed at a homo at 120 ° C temperature 40 minutes until the resin is polymerized. It is allowed to cool to room temperature and two days later it is demoulded, cut, polished and the thickness is calibrated.
    Electrical conductivity and flexural strength tests are performed with the following result:
     Example  Electrical resistance Flexural strength Appearance
     To the  932 MOhm 32 MPa Light loss of surface brightness
    EXAMPLE AJ
    Material agglomerated stone, with antistatic additive 2-ethylhexanoylcholine ethyl sulfate encapsulated in precipitated silica according to EXAMPLE 2.
    Homogeneous mass manufactured from 3 kg of materials with the following composition expressed in percentage by weight:
    Load formed by: 23% ground quartz, 64% crushed quartz and 2% titanium dioxide pigment.
    Antistatic additive 1% with respect to the total and equivalent to 10% with respect to the binder, this encapsulation being acetylcholine ethyl sulfate 10% in silica precipitated 90% according to EXAMPLE 34.
    Binder 10% of the total, formed by unsaturated polyester resin in
    25% styrene and 10% butyl methacrylate diluent with: trimethoxysilylpropyl methacrylate (2%
    with respect to the resin), cumyl hydroperoxide (2% with respect to the resin)
    30
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    Additives are added to the resin and mixed and dispersed therein to form the binder. The charges and the antistatic additive are mixed. The resin with its additives is added to the mixture of fillers and antistatic additive and homogenized in a planetary mixer. The dough is arranged on a mold in whose bottom kraft paper has been placed. It is pressed by vibrocompaction and empty for 2 minutes. The mold is brought to a homo at 120 ° C temperature 40 minutes until the resin is polymerized. It is allowed to cool to room temperature and two days later it is demoulded, cut, polished and the thickness is calibrated.
    Electrical conductivity and flexural strength tests are performed with the following result:
     Example  Electrical resistance Flexural strength Appearance
     AJ  923 MOhm 36 MPa Correct
    AK EXAMPLE
    Material agglomerated stone, with antistatic additive choline chloride encapsulated in precipitated silica according to EXAMPLE 35.
    Homogeneous mass manufactured from 3 kg of materials with the following composition expressed in percentage by weight:
    Load formed by: 23% milled albite feldspar, 64% crushed quartz and 2% titanium dioxide pigment.
    Antistatic additive 1% with respect to the total and equivalent to 10% with respect to the binder, this choline chloride encapsulation being 10% in precipitated silica 90% according to EXAMPLE 35.
    Binder 10% of the total, consisting of unsaturated polyester resin of dicyclopentadiene with: trimethoxysilylpropylmethacrylate (2% with respect to the resin), cumyl hydroperoxide (2% with respect to the resin)
    Additives are added to the resin and mixed and dispersed therein to form the binder. The charges and the antistatic additive are mixed. The resin with its additives is added to the mixture of fillers and antistatic additive and homogenized in a planetary mixer. The dough is arranged on a mold in whose bottom kraft paper has been placed. It is pressed by vibrocompaction and empty for 2 minutes. The mold is brought to a homo at 120 ° C temperature 40 minutes until the resin is polymerized. It is allowed to cool to room temperature and two days later it is demoulded, cut, polished and the thickness is calibrated.
    Electrical conductivity and flexural strength tests are performed with the
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    following result:
     Example  Electrical resistance Flexural strength Appearance
     AK  763 MOhm 31 MPa Correct
    EXAMPLE TO
    Material agglomerated stone, with antistatic additive (R4) N, N, N-trialkyl-alkyl-ammonium in which R1, R2, R3 are CH2CH3; n = 2 and OR4 is OH and the anion is chloride, encapsulated in sepiolite according to EXAMPLE 30.
    Homogeneous mass manufactured from 3 kg of materials with the following composition expressed in percentage by weight:
    Load formed by: 20% ground quartz, 64% crushed quartz and 5% titanium dioxide pigment.
    1% antistatic additive with respect to the total and equivalent to 10% with respect to the binder, this encapsulation being (R4) N, N, N-trialkyl-alkyl-ol-ammonium in which R1, R2, R3 are CH2CH3; n = 2 and OR4 is OH and the anion is chloride, 10% in sepiolite 90% according to EXAMPLE 30.
    Binder 10% formed by unsaturated polyester orthophthalic resin with: trimethoxysilylpropylmethacrylate (2% with respect to the resin), cumyl hydroperoxide (2% with respect to the resin)
    Additives are added to the resin and mixed and dispersed therein. The charges and the antistatic additive are mixed. The resin with its additives is added to the mixture of fillers and antistatic additive and homogenized in a planetary mixer. The dough is arranged on a mold in whose bottom kraft paper has been placed. It is pressed by vibrocompaction and empty for 2 minutes. The mold is brought to a homo at 120 ° C temperature 40 minutes until the resin is polymerized. It is allowed to cool to room temperature and two days later it is demoulded, cut, polished and the thickness is calibrated.
    Electrical conductivity and flexural strength tests are performed with the following result:
     Example  Electrical resistance Flexural strength Appearance
     TO THE  96 GOhm 36 MPa Light loss of surface brightness
    EXAMPLE AM
    Material agglomerated stone, with antistatic additive (R4) N, N, N-trialkyl-alkyl-ol-
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    ammonium in which R1, R2, R3 are CH2CH2CH3; n = 2 and OR4 is OH and the anion is 10% chloride encapsulated in sepiolite according to EXAMPLE 31.
    Homogeneous mass manufactured from 3 kg of materials with the following composition expressed in percentage by weight:
    Load formed by: 20% ground quartz, 64% crushed quartz and 5% titanium dioxide pigment.
    1% antistatic additive with respect to the total and equivalent to 10% with respect to the binder, this being encapsulated (R4) N, N, N-trialkyl-alkyl-ol-ammonium in which R1, R2, R3 are CH2CH2CH3; n = 2 and OR4 is OH and the anion is chloride, 10% in sepiolite 90% according to EXAMPLE 31.
    Binder 10% formed by unsaturated polyester orthophthalic resin with: trimethoxysilylpropylmethacrylate (2% with respect to the resin), cumyl hydroperoxide (2% with respect to the resin)
    Additives are added to the resin and mixed and dispersed therein. The charges and the antistatic additive are mixed. The resin with its additives is added to the mixture of fillers and antistatic additive and homogenized in a planetary mixer. The dough is arranged on a mold in whose bottom kraft paper has been placed. It is pressed by vibrocompaction and empty for 2 minutes. The mold is brought to a homo at 120 ° C temperature 40 minutes until the resin is polymerized. It is allowed to cool to room temperature and two days later it is demoulded, cut, polished and the thickness is calibrated.
    Electrical conductivity and flexural strength tests are performed with the following result:
     Example  Electrical resistance Flexural strength Appearance
     A.M  308 GOhm 39 MPa Light loss of surface brightness
    EXAMPLE AN
    Gel coat type material, with choline chloride antistatic additive without encapsulation. Homogeneous mass manufactured in quantity of 1 Kg in total, with the following composition
    expressed in percentage by weight and added in the following order:
     Order of addition  Component Weight percentage
     one  Neopentyl glycol unsaturated polyester resin 35.00
     2  BYK-A-555 deaerating BYK 0.50
     3  Tetrahydroquinone 0.25
     4  Smoke from Silicon Aerosil 200 from Evonik 1.00
     5  Haloisite 3.4
     6  0.6 Chloride Chloride
     7  Neopentyl glycol unsaturated polyester resin 18.00
     8  Styrene 15.00
     9  Tinuvin 123 UV protector BASF 0.50
     10  0.25 Cobalt Activator
     eleven  Potassium ethylhexanoate 0.15
     12  Dimteilacetoacetamide 0.25
     13  BYK-A-555 deaerating BYK 0.50
     14  Methyl Methacrylate 8.75
     fifteen  Trimethylol Propane Trimethacrylate 3.00
     16  0.10 deaerating silicone
     17  10% phthalocyanine blue in unsaturated polyester, dye paste 13.00
     18  MEK peroxide 2 parts per 100 polyester resin
    As the components are added in the order indicated in the table above, the mass that is formed at 250 rpm is stirred with a cowles shaker. After adding component 17, stirring is continued for 30 min until the material forms. 5 The peroxide activator is added as the last component 18 and stirred for 3 min.
    The material is deposited on a silicone mold and a thickness of 0.5 mm is obtained. When it has polymerized and 5 days have passed, the resistance measurement is performed
    superficial.
     Example  Electrical resistance Appearance
     AN  75 MOhm Dark spots appear in the form of areas
    10 EXAMPLE AO
    Gel coat type material, with antistatic additive choline chloride encapsulated in haloisite according to EXAMPLE 3.
    Homogeneous mass manufactured in quantity of 1 Kg in total, with the following composition
    expressed in percentage by weight and added in the following order:
     Order of addition  Component Weight percentage
     one  Neopentyl glycol unsaturated polyester resin 35.00
     2  BYK-A-555 deaerating BYK 0.50
     3  Tetrahydroquinone 0.25
     4  Smoke from Silicon Aerosil 200 from Evonik 1.00
     5  Encapsulated antistatic according to example 3 formed by 4.00
     15% choline chloride encapsulated in 85% haloisite
     6  Neopentyl glycol unsaturated polyester resin 18.00
     7  Styrene 15.00
     8  Tinuvin 123 UV protector BASF 0.50
     9  0.25 Cobalt Activator
     10  Potassium ethylhexanoate 0.15
     eleven  Dimteilacetoacetamide 0.25
     12  BYK-A-555 deaerating BYK 0.50
     13  Methyl Methacrylate 8.75
     14  Trimethylol Propane Trimethacrylate 3.00
     fifteen  0.10 deaerating silicone
     16  10% phthalocyanine blue in unsaturated polyester, dye paste 13.00
     17  MEK peroxide 2 parts per 100 polyester resin
    As the components are added in the order indicated in the table above, the mass that is formed at 2000 rpm is stirred with a cowles shaker. After adding component 16, stirring is continued for 30 min until forming the material. The peroxide activator is added as the last component 17 and stirred for 3 min.
    The material is deposited on a silicone mold in a thickness of 0.5 mm. When it has polymerized and 5 days have passed, the surface resistance measurement is performed.
     Example  Electrical resistance Appearance
     AO  87 MOhm Correct
    10 AP EXAMPLE
    Gel coat type material, with antistatic additive choline chloride without encapsulation. Homogeneous mass manufactured in quantity of 1 Kg in total, with the following composition
    expressed in percentage by weight and added in the following order:
     Order of addition  Component Weight percentage
     one  Isophthalic Unsaturated Polyester Resin 20
     2  BYK-A-555 deaerating BYK 0.25
     3  Tetrahydroquinone 0.25
     4  Smoke from Silicon Aerosil 200 from Evonik 1
     5  Precipitated sodium aluminosilicate 1.7
     6  Choline Chloride 0.3
     7  Tinuvin 123 UV protector BASF 0.5
     8  0.25 Cobalt Activator
     9  Potassium ethylhexanoate 0.15
     10  Dimteilacetoacetamide 0.25
     eleven  Methyl Methacrylate 6.5
     12  Trimethylol Propane Trimethacrylate 3
     13  0.1 deaerating silicone
     14  T rimethoxysilylpropylmethacrylate 1.5
     fifteen  Alumina 1-100 Jim 64.25
     16  MEK peroxide 2 parts per 100 polyester resin
    As the components are added in the order indicated in the table above, the mass that is formed at 250 rpm is stirred with a cowles shaker. After adding component 15, stirring is continued for 30 min until the material forms. 5 The peroxide activator is added as the last component 16 and stirred for 3 min.
    The material is deposited on a silicone mold, obtaining a 0.5 mm thick layer. When it has polymerized and 5 days have passed, the surface resistance measurement is performed.
     Example  Electrical resistance Appearance
     AP  154 MOhm Darkening spots are observed at some points and the material loses brightness.
    10 EXAMPLE AQ
    Gel coat type material, with antistatic additive choline chloride encapsulated in sodium aluminosilicate according to EXAMPLE 3.
    Homogeneous mass manufactured in quantity of 1 Kg in total, with the following composition
    expressed in percentage by weight and added in the following order:
     Order of addition  Component Weight percentage
     one  Isophthalic Unsaturated Polyester Resin 20
     2  BYK-A-555 deaerating BYK 0.25
     3  Tetrahydroquinone 0.25
     4  Smoke from sllice Aerosil 200 from Evonik 1
     5  Encapsulated antistatic according to example 3 formed by 15% choline chloride encapsulated in 85% sodium aluminosilicate 2
     6  Tinuvin 123 UV protector BASF 0.5
     7  0.25 Cobalt Activator
     8  Potassium ethylhexanoate 0.15
     9  Dimteilacetoacetamide 0.25
     10  Methyl Methacrylate 6.5
     eleven  Trimethylol Propane Trimethacrylate 3
     12  0.1 release mold silicone
     13  T rimethoxysilylpropylmethacrylate 1.5
     14  Alumina 1-100 Jim 61.50
     fifteen  MEK peroxide 2 parts per 100 polyester resin
    As the components are added in the order indicated in the table above, the mass that is formed at 2000 rpm is stirred with a cowles shaker. After adding component 14, stirring is continued for 30 min until the material forms. The peroxide activator is added as the last component and stirred for 3 min.
    The material is deposited on a silicone mold to obtain a 0.5 mm thick layer. When it has polymerized and 5 days have passed, the measurement of
    surface resistance
     Example  Electrical resistance Appearance
     Aq  211 MOhm Correct
    10
    EXAMPLE AR
    Material manufactured using Bulk molding composite (BMC) technique with addition of uncapsulated choline ethyl sulfate.
    First, the resin formed by three components is prepared: Polyester
    15 unsaturated diluted in styrene 65%, low profile additive polyvinyl acetate diluted in
    4% styrene and 31% styrene to obtain 5 kg of material. The unsaturated polyester is a dilute orthophthalic resin that contains 35% styrene. The low profile additive is a polyvinylacetate solution containing 60% styrene, which is mixed in a tank with cowles at 200 rpm for 10 min.
    20 5 kg are manufactured in which per 100 parts of the previous mixture is added in
    parts:
     Order of addition  Component Parts per 100 resin (phr)
     one  Initial initial blend of polyester resin, low profile additive and styrene 100
     2  PBQ 6% inhibitor 0.3
     3  Calcium Carbonate 200
     4  Haloisite 8.5
     5  Choline Ethyl Sulfate 1.5
     6  Release Zinc Stearate 5
     7  10% phthalocyanine blue in unsaturated polyester, coloring paste 2
     8  Trigonox C 1.25
     9  Trigonox 21 0.25
     10  45 cut fiberglass
    The material is mixed in kneader for 10 min. And the cut fiberglass is added and mixed for 1 min. The material is molded for 3 min. at 150 ° C and 7
    Pressure MPa Pieces 150 x 150 mm and 3 mm thick are obtained.
     Example  Electrical resistance Flexion module Appearance
     AR  320 MOhm 7.2 GPa Dark spots appear
    5
    EXAMPLE AS
    Material manufactured using Bulk molding composite (BMC) technique with addition of 15% choline ethyl sulfate encapsulated in haloisite according to example 36.
    First of all, the resin formed by three components is prepared: Unsaturated polyester 10 diluted in styrene 65%, low profile additive polyvinyl acetate diluted in styrene 4% and styrene 31% to obtain 5 kg of material. The unsaturated polyester is a dilute orthophthalic resin that contains 35% styrene. The low profile additive is a polyvinylacetate solution containing 60% styrene, which is mixed in a tank with cowles at 200 rpm for 10 min.
    15 5 kg are manufactured in which per 100 parts of the previous mixture is added:
     Order of addition  Component Parts per 100 resin (phr)
     one  Initial initial blend of polyester resin, low profile additive and styrene 100
     2  PBQ 6% inhibitor 0.3
     3  Calcium Carbonate 200
     4  Choline chloride 15% encapsulated in sodium aluminosilicate according to example 3 10
     5  Zinc Stearate Release  5
     6  10% phthalocyanine blue in unsaturated polyester, coloring paste 2
     7  Trigonox C 1.25
     8  Triqonox 21 0.25
     9  45 cut fiberglass
    The material is mixed in kneader for 10 min. And the cut fiberglass is added and mixed for 1 min. The material is molded for 3 min. at 150 ° C and 7
    Pressure MPa Pieces 150 x 150 mm and 3 mm thick are obtained.
     Example  Electrical resistance Flexion module Appearance
     ACE  402 MOhm 8.9 GPa Bright Right
    AT EXAMPLE
    Material manufactured using Sheet Molding Composite (SMC) technique with the addition of 5 encapsulated choline ethyl sulfate.
    The resin components are prepared in an amount of 10 kg in the following order
    of addition on mixer:
     Order of addition  Component Parts per 100 resin (phr)
     one  100 Orthophthalic Unsaturated Polyester Resin
     2  Styrene 5
     3  5 polyethylene powder
     4  Zinc Stearate 5
     5  10% phthalocyanine blue in unsaturated polyester, dye paste  5
     6  Calcium Carbonate 160
     7  Haloisite 8.5
     8  Choline Ethyl Sulfate Powder 1.5
     9  Trigonox C peroxide 1.5
     10  Magnesium Oxide Paste 3
     eleven  25 mm 100 cut fiberglass
    Components 1 to 10 are mixed in a mixer with cowles shovel at 200 rpm for 10 min. The material is deposited on a polyethylene film and spread. The
    fiberglass cut. A top closure film is placed and passed through a double roller. The formed material is allowed to mature for 4 weeks. The material is molded for 3 min. at 150 ° C and 50 kg / cm2 of pressure. 150 x 150 mm pieces are obtained
    and 3 mm thick.
     Example  Electrical resistance Flexural strength Appearance
     AT  28 MOhm 160 MPa Oily dark spots on surface
    AU EXAMPLE
    Material manufactured using Sheet Molding Composite (SMC) technique with the addition of choline ethyl sulfate encapsulated according to EXAMPLE 36.
    The resin components are prepared in an amount of 10 kg in the following order
     Order of addition  Component Parts per 100 resin (phr)
     one  100 Orthophthalic Unsaturated Polyester Resin
     2  Styrene 5
     3  5 polyethylene powder
     4  Zinc Stearate 5
     5  10% phthalocyanine blue in unsaturated polyester, dye paste  5
     6  Calcium Carbonate 160
     7  15% choline ethylsulfate encapsulation in 85% haloisite according to example 36 10
     8  Trigonox C peroxide 1.5
     9  Magnesium Oxide Paste 3
     10  25 mm 100 cut fiberglass
    Components 1 to 9 are mixed in a mixer with cowles shovel at 200 rpm for 10 min. The material is deposited on a polyethylene film and spread. The cut 5 fiberglass is added. A top closure film is placed and passed through a double roller. The formed material is allowed to mature for 4 weeks. The material is molded for 3 min. at 150 ° C and 50 kg / cm2 of pressure. Pieces 150 x 150 mm and 3 mm thick are obtained.
     Example  Electrical resistance Flexural strength Appearance
     AU  89 MOhm 220 MPa Correct bright
    10
    权利要求:
    Claims (19)
    [1]
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    35
    1. A formulation free of conductive polymers, metals, carbon-based conductive materials, such as carbon black, carbon fibers, graphite, graphene or carbon nanotubes, which provides antistatic effect and / or electric charge heatsink in its application in thermostable resins of unsaturated polyester or in epoxy vinyl ester thermosetting resins and in which the presence of two components is necessary so that the first component can be dispersed in the polymer matrix avoiding the loss of mechanical and aesthetic properties, also preventing the formation of agglomerates or that reacts with the resin components. This formulation is characterized in that it comprises:
    to. First component: a compound based on the cation as such N, N, N-trialkyl-alkyl-ol-ammonium or derivatized in the OH group, and an anion A, as expressed in the following chemical formula:
    n = 1.2 or 3
    OR4 = - hydroxyl, formyl, acetyl, propanoyl, butanoyl, hexanoyl, octanoyl, 2-ethyl-hexanoyl, decanoyl, dodecanoyl, tetradecanoyl, hexadecanoyl, stearoyl, oleoyl or benzoyl
    The anion, A, is inorganic or organic, and can be: chloride, fluoride, bromide, iodide, perchlorate, sulfate, hydrogen sulfate, nitrate, nitrite, dihydrogen phosphate, hydrogen phosphate, phosphate, borate, carbonate, hydrogen carbonate, sulfocyanide, tetrafluroborate, hexafluorophosphate , sulfamate, acetate, propionate, butanoate, formate, oxalate, lactate, glycolate, benzoate, salicylate, citrate, tartrate, p-toluenesulfonate,
    image 1
    image2
    R1, R2, R3 = -CH3i -CH2CH3, -CH2CH2CH3 or -CH2CH2CH2CH3
    5
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    xylenesulfonate, 2-ethylhexylsulfate, octanosulfonate, methanesulfonate, ethanesulfonate, propanesulfonate, methosulfate (methylsulfate), ethosulfate (ethylsulfate), alkyl phosphates, aryl phosphates or saccharinate.
    b. Second component: a support that encapsulates, absorbs, adsorbs, serves as a dispersing solid agent and / or protects the previous anion-cation set (salt), comprised between the following: sodium aluminosilicate, precipitated silica, silica smoke, sepiolite, attapulgite , estevensite-kerolite, bentonite, ball clay, kaolinite, kaolin, metacaolin, haloisite, zeolites, Ti02, Alumina (Al203), bohemite, aluminum trihydroxide, magnesium hydroxide, magnesium oxide, calcium carbonate, magnesium carbonate, calcium magnesium carbonate and / or mixtures thereof
    [2]
    2. A formulation to ensure that thermosetting resins of unsaturated polyester, or epoxy vinyl ester are antistatic or dissipative.
    electric according to claim 1, wherein the group -OR4 is comprised of the following chemical groups: hydroxyl, formyl, acetyl, propanoyl, butanoyl, hexanoyl, octanoyl, 2-ethyl-hexanoyl, decanoyl, dodecanoyl, tetradecanoyl, hexadecanoyl, stearoyl , oleoyl or benzoyl.
    [3]
    3. A formulation to ensure that thermosetting resins of unsaturated polyester, or epoxy vinyl ester are antistatic or load dissipating
    according to claim 1, in which the anion is comprised of the following: chloride, fluoride, bromide, iodide, perchlorate, sulfate, hydrogen sulfate, nitrate, nitrite, dihydrogen phosphate, hydrogen phosphate, phosphate, borate, carbonate, hydrogen carbonate, sulfocyanide, tetrafluroborato, hexafluorophosphate, dicyanamide, sulfamate, acetate, propionate, butanoate, formate, oxalate, lactate, glycolate, benzoate, salicylate, citrate, tartrate, p-toluenesulfonate, xylenesulfonate, 2-ethylhexyl, octane, methanesulfonate, ethanesulfonate, propanesulfonate, methosulfate ( methylsulfate), ethosulfate (ethyl sulfate), alkyl phosphates, aryl phosphates or saccharinate.
    [4]
    4. A formulation according to claim 1 wherein the groups R1, R2, R3 are between the groups -CH3, -CH2CH3, -CH2CH2CH3 or -CH2CH2CH2CH3 and preferably between -CH3 or -CH2CH3 and more preferably are -CH3
    [5]
    5. A formulation according to claim 1 wherein the n is 1, 2 or 3 and preferably equal to 2.
    5
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    30
    [6]
    6. A formulation to ensure that thermosetting resins of unsaturated polyester or vinyl ester epoxy are antistatic according to revindication 1, in which the support that encapsulates, absorbs, adsorbs, serves as a dispersing solid agent and / or protects the anion-cation assembly ( salt), preferably has the following characteristics and is comprised between: precipitated silica with BET between 30 and 250 m2 / gr, silica smoke 200-300 m2 / gr, sodium aluminosilicate (10 to 200 m2 / gr), sepiolite 0, 01-100 pm, attapulgite 0.01-100 pm, estevensite-kerolite 0.01-100 pm, bentonites 0.01-100 pm, ball clay, kaolinite 0.01-100 pm, kaolin 0.01-100 pm , metacaolin 0.1-100 pm, haloisite, zeolite 0.01-100 pm, Ti02 0.01-100 pm, alumina 0.01-100 pm, bohemite 0.01-100 pm, aluminum trihydroxide 0.01- 100 pm, magnesium hydroxide 0.01-100 pm, magnesium oxide 0.01-100 pm, calcium carbonate 0.01-100 pm, magnesium carbonate 0.01-100 pm, calcium magnesium carbonate 0, 01-100 pm and / or mixtures thereof.
    [7]
    7. A formulation according to revindication 6 in which the porous material is mainly between: sodium aluminosilicate (10 to 200 m2 / gr), precipitated silica with BET between 30 and 250 m2 / gr, haloisite, zeolite A 0.01 -100 pm and / or mixtures
    [8]
    8. A formulation according to revindication 6 in which the porous material is sodium aluminosilicate of composition 10 to 14.5 (Si02) 0.5 to 1.5 (Al203) 0.5 to 2 (Na20) and BET surface 50 at 90 m2 / gr
    [9]
    9. A formulation according to revindication 2 in which the OR4 group is preferably between hydroxy, formyl, acetyl, propanoyl or benzoyl.
    [10]
    10. A formulation according to revindication 9 in which the OR4 group is -OH (hydroxyl).
    [11]
    11. A formulation according to revindication 3 in which the anion is primarily between chloride, bromide, fluoride, methosulfate (methylsulfate) ethosulfate (ethylsulfate), saccharinate, perchlorate or nitrate.
    [12]
    12. A formulation according to revindication 3 in which the anion is between chloride, bromide, saccharinate, methosulfate (methylsulfate) or ethosulfate (ethylsulfate).
    [13]
    13. A formulation according to claims 1 to 12, wherein the ratio between the support material, second component, and salt, first component, is in the range of 1 to 40%, preferably between 5 and 25% .
    [14]
    14. A formulation according to claims 1 to 12, wherein the ratio between the support material, second component, and salt, first component, is in the range between 10 and 20%.
    [15]
    15. Composition characterized by comprising a formulation according to the
    5 claims 1 to 14 and an unsaturated polyester resin or vinyl ester epoxy
    where the ratio between the formulation and the unsaturated polyester resin or epoxy vinyl ester is from 1% to 19%, preferably between 2 and 15%.
    [16]
    16. Composition according to claim 15 characterized in that the relationship between the formulation and the unsaturated polyester resin or epoxy vinyl ester is more
    10 preferably 5 to 10%.
    [17]
    17. Use of the formulation of claims 1 to 14 for the preparation of an agglomerated stone composite material characterized in that added to the mixture allows the manufacture of panels, blocks or tiles with antistatic and / or electrical charge dissipating properties.
    18. Use of the formulation of claims 1 to 14 for the preparation of a
    SMC composite material characterized in that added to the mixture allows the manufacture of panels with anti-static and / or electric charge dissipating properties.
    [19]
    19. Use of the formulation of claims 1 to 14 for the preparation of a
    20 BMC composite material characterized in that added to the mixture allows the
    manufacture of panels with anti-static and / or electric charge dissipating properties.
    [20]
    20. Use of the formulation of claims 1 to 14 for the preparation of a gel coat composite material characterized in that added to the mixture allows
    25 the manufacture of panels with anti-static and / or dissipative properties of
    electric charge
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    同族专利:
    公开号 | 公开日
    EP3345965A4|2019-09-11|
    IL257783D0|2018-04-30|
    WO2017037317A1|2017-03-09|
    US10934416B2|2021-03-02|
    EP3345965A1|2018-07-11|
    ES2563903B2|2016-07-06|
    US20180244900A1|2018-08-30|
    CN107922719A|2018-04-17|
    IL257783A|2021-08-31|
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