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    • 专利摘要:
    The invention relates to a general-purpose pigment preparation for coloring plastics.
    公开号:BE1024918B1
    申请号:E2017/5772
    申请日:2017-10-27
    公开日:2018-08-21
    发明作者:Giovanni Broggi
    申请人:Giovanni Broggi；
    IPC主号:
    专利说明:

    (73) Holder (s):
    BROGGI Giovanni 20121, MILANO Italy (72) Inventor (s):
    BROGGI Giovanni 20121 MILANO Italy (54) UNIVERSAL PIGMENT PREPARATIONS FOR COLORING AND STRENGTHENING PLASTICS (57) The invention relates to a pigmentary preparation for general use for coloring plastics.
    BELGIAN INVENTION PATENT
    FPS Economy, SMEs, Middle Classes & Energy
    Publication number: 1024918 Deposit number: BE2017 / 5772
    Intellectual Property Office International Classification: C09D 17/00 C08J 3/20 C08L 67/02 C08J 3/22 C08K 3/00 C08G 63/12 C08K 5/00 C09D 7/40 C09D 7/45
    Issue date: 08/21/2018
    The Minister of the Economy,
    Having regard to the Paris Convention of March 20, 1883 for the Protection of Industrial Property;
    Considering the law of March 28, 1984 on patents for invention, article 22, for patent applications introduced before September 22, 2014;
    Given Title 1 “Patents for invention” of Book XI of the Code of Economic Law, article XI.24, for patent applications introduced from September 22, 2014;
    Having regard to the Royal Decree of 2 December 1986 relating to the request, the issue and the maintenance in force of invention patents, article 28;
    Given the patent application received by the Intellectual Property Office on October 27, 2017.
    Whereas for patent applications falling within the scope of Title 1, Book XI of the Economic Law Code (hereinafter CDE), in accordance with article XI. 19, §4, paragraph 2, of the CDE, if the patent application has been the subject of a search report mentioning a lack of unity of invention within the meaning of §ler of article XI.19 cited above and in the event that the applicant does not limit or file a divisional application in accordance with the results of the search report, the granted patent will be limited to the claims for which the search report has been drawn up.
    Stopped :
    First article. - It is issued to
    BROGGI Giovanni, Via San Marco 24, 20121 MILANO Italy;
    represented by
    OFFICE KIRKPATRICK S.A., Avenue Wolfers 32, 1310, LA HULPE;
    a Belgian invention patent with a duration of 20 years, subject to payment of the annual fees referred to in article XI.48, §1 of the Code of Economic Law, for: UNIVERSAL PIGMENTARY PREPARATIONS TO COLOR AND STRENGTHEN PLASTIC MATERIALS .
    INVENTOR (S):
    BROGGI Giovanni, Via San Marco 24, 20121, MILANO;
    PRIORITY (S):
    10/28/2016 IT 102016000109323;
    DIVISION:
    divided from the basic application: filing date of the basic application:
    Article 2. - This patent is granted without prior examination of the patentability of the invention, without guarantee of the merit of the invention or of the accuracy of the description thereof and at the risk and peril of the applicant (s) ( s).
    Brussels, 08/21/2018, By special delegation:
    B E2017 / 5772
    Title:
    UNIVERSAL PIGMENT PREPARATIONS FOR COLORING AND STRENGTHENING PLASTICS
    DESCRIPTION
    FIELD OF THE INVENTION
    The present invention relates to pigment preparations intended to color and strengthen plastics, which contain pigments and / or other additives and / or fillers; and their use as colorant concentrates.
    BACKGROUND OF THE INVENTION
    In order to obtain plastic and rubber articles and manufactured articles, it is generally necessary to introduce polymers into the basic raw materials, namely substances which are suitable for giving them the characteristics which are desired in the finished product. . These substances can be: substances which give a color to the material, such as pigments or dyes, or substances which give functional properties to manufactured articles, such as better resistance to fire and / or light, or even substances which improve the mechanical and / or thermal properties of the finished product. Often additives are also used to protect the polymer during the process of transformation into a manufactured article, such as thermal stabilizers, thermo-oxidants, fluidizing agents, etc., commonly defined as process additives, since the transformation of the material Plastic in manufactured articles is generally made at high temperatures and in the presence of significant mechanical stresses.
    Instead of adding these substances directly to the polymer to be modified, industrial practice mainly uses an indirect technology: the masterbatch technology.
    Masterbatches, also known as pigment concentrates, are formulations made up of a basic substance, commonly called a carrier, and large amounts of at least one additive.
    Masterbatch technology involves the preliminary preparation of a
    Bl concentrate containing the desired additives, then adding this concentrate to the base polymer in amounts calculated so as to obtain the desired percentages of additive (s) in the product. The choice of masterbatch technology results from questions of cost, safety in the handling of additives, etc. The masterbatch is often prepared by specialized companies other than those which will later use it in the transformation into final plastic products.
    The solid support present in pigment preparations is typically a polymeric material, a waxy product or a mixture thereof. Since the support will have to be mixed with the polymer to be modified, and since in the end it will remain incorporated in the final product, it is essential that it is compatible and easily miscible with the polymer to be modified in the finished product.
    The great complexity of this field depends, in addition to the number of supports (a few tens), essentially on the combination between them and the number of colors necessary for each support. Each encoder is prepared by mixing the pigments necessary for each shade requested, namely by mixing coloring additives (for example to obtain green, the white pigment is mixed with a yellow pigment and a blue pigment) with the support. The mixture is extruded and then granulated.
    Therefore, it is clear that the production of masterbatches is made to measure and must therefore be carried out whenever the colors cannot be obtained by the use of a single pigment. This complexity requires very laborious management of supply and storage, some of which eventually becomes slow-moving stocks - materials. Consequently, these materials remain stored for long periods, and can therefore become unsaleable or difficult to sell lots - a problem that inevitably increases with the number of products to be managed.
    A primary object of the present invention is therefore to provide a “universal” pigment preparation, capable of eliminating this complexity and therefore capable of ensuring less costly management of the production of colored manufactured articles.
    It must be taken into account that the system currently employed based on
    B E2017 / 5772 extrusion does not allow organic pigment concentrates above 40% on average.
    Patent EP 0910603 B1 describes the production of masterbatches or concentrates of additives using low energy mixing processes. 5 additive particles are held together by carrier particles which retain their particulate identity, so that the masterbatch is composed of agglomerates of carrier particles and agglomerate particles.
    US3778288 discloses a process in which pigments and dispersants, such as Fischer-Tropsch waxes, are combined and granulated using a high intensity mixture. The granules obtained have a size between 10 and 70 mesh (2000 to 210 μm) with a yield of 90-95% (column 4, lines 45-46). The smaller particles have a lower dispersion than the larger particles (column 8, lines 67-68).
    The object of the present invention is therefore to provide universal pigment preparations 15 which, however, overcome the disadvantages of previously known preparations.
    More specifically, the main objects of the present invention are:
    - universality of use of pigment products,
    - low complexity of the production process,
    - reduction of stocks,
    - reduction in conversion costs,
    - high concentration of pigments,
    - improvement of coloring and physicochemical properties,
    - conformity of final products with current standards in the food, medical, or even for toys fields.
    SUMMARY OF THE INVENTION
    The inventors of the present invention have discovered that certain specific dispersing agents also have the characteristics of a wetting agent. These compounds enabled the inventors to prepare pigment preparations of general use for coloring plastics.
    In one aspect, the present invention relates to a pigment preparation comprising, consisting essentially of, or consisting of:
    B
    at least one wetting dispersing agent chosen from the group consisting of a wax-based powder treatment additive with groups having an affinity for the pigments, acid polyester additive with a group having an affinity for the pigments, modified polyether with high affinity groups for pigments, styrene and polyether copolymers, maleic acid amides, amphiphilic copolymers, polyacrylate modified with high affinity groups for pigments, polyester block copolymer, polyurethane polymer high molecular weight, polyester-polyamine-polyolefin terpolymers, and polysiloxanes modified with epoxy or urethane groups, said a wetting dispersing agent having a melting point between 50 and 150 ° C, and
    - at least one pigment additive chosen from the group consisting of an inorganic pigment, an organic pigment, carbon black and dyes, and
    - optional additives, where the particle diameter D 50 (in number) of the at least one pigmentary additive of the pigmentary preparation is between 0.5 and 3.5 μm, and the pigmentary preparation contains at least 60% in weight of the at least one pigment additive relative to the total weight of the pigment preparation.
    According to the invention, the only essential ingredients of the pigment preparation are at least one wetting dispersing agent and at least one pigment additive. The inventors have discovered a group of compounds capable of having wetting properties, that is to say capable of reducing the interfacial tension of agglomerates of primary pigment particles, that is to say capable of stabilizing said primary pigment particles -r which prevents their re-agglomeration. These wetting dispersing agents preferably include pigment affinity groups, such as aromatic rings, polyethers, hydrogen-bonded groups, for example groups containing nitrogen atoms, eg. primary, secondary and tertiary amines, and groups containing amides, imides and imines, caxboxylic acid groups, hydroxy groups, carbonyl groups and carboxyl groups. For polymeric or oligomeric wetting dispersants, the affinity groups for
    B pigments can be part of the skeleton or be incorporated into a side chain.
    Given this double property, it is possible to avoid wetting and dispersing agents specific for a given polymer during the coloring of the polymers. The wetting dispersants according to the invention have been found to be compatible with all families of coloring plastics. In this way, the pigment preparations according to the invention allow a universal coloring system, because they benefit from a universality of use; that is, they can be used in several polymers, for example in at least three different polymers. Examples of polymers include, without limitation, polymers based on polyethylene, polystyrene, SAN, HIPS, ABS, ASA, polymers of polyvinyl chloride type, polyacrylates, polyamides, polycarbonates, polyesters, polyurethanes and thermoplastic elastomers. Mixed with a polymer so that the content of pigmentary filler is between 0.5 and 1% by weight, this results in a colored composition which preferably has a coloring power at least 20% better, at least 25% better, at least 30 % better, at least 35% better, at least 40% better, for example, 20-50% better than for a mixture of the same composition prepared by adding each component individually in a mixer and combining the components (i.e. pigment load , wetting dispersing agent, polymer). Preferably, the pigment preparation provides this improvement in coloring power to at least three different polymers.
    In one aspect, the invention relates to a final pigment preparation, in which the at least one pigment additive has a particle diameter D 5 o (in number) between 0.5 and 3.5 μm, and contains at least 60% by weight of the at least one pigment additive relative to the total weight of the pigment preparation. The particle size of the pigment additive in the final pigment preparation indicates the degree of dispersion of the pigment additive in the pigment preparation. Before grinding, the pigment additive powder is in the form of agglomerated and / or aggregated particles typically having a particle size greater than 7 μm, for example 7 to 10 μm. For organic pigments, the aggregates contain several pigment crystallites that have been grown together
    B to their surfaces. The crystallites and aggregates of pigment meet at their edges and at their corners to form agglomerates. The grinding process separates the organic pigment aggregates from each other using the wetting dispersing agent and also reduces their size, and the wetting dispersing agent prevents individual crushed particles which may include single crystallites or particles primary to re-adhere or to flocculate. Conversely, carbon black is an aggregate of primary particles configured similarly to a bunch of grapes. The primary particles adhere to each other by covalent interactions, and the individual aggregates are generally not broken down into primary particles by grinding. The carbon black aggregates adhere to each other through non-covalent interactions to form agglomerates. In this case, the grinding process separates the carbon black aggregates from each other, and the wetting dispersing agent prevents them from re-agglomerating.
    The pigment preparation according to the invention can be obtained in the form of a fluid powder or in microgranules which can be measured each time by sieving, for example with a Digital Electromagnetic Sieve Shaker by Filtra Vibration mod. FTL 0200.
    In a preferred embodiment of microgranules, the particle size of all the microgranules of the pigment preparation is in the range from 60 to 500 μm, more preferably from 80 to 350 μm, as measured (for example with a Digital Electromagnetic Sieve Shaker by Filtra Vibration mod. FTL 0200 / Preferably, the microgranules are ready-to-use microgranules containing all the active ingredients and all the additives (which it is desired to use in the masterbatch composition) to be used as ready-to-use pigment preparation .
    When the definition "pigment additive" is used in the present invention, any pigment additive chosen from the group consisting of mineral pigment, organic pigment, carbon black and dyes is understood.
    Unless otherwise specified, when the particle diameter D 10 , D 5 o and D 90 of the pigment additive is indicated in the present invention, reference is made to a particle diameter (in number) of the at least one additive pigment measured in the final pigment preparation by dispersing the final pigment preparation in a solvent and analyzing the dispersion with a laser granulometer, for example with a Beckman Coulter laser granulometer Particle size Analyzer, optical model Fraunhofer.rf780z. The particle size of the pigment additive in the final pigment preparation can be obtained by dispersing the pigment preparation in a suitable solvent, for example butyl acetate. The dispersing and wetting agent is completely dissolved under the test conditions, and therefore the device only measures the size of the ground pigment dispersed in the solvent. D 10 is greater than or equal to the diameter of 10% of the particles in a given population; D 50 is greater than or equal to the diameter of 50% of the particles in the population; and D 90 is greater than or equal to the diameter of 90% of the particles in the population.
    When the granulometry of the microgranules or of the powder is indicated in the present invention, the particle diameter is understood to be measured by suitable filters.
    When the definition “fluid powder” is used in the present invention, it is a question of indicating particles of the final pigment preparation having a particle size less than 50 μm.
    The pigment preparations of the invention are preferably in the form of a fluid powder or of microgranules. Otherwise or in addition, the pigment preparation is in the form:
    a) of a fluid powder having D 2 o of at least 0.8 pm and D 90 up to 5 pm measured in the dry state by a laser granulometer, for example a Malvern Mastersizer 2000 granulometer equipped with a accessory for introducing the Scirocco 2000 dry powder sample at a pressure of 3.5 bar, or
    b) microgranules having D 20 of at least 10 μm and D 90 up to 1000 μm measured in the dry state by a laser granulometer at a pressure of 3.5 bar.
    All the embodiments of the pigment preparation as microgranules preferably have a particle size of the ingredients in the range from 60 to 500 μm, more preferably from 80 to 350 μm.
    The at least one pigment additive of the final pigment preparation in all embodiments of the invention preferably also has a particle diameter D 90 (by number) in the range of 0.9 to 4 µm.
    The at least one pigment additive of the final pigment preparation in all of the embodiments of the invention preferably also has a particle diameter D 10 (in number) in the range of 0.5 to 1 µm.
    In another aspect, the invention relates to a process for the preparation of the pigment preparation of the invention, in which the ingredients are treated with an apparatus capable of inferring a particle diameter D 5 o (in number) of at least a pigment additive in the range of 0.5 to 3.5 µm.
    In a preferred aspect, the invention describes the pigment preparation according to the invention, where the pigment preparation is obtained by a pigment composition by a process comprising the following steps:
    1) introduction into a mill, preferably a dry mill, of a pigment composition comprising, consisting essentially of, or consisting of:
    - at least one wetting dispersing agent chosen from the group consisting of a wax-based powder treatment additive with groups having an affinity for the pigments, acid polyester additive with a group having an affinity for the pigments , modified polyether with high affinity groups for pigments, styrene and polyether copolymers, maleic acid amides, amphiphilic copolymers, modified polyacrylate with high affinity groups for pigments, polyester-based block copolymer, high molecular weight polyurethane polymer, polyesterpolyamine-polyolefin terpolymers, and polysiloxanes modified with epoxy or urethane groups, said a wetting dispersing agent having a melting point between 50 and 150 ° C,
    - at least one pigment additive chosen from the group consisting of an inorganic pigment, an organic pigment, carbon black and dyes, and
    - optional additives,
    2) mixing and grinding of the pigment composition of step 1);
    3) unloading of the pigment preparation thus obtained in the form of, ,,. . ,. BE2017 / 5772 fluid powder or microgranules.
    Preferably, in step 1), other additives can be added, such as antistatic agents, fillers, etc. which will be discussed elsewhere herein.
    The wetting dispersing agent preferably has a number average molecular weight of 5,000 to 35,000 g / mol. Because the pigment additive is preferably loaded into the mill in the solid state, the resulting pigment preparation preferably has low contents of water and other solvents, for example, less than 3% by weight, less than 2.5%, or less than 2%. For example, the pigment preparation may contain less than 3% by weight, less than 2.5%, or less than 2% of water.
    Without wishing to be bound to a theory and it will appear from the detailed description and examples, the method according to the invention leads to superior grinding and disintegration of the primary particles of the pigment, and consequently to their excellent homogenization and dispersion . The process according to the present invention makes it possible to obtain homogeneity and fineness of grinding (comparable to those obtained by the traditional extrusion process) with a very fine dispersion of particles, which makes it possible to overcome the drawbacks of pigment preparations in the state art.
    The method according to the invention makes it possible to obtain a pigment preparation in step 3) in the form of a fluid powder or of microgranules, the at least one pigment additive in the pigment preparation having a particle diameter D 5 o (in number ) in the range of 0.5 to 3.5 µm; also a particle diameter D 9 o (by number) in the range of 0.9 to 4 µm; and also a particle diameter D 10 (in number) in the range of 0.5 to 1 μm, measured by a laser granulometer according to its dispersion in solvent, for example, with a Beckman Coulter laser granulometer Particle size Analyzer, optical model Fraunhofer.rf780z.
    Advantageously, the microgranule of the invention is a ready-to-use product.
    Consequently, the microgranular pigment preparations according to the invention are universal, with a high pigment concentration and a narrow particle size (60-500 μm).
    In another aspect, the invention relates to a universal coloring system
    B comprising a limited number of basic colors corresponding to a limited set of pigment preparations suitable for the preparation of manufactured articles of plastic and rubber having different shades of color. The pigment preparations according to the invention allow the preparation of color shades by simple dry mixing of basic single-color (single pigment) dyed preparations according to the invention (approx. 16-22) without the need for personalized treatment. mixing pigments by the extrusion process.
    Consequently, the invention also relates to a coloring system comprising a series of pigment preparations having desired shades (RAL (ReichsAusschuss für Lieferbedingungen), NCS (Natural Color System), BS (British Standards), etc.) which can be simply obtain by mixing at least two pigment preparations according to the invention.
    Therefore, another aspect of the invention relates to a use of the pigment preparation according to the invention for coloring all kinds of plastics, for example polymers based on polyethylene, polystyrene, SAN, HIPS, ABS, ASA, polymers of polyvinyl chloride type, polyacrylates, polyamides, polycarbonates, polyesters, - polyurethanes and thermoplastic elastomers. Preferably, when the composition of the colored plastic includes 0.5 to 1% by weight of the pigmentary additive, it has at least 20% better coloring power, for example 20-50% better, than a mixture having the same composition but prepared by pouring each component individually into a mixer and combining the components into a uniform mixture.
    Preferably, a given pigment preparation is suitable for coloring at least three kinds of plastics, for example, at least three among polymers based on polyethylene, polystyrene, SAN, HIPS, ABS, ASA, polymers of polyvinyl chloride type, polyacrylates, polyamides, polycarbonates, polyesters, polyurethanes and thermoplastic elastomers. Preferably, each of a first, a second and a third uniform mixture of the pigment preparation with a first, second and third polymer such that the first, second and third mixtures obtained contain 0.5 to 1% by weight of pigment has at least 20% better coloring power, for example, 20-50% better, than a mixture having the same composition but prepared by pouring each component individually into a mixer and combining the components into a uniform mixture.
    A plastic material is chosen, for example, from polyethylene products (eg HDPE (high density polyethylene), LDPE (low density polyethylene), LDPE (linear low density polyethylene), PEMD (medium density polyethylene), EVA (ethylene acetate vinyl), EVOH (ethylene polyvinyl alcohol)), polypropylene products (eg PP (polypropylene), copolymers of PP, EPR (ethylene-propylene rubber), EPDM (ethylene-propylene-diene rubber)), styrenic products (eg PS (polystyrene), SAN (styrene-acrylonitrile copolymer), HIPS (polystyrene bhoc), ABS (acrylonitrilebutadiene-styrene), ASA (acrylic-styrene-acrylonitrile copolymers), polymers of vinyl chloride type (eg PVC ( polyvinyl chloride)), plasticized or not, acrylic polymers (eg PMMA (polymethyl methacrylate), polyacrylates), polyamides (eg PA6, PA6,6, PA11, PA12, and their copolymers), polycarbonates and their mixtures (eg PC / ABS (polycarbonate / acryionitrile-but adiene-styrene), PC / polyesters), polyesters (ex. PET (polyethylene terephthalate),. PBT (polybutylene terephthalate), copolyesters), polyurethanes (eg TPU (thermoplastic polyurethane)), thermoplastic elastomers (eg, TPO (thermoplastic olefin), TPV (thermoplastic vulcanis)). Polyethylene and polypropylene products can be obtained using metallocene catalysts or other polymerization processes known to those skilled in the art.
    In addition, and surprisingly, the pigment preparation according to the invention has made it possible to improve the technical properties and the mechanical performance of the final colored plastic product, as will become apparent from the experimental part of the invention.
    Specifically, the melt index data (MFR) demonstrate the possibility of processing and the good dispersion of the colored samples (nonsignificant differences compared to the non-colored sample). The Izod test (impact resistance) showed much higher results (+ 77%) for the colored samples (with the pigment preparations according to the invention) compared to the non-colored sample, as confirmed by examining the zones
    B prone to fracture, which showed homogeneous discoloration and a well-developed deformation process. The Rockwell hardness test brought to light, before aging on Xenotest, significantly higher values (+ 37%) for samples colored by the pigment preparation according to the invention and after 1000 hours of aging on Xenotest, values which indicate a opposite behavior between colored and non-colored samples. While the colored samples virtually retained their original values, showing only a moderate change, the non-colored sample had undergone a large reduction. This phenomenon confirmed the increase in the fragility of the uncoloured sample (as confirmed by the results of the impact test). The results of the color resistance test, measured after 1000 hours of exposure to Xenotest, were extraordinary for the colored samples. No discoloration was observed in colorimetric analysis or on the gray levels. In short, the behavior of the colored samples was significantly better than that of the non-colored sample.
    DESCRIPTION OF THE FIGURES
    Figure 1 is the graph of the dimensional values of the pigment additive of the final pigment preparation of Example 1; and
    Figure 2 is the graph of the dimensional values of the pigment additive of the final pigment preparation of Example 6.
    DETAILED DESCRIPTION OF THE INVENTION
    In one aspect, the present invention therefore relates to a pigment preparation comprising, consisting essentially of, or consisting of:
    at least one wetting dispersing agent chosen from the group consisting of a wax-based powder treatment additive with groups having an affinity for the pigments, acid polyester additive with a group having an affinity for the pigments, polyether modified with high affinity groups for pigments, copolymers of styrene and polyethers, maleic acid amides, amphiphilic copolymers, polyacrylate modified with high affinity groups for pigments, polyester-based block copolymer, polyurethane polymer high molecular weight, polyester-polyamine-polyolefin terpolymers, and iS modified polysiloxanes with epoxy or urethane groups, said a wetting dispersing agent having a melting point between 50 and 150 ° C, and
    - at least one pigment additive chosen from the group consisting of an inorganic pigment, an organic pigment, carbon black and dyes, and
    - optional additives, in which the particle diameter D 5 o (in number) of the at least one pigmentary additive of the pigmentary preparation is between 0.5 and 3.5 μm, and the pigmentary preparation contains at least 60 % by weight of the at least one pigment additive relative to the total weight of the pigment preparation.
    As specified above, when the term “pigment additive” is used in the present invention, a pigment additive is chosen from the group consisting of an inorganic pigment, an organic pigment, carbon black and dyes. The term high molecular weight preferably indicates a number average molecular weight between 5000 and 35000 g / mol. Amphiphilic copolymers are copolymers including both hydrophilic and hydrophobic monomers randomly arranged in blocks, or using some other arrangement, such as a gradient.
    For example, a pigment additive can be one or more of the following compounds:
    Color Pigment Color Index White Titanium dioxide p. White 6 Yellow Yellow iron oxide p. Yellow 42 ^ Yellow Monoazoic p. Yellow 168
    B E2017 / 5772
    Yellow Monoazoic p. Yellow 62 Yellow Isoindoiinone p. Yellow 109 Yellow Isoindoiinone p. Yellow 110 Yellow Yellow iron oxide p. Yellow 119 Yellow Antraquinone p. Yellow 199 Yellow Disazocondensation p. Yellow 128 Yellow Disazocondensation p. Yellow 93 Yellow Bismuth vanadate p. Yellow 18¾ Yellow Mixed metal oxide p. Yellow 216 Yellow Diaryiid p. Yellow 83 Yellow Monoazoic p. Yellow 66 ' Yellow Irgalite p. Yellow 13 Yellow Irgalite p. Yellow 14 Yellow Irgalite p. Yellow 62 ' Yellow Irgalite p. Yellow 83 Yellow Benzimidazolone p. Yellow 180 Yellow Benzimidazolone p. Yellow 161 Yellow Diaryiid p. Yellow 17
    BE2017 / 5772
    Yellow Quinophthalone p. Yellow 138 Yellow Monoazoic p. Yellow 74 Yellow Isoindoline p. Yellow 139 Orange Diketopyrroiopyrrole (DPP) p. Orange 73 Orange Isoindoline p. Orange 61 Orange Diketopyrroiopyrrole (DPP) p. Orange 71 Orange Benzimidazolone p. Orange 64 Orange Dianisidine p. Orange 16 Orange Azoic p. Orange 83 Orange Disazopyrazolone p. Orange 34 Red Red iron oxide p. Red 101 Red Diketopyrroiopyrrole (DPP) p. Red 254 Red Diketopyrroiopyrrole (DPP) p. Red 255 Red Disazocondensation p. Red 166 Red Disazocondensation p. Red 144S Red Azo condensation p. Red 214 Red Antraquinone p. Red 177
    BE2017 / 5772
    Red Perylene p. Red 179 Red Benzidine p. Red 38 Red Azoi'que p. Red 60 Red Antraquinone p. Red 177 1 ν ' Red Monoazoic p. Red 185 Red Cinquasia Magenta p. Red 202 Red Quinacridone p. Red 207 Red Azonaphtol AS p. Red 170 Red Quinacridone p. Red 122 Red Azonaphtol AS p. Red 146 1 ν 'Purple Dioxin p. Purple 23 Purple Dioxin p. Purple 37 Purple Quinacridone p. Purple 19 Blue Phthalo Blue Alfa p. Blue 15: 1 Blue Phthalo Blue Beta p. Blue 15: 3-- Blue Phthalo Blue Alfa p. Blue 15: 0 Blue Phthalo blue p. Blue 15: 2
    B E2017 / 5772
    Blue Phthalo blue p. Blue 15: 4 Blue Idanthrone p. Blue 60 Green Phthalo green p. Green 7 Green Phthalo green p. Green 36 Brown Chromium titanate p. Brown 24»» * Black Carbon black p. Black 7 Black Carbon black p. Black 6
    The pigment preparation according to the invention is in the form of a fluid powder or of microgranules.
    The pigment preparation according to the invention contains at least 60% by weight of at least one pigment additive relative to the total weight of the pigment preparation, more preferably 70%, even more preferably 85%, for example up to 95% weight.
    The pigment preparation in the form of microgranules has a particle size of its ingredients between 60 and 500 μm, more preferably between 80 and 350 μm as measured (for example, with a Digital Electromagnetic Sieve Shaker by Filtra Vibration mod. FTL 0200 /
    The at least one pigment additive in the final pigment preparation according to the invention also has a particle diameter D 90 (by number) in the range of 0.9 to 4 µm.
    The at least one pigment additive in the final pigment preparation according to the invention also has a particle diameter D 10 (in number) in the range of 0.5 to 1 µm.
    The pigment composition intended to obtain the pigment preparation according to g
    the invention further comprises other optional additives selected from the group consisting of heat, oxygen (antioxidants) and light stabilizers, carriers of electrical charges (antistatic) and heat, thermal additives , antiblocking additives, anti-sag additives, antioxidant additives, anti-static additives, UV stabilizing additives, fillers, anti-fibrillation agents, process aids, bulking agents , drying / compatibilizing additives, lubricants, clarification / clarification additives, flame retardants, optical brighteners and tracing additives, slipping agents. Organophosphites and phenolic antioxidants can be cited as heat stabilizers.
    Thermally conductive plastics, graphite, aluminum nitride and boron nitride can be cited as heat carriers.
    Silica, talc, calcium carbonate, aluminosilicate ceramics, mica, bis-amides, primary and secondary amides, organic and metallic stearates, silicones and polytetrafluoroethylene can be mentioned among the antiblocking additives.
    Electrically conductive fillers, glycerol monostearate, ethoxylated fatty acid amides, diethanolamides and polyether block amides can be cited among the antistatic additives.
    Oxanilides, benzophenones, benzotriazoles and hydroxyphenyltriazines can be cited as UV stabilizers.
    Calcium carbonate, kaolin, barium sulfate, talc, wollastonite, silica and its derivatives such as sublimed silica, and mica can be mentioned among the charges.
    Calcium carbonate, talc and natural and synthetic rubbers can be mentioned among the anti-fibrillation agents.
    Fluoropolymers, precipitated calcium carbonate and metal stearates can be mentioned among the process aids.
    Aliphatic hydrocarbons, labile nitrogen compounds and mixtures of sodium carbonate or bicarbonate and citric acid may be cited among the blowing agents.
    Stearic acid, benzoic acid, - copolymer of styrene and anhydride
    B maleic, and the copolymer of styrene and acrylonitrile can be mentioned among the compatibilizing additives.
    Molybdenum sulfide and graphite can be mentioned among the lubricants.
    Isophthalic and terephthalic acids, mixtures of organic diacids and group II oxides, hydroxides, or acids, talc, sodium benzoate and ionomers can be cited among nucleation / clarification.
    Halogenated organic compounds can be cited among the flame retardants.
    Bis-benzoxazole derivatives such as the benzotriazole phenylcoumarins, the naphthotriazole phenylcoumarines and triazine phenylcoumarines can be cited among the optical bleaching agents.
    Amides of unsaturated fatty acids, secondary amides and waxes can be cited among the slippery additives.
    Hindered phenols, phosphites, · phosphonites, secondary aromatic amines can be listed among antioxidants.
    Hindered-amine Light Stabilizers (HALS) or HAS (Hindered-amine Stabilizers), benzophenones and benzotriazoids can be listed among the light stabilizers.
    In another aspect, the invention relates to a process for preparing the pigment preparation according to the invention, in which the ingredients are treated with an apparatus capable of giving a particle diameter D 50 (in number) of the smallest pigment additive in the range between 0.5 and 3.5 μm and producing an amount of 60% by weight of at least one pigmentary additive relative to the total weight of the pigmentary preparation. The amount of the at least one pigment additive is at least 60%, preferably 70%, more preferably 85% relative to the total weight of the pigment preparation.
    According to the invention, the pigment preparation can preferably be obtained by the pigment composition.
    More preferably, the pigment preparation can be obtained by a process which comprises the following stages;
    1) introduction into a dry grinding apparatus of a pigment composition according to the invention comprising, consisting essentially of, or consisting of:
    at least one wetting dispersing agent chosen from the group consisting of a wax-based powder treatment additive with groups having an affinity for the pigments, acid polyester additive with a group having an affinity for the pigments, modified polyether with high affinity groups for pigments, styrene and polyether copolymers, maleic acid amides, amphiphilic copolymers, modified polyacrylate with high affinity groups for pigments, polyester-based block copolymer, polyurethane polymer high molecular weight, polyester-polyamine-polyolefin terpolymers, and polysiloxanes modified with epoxy or urethane groups, said a wetting dispersing agent having a melting point between 50 and 150 ° C, and
    - at least one pigment additive chosen from the group consisting of an inorganic pigment, an organic pigment, carbon black and dyes, and
    2) mixing and dry drying of the ingredients of step 1), and
    3) unloading of the pigmentary preparation thus obtained in the form of a fluid powder or of microgranules.
    A dry mill is preferred in the present invention over an air jet mill or a wet mill. In fact, the dry mill allows to apply an adequate milling force, while the air jet mill deploys too much energy, which compromises the post-treatment of the dispersed pigment particles, and therefore the stability of the final color. On the other hand, the wet grinder generally cannot disperse the pigment particles up to a particle size <15 µm and requires an additional drying step which makes the whole process more expensive.
    In the above process, all known organic and mineral pigments, carbon blacks and dyes are suitable for use in preparing a pigment preparation.
    Examples of pigment additives are listed above.
    S
    The preferred dry mill used in the process according to the invention can have at least two rotors and can be discontinuous or continuous.
    In a preferred embodiment, the pigment preparation can be obtained by a process comprising the following steps:
    1) introduction into a mill equipped with at least two rotors, at least one rotor preferably being a paddle rotor, of the pigment composition as described above;
    2) mixing and grinding of the pigment composition;
    3) unloading of the pigment preparation thus obtained.
    The continuous and batch devices used in the above processes both make it possible to obtain a pigment preparation in step 3) in the form of a fluid powder or in microgranules and comprising at least one pigment additive with a particle diameter Dgo (in number) in the range of 0.5 to 3.5 µm.
    The discontinuous dry mill comprises two to seven rotors, for example, three, four, five or six rotors, preferably four.
    When using the batch mixer, the average peripheral speed VPE is in the range of 5 to 50 m / s and step 2) of mixing and dry grinding is preferably carried out for 10 min to 90 min, for example from 15 to 90 min or 20 to 90 min, until reaching a temperature between 50 and 150 ° C.
    Without wishing to be bound by a theory, the inventors of the present invention believe that the final particle diameters of the at least one pigment additive and that the fineness of grinding of the pigment preparation are essential to the final performance of the product (dispersibility and power dye).
    All the devices which allow a large number of repeated impacts between the particles and parts of the device, such as rotors, and therefore impacts to the particles of ingredients of the invention, are suitable for the invention.
    The fineness of the pigment additive in the pigment preparation is correlated with the number of impacts that the pigment particles have undergone when they bump against each other and against the rotors, and against the internal envelope of the mill chamber. Without wishing to be bound by a theory, it is believed that the action of grinding a dry mill over an extended period of time, for example from 10 to 90 min, distributes the wetting dispersing agent evenly between the particles of the pigment additive without requiring the use of water or another solvent.
    Preferential aspects of the VPE, durations and final temperatures can be established as a function of the characteristics of the ingredients, preferably of the at least one additive chosen from the group consisting of an inorganic pigment, an organic pigment, carbon black and dyes to be treated (eg density, oil absorption capacity, specific surface, etc.).
    The product obtained in step 3) in the form of a fluid powder or of microgranules is discharged and advantageously packaged.
    Preferably, the dust-free microgranules have a particle diameter in the range between 80 and 350 µm.
    When the dry mill is discontinuous, a granulation unit can also be provided when the product of step c) is a fluid powder. Otherwise, the discontinuous apparatus makes it possible to obtain dust-free microgranules having a particle size in the range between 60 and 500 μm, more preferably from 80 to 350 μm as measured (for example with a Digital Electromagnetic Sieve Shaker by Filtra Vibration mod FTL 0200).
    Preferably, the granulation step is done via a worm feed system which forces the product having reached the preferred temperature in the range between 60 ° C and 140 ° C to rotate with a regular vortex, which causes the formation of very homogeneous spherical granules. The peripheral speed (VPE) of the screw feed system is preferably between 15 and 50 m / s. After about five minutes, uniform microgranules are formed. The temperature is preferably brought below 50 ° C., which causes the complete resolidification of the support and stabilizes the spherical granules.
    The dust-free microgranules obtained have the form of uniform microgranules with a narrow particle size curve for a particle size in the range between 60 and 500 μm, more preferably between 80 and 350 μm as measured (for example with a Digital Electromagnetic Sieve Shaker by Filtra Vibration mod. FTL 0200).
    The performances of the pigment preparations according to the invention, namely the superior qualities of disaggregation and / or disaggregation of the pigment particles, homogeneity of dispersion, as well as dispersibility and coloring power as indicated in the experimental part, are comparable and, in certain cases , even better than the performance that can be obtained with the ß process
    traditional extrusion. The surprising characteristic of the present pigment preparation is the fact that the final pigment preparation maintains these performances with a percentage of at least 60%, more preferably 70%, even more preferably 85%, preferably up to 95% by weight. at least one pigment additive relative to the total weight of the pigment preparation.
    As is clearly indicated in the following experimental part, the fineness of the ground particles of the at least one pigment additive of the final pigment preparations of the invention is represented by an advantageously limited range.
    The final pigment preparation of the invention has exceptional homogeneity, deriving from the fact that the particle size D 90 (in number) of the particles of ground pigment is at most 4 μm, with very few particles of more than 5 μm .
    As specified above, the universal pigment preparations comprise at least 60%, more preferably 70% by weight of at least one pigment additive relative to the total weight of the pigment preparation, preferably 85% of organic pigments and preferably up to 95% mineral pigments.
    Since the pigment preparations according to the invention are universal and have a high concentration of pigments, another aspect of the invention relates to a universal coloring system comprising a limited number of basic colors corresponding to a limited set of pigment preparations suitable for the preparation of 'plastic and rubber products with different colors. The pigment preparations according to the invention allow the preparation of colors by simple dry mixing of the basic single-color pigment preparations according to the invention (approximately 16-22) without the need for personalized treatment of the pigment mixture with the extrusion process.
    Consequently, the invention also relates to a coloring system comprising a series of pigment preparations having desired shades (RAL, NCS, BS etc.) which can be obtained by dry mixing of at least two pigment preparations according to the invention.
    B
    The coloring system can be used for any plastic material. Preferably, any given coloring system can be used for at least three plastics.
    Therefore, in another aspect, the invention relates to a use of the pigment preparation according to the invention for coloring all kinds of plastics.
    A plastic material is chosen, for example, from polyethylene products (eg HDPE, LDPE, LDPE, PEMD, EVA, EVOH, even obtained from metallocene catalytic systems), polypropylene products (e.g. PP (even obtained from from metallocene catalytic systems), copolymers of PP, EPR, EPDM), styrenic products (eg PS, SAN, HIPS, ν '
    ABS, ASA), vinyl chloride type polymers (eg PVC (polyvinyl chloride)), plasticized or not, acrylic polymers (eg PMMA, polyacrylates), polyamides (eg PA6, PA6,6, PA11 , PA12, and their co-polymers), polycarbonates and their mixtures (e.g. PC / ABS (polycarbonate / acrylonitrilebutadiene-styrene), PC / polyesters), polyesters (e.g. PET, PBT, copolyesters), ν 'polyurethanes (e.g. . TPU), thermoplastic elastomers (eg TPO, TPV). The invention will now be illustrated by examples without limitation of the invention.
    Experimental part
    Preparations according to the invention
    All the pigments used are indicated below by the designation of their color index universally used for the identification of pigments.
    Example 1
    Preparation of the XP303-C pigment preparation (pigment concentration =
    %)
    6800 g of Red 254 pigment (available under the name SR2P from the company Cinic) were mixed and ground with 1200 g of the dispersing agent Disperplast 1018 supplied by (company BYK.
    The dry mill was a batch machine with 4 rotors.
    B
    Process parameters: 1 min at a peripheral speed of 6 m / s, 14 msn at a peripheral speed of 15 m / s then 6 min at a peripheral speed of 25 m / s; the temperature reached 72 ° C.
    The pigment preparation thus obtained corresponded to microgranules, with the following dimensional values, of particle size of the pigment additive in the pigment preparation, analyzed in dispersion in butyl acetate by means of a Beckman Coulter laser granuiometer:
    D 10 = 0.571 pm
    D 5 o = 0.790 pm
    DG 0 - 1.034 pm
    Granulometry of microgranules: in the range from 80 ′ to 350 μm.
    Example 2
    Preparation of the XP901 pigment preparation (pigment concentration =
    %)
    6,400 g of PBL-7 carbon black pigment (Special Black 100 carbon black from the Orion company) and 1,600 g of the Disperplast 1018 dispersant from the BYK company were mixed and ground by a discontinuous dry mill equipped with 4 rotors . Process parameters: 1 min at a peripheral speed of 6 m / s, 14 min at a peripheral speed of 15 m / s then 6 min at a peripheral speed of 25 m / s; the temperature reached 132 ° C. The composition obtained was in the form of dust-free microgranules.
    D 50 , measured as in Example 1, of the pigment additive in the pigment preparation = 1.5 μm
    Granulometry of microgranules: 80-350 pm
    Example 3
    Preparation of the XP307C pigment preparation (pigment concentration =
    %)
    5400 g of Red 101 pigment (Bayferrox 130 M from the company Lanxess) were mixed and ground by a batch mill equipped with 4 rotors with 600 g of the dispersant Disperplast 1018 from the company BYK.
    g
    Process parameters: 1 min at a peripheral speed of 6 m / s, 14 min at a peripheral speed of 25 m / s. The temperature reached 50 ° C.
    The composition obtained was in the form of a fluid powder.
    D 50 , measured as in Example 1, of the pigment additive in the pigment preparation = 1.2 μm
    Powder particle size <50 µm
    Example 4
    Preparation of the XP001 PW6 pigment preparation (pigment concentration = 90%)
    5400 g of pigment PW6 101 (CR-826 from Tronox) were mixed and ground by a batch mill fitted with 4 rotors with 600 g of dispersant Disperplast 1018 from BYK.
    Process parameters: 1 min at a peripheral speed of 6 m / s, 14 min at a peripheral speed of 25 m / s then 6 min at a peripheral speed of 30 m / s;
    The composition obtained was in the form of micro-granules.
    D 50) measured as in Example 1, of the pigment additive in the pigment preparation = 0.7 pm Granulometry: 80-350 pm k-Exempie 5
    Preparation of the XP105-C pigment preparation (pigment concentration =
    %)
    4800 g of the pigment PY139 (Paliotol L2140 from the company BASF) were mixed and ground by a batch mill equipped with 4 rotors, with 1200 g of the dispersant Disperplast 1018 from the company BYK.
    Process parameters: 1 min at a peripheral speed of 6 m / s, 14 min at a peripheral speed of 15 m / s, The temperature reached 52 ° C.
    The preparation thus obtained was in the form of a fluid powder.
    D 50î measured as in Example 1, of the pigmentary additive in the pigmentary preparation = 1.6 μm
    Particle size of the powder <50 pm
    B E2017 / 5772
    Example 6
    Preparation of the XP502-C pigment preparation (pigment concentration =
    %) r ' 5 4800 g of Blue Phthalo pigment PB 15: 1 (MP PV Blu Solido a 4R from the company
    Clariant) were mixed and milled with a batch dry mill equipped with 4 rotors with 1200 g of dispersant Disperplast 1018 from BYK.
    Process parameters: 1 min at a peripheral speed of 6 m / s, 14 min at a peripheral speed of 15 m / s.
    The preparation thus obtained was in the form of a fluid powder and was analyzed in suspension in butyl acetate using a Beckman Coulter laser granulometer, optical model Fraunhofer.rf780z. The particle size of the pigment additive in the pigment preparation was:
    Dio = 0.746 pm 15 D 5 o = 1.526 pm
    Dg 0 = 3.269 pm
    Particle size of the powder <50 µm as measured with a Digital Electromagnetic Sieve Shaker by Filtra Vibration mod. FTL 0200
    2Q Example 7
    Preparation of the green color for the coloring system according to the invention
    To obtain a shade of green, three products according to the invention were dry mixed (duration = 2 minutes) using a mixer: the product XP001 PW6 prepared in Example 4 (dosage = 75% of the product of l example 4, which is white with a pigment concentration of 25 90%) + product XP502 PB-C 15: 1 prepared in example 6 (dosage = 39% of the product of example 6 with a pigment concentration 80%) + the product XP105-C PY139 prepared in Example 5 (dosage = 1.63% of the product in Example 5 with a pigment concentration of 80%) which is yellow. We got a green color. The green color was perfectly
    3Φ homogeneous on visual examination.
    Example 8
    B
    Preparation of a dark blue color for the mixing system according to the invention
    To obtain a dark blue color, three products according to the invention were dry mixed (duration = 2 minutes) using a normal mixer: the product of Example 2 XP901 PBL-7 (dosage 30% of the product of 'example 2, which is black with a pigment concentration of 80%) + XP001 PW6 of example 4 (dosage = 70% of the product of example 4, which is white with a pigment concentration of 90% ) + XP502-C PB 15: 1 from Example 6 (dosage = 16.25% of the product from Example 6 which is blue with a pigment concentration of 80%). A dark blue color is obtained if the preparations according to the invention have been dry mixed. A dark blue color is obtained which is perfectly comparable to the quality which can be obtained with a known masterbatch treated by the traditional extrusion process.
    Example 9
    Evaluation of samples colored by pigment preparations according to the invention
    ABS / SAN plates were prepared according to the following process:
    Sample 1: colored plate with XP3Q3-C
    In an extruder of CDM ENGINEERING srl, model ES-65, ABS + SAN (50-50%) was introduced together with the preparation of Example 1 (XP303-C), the latter up to 0.70% in weight.
    The extrusion temperatures were:
    Cylinder 1: 200 ° C, Cylinder 2: 210 ° C, Cylinder 3: 230 ° C, Cylinder 4: 240 ° C, Cylinder 5: 235 ° C, plate: 230 ° C, head: 230 ° C.
    The product leaving the extruder was then printed with an IMEX ITALY press, SM 50T. The molding temperatures were: Zone 1: 220 ° C, Zone 2: 230 ° C, Zone 3: 240 ° C, nozzle: 230 ° C.
    Sample 2: ABS-SAN plate stained with XP307C
    According to the procedure and with the same equipment as sample 1, sample 2 was produced with the preparation XP307C of example 3 at a rate of 0.60% by weight.
    Sample 3: non-colored ABS-SAN plate
    Following the procedure and with the same equipment as sample 1, sample 3 was produced using a non-cross-linked ABS-SAN mixture.
    The three samples thus prepared were subjected to the following tests (carried out by THE POLYTECHNICAL UNIVERSITY OF MILAN, DEPARTMENT OF CHEMICAL MATERIALS AND CHEMICAL ENGINEERING Giulio Natta Polytechnic Laboratory for Testing on Polymers):
    - color resistance (before and after Xenotest);
    - Fluidity index (MFR);
    - thermogravimetric analysis;
    - Rockwell hardness;
    - Izod notched;
    - migration;
    - resistance to chemicals (ESC).
    Aging tests (Xenotest) according to ISO 4892-2: 2006 (AMF2009) with Solarbox 3000e equipment and exposure to xenon, irradiance: 550W / m z , lamp: 2500 W; intensity measured on the surface of the sample, air-cooled; filter: OUTDOOR UV filter (280 nm) installed between the lamp and the test chamber; thermometer: BST (black-standard thermometer); temperature: 65 ± 3 ° C (lamp on); cycle: continuous radiation.
    The following tests were carried out on the samples before and after aging (Xenotest):
    Color resistance: by the UNI EN 20105 / A02: 1996 process, gray scale according to the process with color variation between 1 and 5 (Ί = maximum variation; 5 = no change);
    Fluidity index: by the ASTM D1238: 2013 process (load = 5 kg; test temperature = 230 ° C)
    Rockwell hardness: by the UNI EN ISO 2039-2: 2001 process
    Izod impact test: using the UNI EN ISO 180: 2009 process.
    Color variation (UNI EN 20105 / A02: 1996): initial and after Xenotest Global migration in water: Color migration according to the method of the Italian Ministry of Health, DM 74, April 6, 2004, just placing the samples 1-3
    B E2017 / 577.2 made for 24 hours in contact with water at a temperature of around 40 ° C.
    The results shown in Table 1 were obtained.
    Table 1
    Samplen ° MFR(g / 10 min) Izod test (kj / m 2 ) Rockwell hardness scale R Grayscale Colorvariation Migration(ppm) new afterXenotest new afterXenotest new afterXenotest --afterXenotest afterXenotest 1 8.58 9.08 14.0 5.14 115.4 112.6 5 2.13 0 2 8.22 10.08 15.2 6.51 115.7 113.1 5 0.82 0 } 3 11.19 11.96 8.28 2.62 83.8 108.5 % 14.42 0
    The LIM data, as shown in Table 1, demonstrate the possibility of processing and the good dispersion of the colored samples (non-significant differences when compared to the non-colored sample). The Xenotest results show minimal variations, both for the non-colored sample (sample 3) and for the two samples colored by the preparations according to the invention (samples 1 and 2). In all cases, the variations observed, approximately 1-2 units, are less than the range of known color samples subjected to 1000 hours of aging.
    2Q by the Xenotest.
    The Izod test (impact resistance) shows very superior results (+ 77%) for colored samples (with pignientaires preparations according to the invention) compared to unstained samples, èomme confirmed by examining the areas 25 subjected to fracture which have mounted a homogeneous discoloration and a well-developed deformation process. On the other hand, the fracture surface of the colored sample 3 was less homogeneous, showing areas with irregular depressions.
    The largest decrease in initial value after 1000 hours of aging
    2Q by the Xenotest was detected compared to sample 3 (non-colored).
    The Rockwell hardness test shows:
    B
    a) before aging by Xenotest, significantly higher values (+ 37%) for samples colored by the pigment preparation according to the invention;
    b) after 1000 hours of aging by Xenotest, the values indicate opposite behavior between the colored and non-colored samples. While the colored samples virtually retained their original values, showing only a moderate change, the non-colored sample underwent a sharp reduction. This phenomenon confirmed the increased fragility of the uncoloured sample (as confirmed by the results of the impact test).
    The results of the color resistance test, measured after 1000 hours of exposure to Xenotest, were extraordinary for the colored samples. No discoloration was observed in colorimetric analysis and on the gray scale. In short, the behavior of the colored samples was significantly better than that of the non-colored sample.
    In all samples, total migration, under specific test conditions, was found to be below detection limits.
    All samples were eligible for food contact.
    Example 10
    Evaluation of colored samples with a pigment preparation according to the invention
    The pigment preparation according to Example 1 (XP303 C) was compared with the pure pigment by coloring polypropylene.
    The tests were carried out with the following instruments:
    Analytical balance (precision: 0.001g), precision balance (precision: 0.01 g), mixer (model: CY-37, rotation speed: 0-55rpm, clock: 0.1s99.99h, power motor: 90-180 W, internal cylinder diameter: 50 mm, depth: 60 mm), twin screw extruder (model: CTE 20, speed: 600 rpm, motor power: 4 kW, L / D = 56, diameter: 21.7 mm) machine for injection molding (model: HTF58X1, screw model: A-D26, closing force: 580 kN, injection volume: 66.pm 3 ); spectrophotometer (Model: Konica-Minolta CM-2600d)
    The polypropylene samples were tested at pigment contents of 0.5% or 0.1%.
    The procedure consisted of a manual mixing of polypropylene resin, of pigment powder or of pigment preparation XP303 C of Example 1 of the invention and of silicone oil until a homogeneous mixture was produced. The resulting mixture was injection molded to make pellets. The two samples (comparative and according to the invention) exhibited good dispersibility.
    No visible stain is detected.
    The process according to the invention has significantly improved the FPV (filtration value measured according to DIN EN 13900-5).
    Filtration value using pure pigment = 5.250 bar / g; XP303 C = 2,420 bar / g
    In 1:10 reduction, the preparation XP303 C according to the invention has a stronger coloring power.
    At a pigment content of 0.5% or an equal content of preparation (corresponding to 15% less pigment), the preparation XP303 C according to the invention had a coloring power 130% stronger than the pure pigment. The dispersibility clearly indicated that the preparation XP303 C seion the invention had better dispersibility, demonstrated again by measuring the filtration value.
    Example 11
    Evaluation of samples colored by a pigment preparation according to the invention
    HP 714 and HP 729 (pigment concentration = 90 %%
    HP 714: 4500 g of Brown 24 pigment (Heucodur Yellow G 9239 from Heubach) were mixed and ground by a batch mill equipped with 3 rotors with 500 g of Disperplast 1018 dispersant from BYK.
    Process parameters: 1 min at a peripheral speed of 6 m / s, 29 min at a peripheral speed of 30 m / s, the temperature reached 1/10 ° C.
    B E2017 / 5772
    The composition obtained was in the form of granules.
    Granule size of granules <500 μm HP 729: 4500 g of Brown 24 pigment (Heucodur Yellow G 9239 from the company Heubach) were mixed and ground by a discontinuous mill equipped with 3 rotors with 500 g of dispersant P 4100 (liquid at temperature BYK.
    Process parameters: 1 min at a peripheral speed of 6 m / s, 29 min at a peripheral speed of 30 m / s, the temperature reached 110 ° C.
    The composition obtained was in the form of granules.
    Granule size <500 µm
    The pigment preparations (HP 714 and HP 729) were compared by TABS dye according to the test according to DIN EN ISO 294-1.
    The tests were carried out with the following instruments:
    Precision balance (precision: 0.002 g), twin screw extruder (model: Leistritz, ZSE 18HP-35D, rotation speed: 125 rpm, motor power:
    9.4 kW, L / D = 35, diameter: 18 mm), injection molding machine (model: Arburg, 300C 500-170, screw model: 30 L 873 SW, injection volume: 13.5 cm 3 ); spectrophotometer (model: Datacolor, Spectraflash SF 300)
    Measuring the coloring power: The relative coloring power is calculated from the reduction compared to the standard in accordance with DIN EN ISO 787-24.
    r The acrylonitrile butadiene styrene (ABS) samples were tested at a pigment content of 0.1%, a reduction of 1:10.
    The preparation HP 714 showed a significantly better dispersibility than that of HP 729. This was demonstrated by the difference in coloring power. The coloring power of HP 714 was 37% higher than that of HP 729.
    Reduction 1:10 / 0.1% P gment, 1% TiO 2 / Twin screw extruder ABS Product AL Aa Ab AC AH. ΔΕ Strength HD G 9235 # 11721756-0 Standard HP 714 -0.3 -0.1 0.3 0.3 0.1 0.5 105.7 HP 729 1.4 -0.9 -1.3 -1.5 0.7 2.1 76.6
    Another indication of better dispersibility was the quality of the batches
    B E2017 / 5772 prepared. Prior to injection molding, each color preparation was premixed with the carrier material (ABS) using a twin screw extruder. Unlike HP 714, the iot product of HP 729 was inhomogeneous, containing granules with very different coloring powers.
    5 As regards the only difference between the two preparations, the dispersing agent P 4100 was not suitable for coloring TABS.
    Example 12 Comparative example
    Preparation of the pigment preparation (pigment concentration = 80%)
    1760 g of Monarch 1100 carbon black (available from Cabot Corporation) were mixed and ground with 440 g of the dispersing agent Atmer 116 (liquid at room temperature) supplied by the company CRODA.
    s
    The dry mill was a batch machine with 3 rotors.
    Process parameters: 1 min at a peripheral speed of 6.1 m / s then 39 min at a peripheral speed of 31 m / s; the temperature reached 66 ° C.
    The pigment preparation thus obtained was in the form of a powder.
    A masterbatch containing 30% carbon black was obtained by mixing the pigment preparation with a styrene acrylonitrile polymer
    2Q (Kostil! B755) using a 1644 I Banbury mixer from Farrel Corporation.
    The following process conditions were applied: chamber temperature of 40 ° C; rotor temperature of 40 ° C; mixing time after flow 90 s; dynamic pressure of 4.2 bar; and rotor speed of 182 rpm. The product was spilled at 190 ° C. The product has been cooled and ground into coarse granules
    2 5 with a Paliman PS3 grinder with 3 rotating blades.
    The masterbatch was then diluted (30 ± 5% carbon black in the acrylonitrile butadiene styrene polymer GP22) by extrusion on a single screw (LabTec - 30 mm, 30 L / D, temperature of the mold in the hopper: 220- 220-220-210200 ° C), and cut into tablets by a cylindrical cutting system.
    The tablets were dried overnight at 70 ° C.
    The product obtained was again diluted with ABS GP22 from 5 to 0.75% carbon black during the injection molding in plates and plates for impact test. The molding temperatures were: Zone 1: 200 ° C, Zone 2: 220 ° C ^ Zone 3: 240 ° C, nozzle: 230 ° C.
    A comparative masterbatch of acrylonitrile styrene polymer was prepared using Black Pearls 1100 carbon black (Cabot Corporation), a carbon black having the same surface area as Monarch 1100 carbon black but produced in tablet form, using the same process as described above for the pigment preparation. The masterbatch (30% by weight of carbon black) was diluted and formed into plates and plates, for impact testing as described above.
    The color of the plates was analyzed according to L * a * b * with an UltraScan Vis from Hunterlab,
    The Izod impact resistance of the notched specimens was measured according to ISO 180 / A: 2000 by a CEAST Pendulum impact tester.
    Results:
    ValueL * (u.a) Impact resistance KJ / m 2 BP1100 without binder 7.68 11.4 dispersantM1100 / Atmer 116 8.44 9.4
    The above data shows that the use of the dispersant Atmer 116, which is a liquid at room temperature, to form the pigment preparation, and disadvantageous both for color performance and for resistance to s
    the impact of plastics prepared with the pigment preparation, compared to plastics prepared with pure pigment.
    BE2017 / 5772
    权利要求:
    Claims (38)
    [1]
    1. Pigment preparation containing:
    at least one wetting dispersing agent selected from the group consisting of a wax-based powder treatment additive with groups having an affinity for pigments, acid polyester additive with a group having an affinity for pigments, polyether modified with high affinity groups for pigments, styrene and polyether copolymers, maleic acid amides, amphiphilic copolymers, polyacrylates modified with high affinity groups for pigments, polyester-based block copolymers, polyurethane polymer with high molecular weight, polyester-polyamine-polyolefin terpolymers, and polysiloxanes modified with epoxy or urethane groups, said a wetting dispersing agent having a melting point between 50 and 150 ° C., and at least one pigmentary additive chosen from the group consisting of a mineral pigment, an organic pigment, carbon black and dyes, where the particle diameter D 50 (in number ) of the at least one pigmentary additive in the pigmentary preparation is in the range of 0.5 to 3.5 μm, and the pigmentary preparation comprises at least 60% by weight of the at least one pigmentary additive relative to the total weight of the pigment preparation.
    [2]
    2. Pigment preparation according to claim 1, the pigment preparation containing less than 3% water.
    [3]
    3. Pigment preparation according to one of claims 1 and 2, wherein the wetting dispersing agent has a number average molecular weight between 5000 and 35000.
    [4]
    4. Pigment preparation according to any one of claims 1 to 3, the pigment preparation being in the form of:
    a) a fluid powder comprising particles with D 2 o of at least 0.8 pm and D 90 up to 5 pm measured by a laser granulometer in the dry state under a pressure of
    3.5 bar, or
    BE2017 / 5772
    b) microgranules comprising granules with D 2 o of at least 10 μm and D 90 up to 1000 μm measured by a laser granulometer in the dry state under a pressure of 3.5 bar.
    [5]
    5. Pigment preparation according to claim 4, wherein the microgranules have a particle size in the range between 60 and 500 μm, preferably between 80 and 350 μm
    [6]
    6. Pigment preparation according to any one of claims 1 to 5, in which the mean particle diameter D 90 (by number) of the at least one pigment additive in the pigment preparation is in the range from 0.9 to 4 pm.
    [7]
    7. Pigment preparation according to any one of claims 1 to 6, wherein the average particle diameter D10 of the at least one pigment additive in the pigment preparation is in the range of 0.5 to 1 µm.
    [8]
    8. Pigment preparation according to any one of claims 1 to 7, the pigment preparation containing at least 70% by weight of the at least one pigment additive relative to the total weight of the pigment preparation.
    [9]
    9. Pigment preparation according to any one of claims 1 to 8, the pigment preparation containing at least 85% by weight of the at least one pigment additive relative to the total weight of the pigment preparation.
    [10]
    10. Pigment preparation according to any one of claims 1 to 9, further containing at least one additive chosen from the group consisting of heat stabilizers, antioxidants, light stabilizers, antistatic agents, transporters heat, anti-blocking additives, anti-sag additives, UV stabilizing additives, fillers, anti-fibrillation agents, process aids, blowing agents, drying / compatibilizing additives, lubricants , nucleation / clarification additives, flame retardants,
    BE2017 / 5772 optical brighteners / tracing additives, slipping agents.
    [11]
    11. Pigment preparation according to claim 10, wherein the fillers comprise at least one member of the group consisting of calcium carbonate, kaolin, barium sulphate, talc, wollastonite, silica, sublimed silica, mica, and any of their mixtures.
    [12]
    12. Pigment preparation according to any one of claims 1 to 11, the pigment preparation being miscible with at least three polymers chosen from polymers based on polyethylene, polystyrene, SAN, HIPS, ABS, ASA, polymers of polyvinyl chloride type , polyacrylates, polyamides, polycarbonates, polyesters, polyurethanes and thermoplastic elastomers.
    [13]
    13. Pigment preparation according to any one of claims 1 to 12, the pigment preparation being produced by a process comprising: the introduction into a grinder comprising at least two rotors of the wetting dispersing agent and the pigment additive;
    mixing and grinding the wetting dispersant and the pigment additive to disperse the pigment additive with the wetting dispersing agent; and the recovery of the resulting pigment preparation in the form of a fluid powder or in the form of microgranules.
    [14]
    14. Pigment preparation according to claim 13, wherein the average peripheral speed (VPE) of the at least two rotors during mixing and grinding is in the range of 5-50 m / s.
    [15]
    15. Pigment preparation according to claim 13 or 14, wherein the duration of the complete process is from 10 min to 90 min and the temperature is from 50 to 150 ° C.
    [16]
    16. Pigment preparation according to any one of claims 13 to 15, wherein the grinder comprises at least two rotors, at least one rotor being a rotor with blades.
    BE2017 / 5772
    [17]
    17. Pigment preparation according to any one of claims 13 to 16, wherein the grinder is a dry grinder.
    [18]
    18. Pigment preparation according to any one of claims 1 to 17, wherein a mixture of the pigment preparation with a polymer chosen from polymers based on polyethylene, polystyrene, SAN, HIPS, ABS, ASA, polymers of polyvinyl chloride type , polyacrylates, polyamides, polycarbonates, polyesters, polyurethanes and thermoplastic elastomers such that the mixture includes 0.5 to 1% by weight of the pigment additive shows a coloring power at least 20% better than a mixture of the same composition but prepared in pouring each ingredient into a blender and mixing the ingredients.
    [19]
    19. A coloring system comprising several pigment preparations of a desired color which can be obtained by dry mixing of at least two pigment preparations according to any one of claims 1 to 18.
    [20]
    20. Use of the pigment preparation according to any one of claims 1 to 18 for coloring a plastic material.
    [21]
    21. A colored composition comprising the pigment preparation according to any one of claims 1 to 18 and a plastic material.
    [22]
    22. A colored composition according to claim 21, in which the plastic material is chosen from polyethylene products, polypropylene products and their copolymers, polystyrene and its copolymers, polymers of polyvinyl chloride type, acrylics, polyacrylates, homopolymers and polyamide copolymers, polycarbonates and mixtures of polycarbonates, polyester homopolymers and copolymers, polyurethanes and thermoplastic elastomers.
    [23]
    23. A colored composition according to claim 21 or 22, in which the plastic material is chosen from HDPE, LDPE, LPEBD, PEMD, EVA, EVOH,
    BE2017 / 5772 polyethylene products from metallocene catalyst systems, PP, polypropylene products produced from metallocene catalyst systems, EPR, EPDM, PS, SAN, HIPS, ABS, ASA, PVC, PMMA, PA6, PA6,6, PA11, PA12, PC / ABS blends, PC / polyester blends, PET, PBT, TPU, TPO, and TPV.
    [24]
    24. A colored composition according to any one of claims 21 to 23, the colored composition containing 0.5 to 1% by weight of the pigment additive and having a coloring power at least 20% better than a mixture having the same composition but prepared by pouring each component individually into a blender and combining the components into a uniform mixture.
    [25]
    25. Pigment preparation containing:
    at least one wetting dispersing agent selected from the group consisting of a wax-based powder treatment additive with groups having an affinity for the pigments, acid polyester additive with a group having an affinity for the pigments, polyether modified with high affinity groups for pigments, styrene and polyether copolymers, maleic acid amides, amphiphilic copolymers, polyacrylates modified with high affinity groups for pigments, polyester-based block copolymers, polyurethane polymer with high molecular weight, polyester-polyamine-polyolefin terpolymers, and polysiloxanes modified with epoxy or urethane groups, said a wetting dispersing agent having a melting point between 50 and 150 ° C; and at least one pigment additive chosen from the group consisting of an inorganic pigment, an organic pigment, carbon black and dyes, in which the pigment preparation contains at least 60% by weight of the at least one pigment additive relative to the total weight of the pigment preparation, and where each of a first, a second and a third uniform mixture of the pigment preparation with a first, a second and a third polymer such that the first, second and third blends obtained contain 0 , 5 to 1% by weight of pigment has a coloring power at least 20% better than a mixture having the same composition but prepared by pouring
    BE2017 / 5772 individually each component in a mixer and by combining the components in a uniform mixture, the first, second and third polymers being three different polymers chosen from the group consisting of polymers based on polyethylene, polystyrene, SAN, HIPS, ABS, ASA, polymers of polyvinyl chloride type, polyacrylates, polyamides, polycarbonates, polyesters, polyurethanes and thermoplastic elastomers.
    [26]
    26. A method of manufacturing a pigment preparation comprising: the introduction into a grinder of at least one wetting dispersing agent chosen from the group consisting of a wax-based powder treatment additive with groups having an affinity for pigments, additive based on acidic polyester with a group having an affinity for pigments, polyether modified with groups with high affinity for pigments, copolymers of styrene and polyethers, amides of maleic acid, amphiphilic copolymers, polyacrylates modified with high affinity groups for pigments, polyester-based block copolymers, high molecular weight polyurethane polymer, polyester-polyamine-polyolefin terpolymers, and polysiloxanes modified with epoxy or urethane groups, said wetting agent having a point of melting between 50 and 150 ° C, and at least one pigmentary additive chosen from the group consisting of a pigm ent mineral, an organic pigment, carbon black and dyes, the mill comprising at least two rotors;
    mixing and grinding the wetting dispersing agent and the at least one pigmentary additive together to form the pigmentary preparation, the average peripheral speed of the grinder being from 5 to 50 m / s; and recovering the pigment preparation, the pigment preparation containing at least 60% by weight of the at least one pigment additive.
    [27]
    27. The method of claim 26, wherein the mixing and grinding are carried out for 10 to 90 min.
    [28]
    28. The method of claim 26 or 27, wherein the maximum temperature
    BE2017 / 5772 produced by the mixture of wetting dispersing agent and pigmentary additive during mixing and grinding is between 50 and 150 ° C.
    [29]
    29. Method according to any one of claims 26 to 28, in which the particle diameter D 90 (in number) of the at least one pigment additive in the pigment preparation recovered is between 0.9 and 4 μm.
    [30]
    30. A method according to any one of claims 26 to 29, wherein the particle diameter D 10 (in number) of the at least one pigment additive in the pigment preparation recovered is in the range of 0.5 to 1 µm .
    [31]
    31. Process according to any one of claims 26 to 30, in which the particle diameter D 50 (in number) of the at least one pigment additive in the pigment preparation recovered is between 0.5 and 3.5 μm.
    [32]
    32. The method according to any one of claims 26 to 31, wherein the mill is a dry mill.
    [33]
    33. Method according to any one of claims 26 to 32, in which at least one of the rotors is a paddle rotor.
    [34]
    34. Method according to any one of claims 26 to 33, wherein the wetting dispersing agent has a number average molecular weight between 5000 and 35000.
    [35]
    35. Method according to any one of claims 26 to 34, wherein the pigment preparation recovered is in the form of:
    a) fluid powder comprising particles with D 2 o of at least 0.8 pm and D 90 up to 5 pm measured by a laser granulometer in the dry state under a pressure of 3.5 bar, or
    b) microgranules comprising granules with D 2 o of at least 10 pm and D 90 up to 1000 pm measured by a laser granulometer in the dry state under a
    BE2017 / 5772 pressure of 3.5 bar.
    [36]
    36. Method according to any one of claims 26 to 35, wherein the pigment preparation recovered is in the form of microgranules having a
    5 particle size in the range between 60 and 500 µm, preferably between 80 and 350 µm.
    [37]
    37. Method according to any one of claims 26 to 36, wherein the pigment preparation recovered is in the form of a fluid powder having
    10 a particle size of less than 50 µm.
    [38]
    38. The method according to any of claims 26-37, wherein further introducing comprises introducing at least one additive selected from the group consisting of heat stabilizers, antioxidants, light stabilizers, agents
    15 anti-static, heat transporters, anti-blocking additives, anti-sag additives, UV stabilizing additives, fillers, anti-fibrillation agents, process aids, blowing agents, drying additives / compatibilizers, lubricants, nucleation / clarification additives, flame retardants, optical brighteners / tracing additives, slip agents.
    BE2017 / 5772
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    同族专利:
    公开号 | 公开日
    CN110225948A|2019-09-10|
    IT201600109323A1|2018-04-28|
    US20190338085A1|2019-11-07|
    PL430464A1|2020-07-27|
    BE1024918A1|2018-08-09|
    WO2018078072A1|2018-05-03|
    FR3058145A1|2018-05-04|
    JP2020517756A|2020-06-18|
    FR3058145B1|2021-05-07|
    KR20190086455A|2019-07-22|
    DE112017005419T5|2019-07-18|
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    法律状态:
    2018-10-22| FG| Patent granted|Effective date: 20180821 |
    优先权:
    申请号 | 申请日 | 专利标题
    IT102016000109323|2016-10-28|
    IT102016000109323A|IT201600109323A1|2016-10-28|2016-10-28|UNIVERSAL PIGMENTARY PREPARATIONS FOR COLORING AND REINFORCING PLASTIC MATERIALS|
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