General-purpose pigment preparation for reinforcing and coloring plastics

Abstract

The present invention relates to a pigment preparation which has a versatility for the dyeing of plastics.

Description

[0001] This application is a divisional application of Chinese invention patent application (invention title: general-purpose pigment formulation for reinforcing and coloring plastics, application date: October 27, 2017; application number: 2017800735866). Technical Field

[0002] This invention relates to pigment formulations (pigment preparations) intended for use in reinforcing and coloring plastic materials, and their use as dye concentrates, said pigment formulations comprising pigments, and / or other additives and / or fillers. Background Technology

[0003] To obtain objects and finished products made of plastics or rubber, it is generally necessary to introduce polymers into the base raw materials; that is, substances suitable for imparting the desired properties to them in the final product. These substances can be: substances that impart color (color) to the material, such as pigments or dyes; or substances that impart functionality to the finished product (e.g., improved resistance to fire and / or light); or even substances that improve the mechanical and / or thermal properties of the final product. Typically, additives (often defined as process additives) are also used to protect the polymer during the conversion to the finished product, such as heat stabilizers, thermal oxidants, fluidizing agents, etc., because the conversion of plastic materials to finished products usually takes place in the presence of elevated temperatures and associated mechanical forces.

[0004] Instead of adding these substances directly to the polymer to be modified, industrial practice mainly uses indirect techniques (masterbatch technology).

[0005] Masterbatch (also known as pigment concentrate) is a formulation consisting of a base (usually called a carrier) and a large number of one or more additives.

[0006] Masterbatch technology involves: initially (pre-processing) a concentrate containing the desired additives, and then adding the concentrate to a base polymer in an amount calculated to obtain the desired percentage of additives in the finished product. The choice of masterbatch technology is based on factors such as cost and the safety of additive handling. Masterbatches are typically prepared by specialized companies (rather than those that use them later in the conversion to the final plastic product).

[0007] Solid carriers present in pigment formulations are typically polymeric materials, waxes, or mixtures thereof. Since these carriers inevitably mix with the polymer to be modified and ultimately remain bound in the final product, it is essential that they be compatible with and easily miscible with the polymer in the final product.

[0008] Besides depending on the number of carriers (dozens), the high complexity of this field also depends primarily on the combination of these carriers with the required amount of color for each carrier. Each color is prepared by mixing the pigments (i.e., coloring additives) required for the desired hue (for example, to obtain green, white pigment is blended with yellow and blue pigments) with the carrier. This mixture is then extruded and then granulated.

[0009] Therefore, it is clear that masterbatch production is bespoke, and thus, for hues that cannot be obtained using a single pigment, masterbatch production must be carried out every time. This complexity requires very labor-intensive supply and storage management, which translates into slow-moving stock in terms of time—that is, slow material turnover. Consequently, such materials remain in warehouses for extended periods and can thus become unsellable or nearly unsellable batches, a problem that inevitably increases with the number of products that need to be managed.

[0010] Therefore, the main objective of this invention is to provide a “universal” pigment formulation that eliminates the aforementioned complexity and thus provides less expensive management for the production of colored finished products.

[0011] It should be taken into account that the currently used extrusion-based systems do not allow for an average of more than 40% organic pigment concentrate.

[0012] Patent EP0910603B1 describes the production of masterbatches or additive concentrates using a low-energy mixing process. The additive particles are held together by carrier particles whose particulate properties (identity) cause the masterbatch to consist of aggregates of the carrier particles, thus agglomerating the particles.

[0013] US3778288 discloses a method in which pigments and dispersants (e.g., Fischer-Tropsch wax) are combined and granulated using high-intensity mixing. The resulting particles have a size of 10-70 mesh (2000-210 micrometers) and a yield of 90-95% (Column 4, lines 45-46). Compared to larger particles, smaller particles exhibit poor dispersibility (Column 8, lines 67-68).

[0014] Therefore, the object of the present invention is to provide a universal pigment formulation that overcomes the disadvantages currently known.

[0015] More precisely, the main objective of this invention is:

[0016] - The versatility of pigment products in use,

[0017] - Low (minor) complexity of the production process;

[0018] - Decreased inventory;

[0019] - Reduced switching costs;

[0020] - High pigment concentration;

[0021] - Enhancement of coloring and physicochemical properties;

[0022] - The final product complies with current standards used in the food, pharmaceutical, or even toy industries. Summary of the Invention

[0023] The inventors of this invention have discovered that some specific dispersants also possess the characteristics of wetting agents. These compounds allow the inventors to prepare pigment formulations with general applications for coloring plastics.

[0024] In one aspect, the present invention relates to pigment formulations comprising, substantially composed of, or composed of the following substances:

[0025] - At least one dispersing and wetting agent selected from wax-based powdered processing additives having pigment-affinity groups, acid polyester-based additives having pigment-affinity groups, modified polyethers with highly pigment-affinity groups, copolymers of styrene and polyethers, amides of maleic acid, amphiphilic copolymers, modified polyacrylates with highly pigment-affinity groups, polyester-based block copolymers, high molecular weight polyurethane polymers, polyester-polyamine-polyolefin terpolymers, and modified polysiloxanes having epoxy or urethane groups, wherein the at least one dispersing and wetting agent has a melting point in the range of 50-150°C; and

[0026] - At least one pigment additive selected from inorganic pigments, organic pigments, carbon black, and dyes; and

[0027] - Optional additives,

[0028] Wherein, the particle diameter D50 (by quantity) of the at least one pigment additive in the pigment formulation ranges from 0.5 to 3.5 μm, and

[0029] The pigment formulation contains at least 60% by weight of the at least one pigment additive relative to the total weight of the pigment formulation.

[0030] According to the present invention, the only essential components of the pigment formulation are the at least one dispersing and wetting agent and the at least one pigment additive.

[0031] The inventors have discovered a group of compounds that possess wetting properties, namely, the ability to reduce the interfacial strength of agglomerates of primary (first-stage) pigment particles, i.e., the ability to stabilize the primary pigment particles and thus prevent their re-agglomeration. Such wetting and dispersing agents preferably comprise: pigment-affinity groups such as aromatic rings; polyethers; hydrogen-bonding groups, such as nitrogen-containing groups, like primary, secondary, and tertiary amines, and groups comprising amides, imides, and imines; carboxylic acid groups; hydroxyl groups; carbonyl groups; and carboxyl groups. For polymeric or oligomeric wetting and dispersing agents, the pigment-affinity groups may be part of the main chain or incorporated into the side chains.

[0032] Given this dual nature, wetting and dispersing agents specific to a single polymer can be avoided during the tinting process of polymers. The wetting and dispersing agents of the present invention are compatible with all families of plastics to be tinted. In this way, the pigment formulations of the present invention allow for universal tinting systems because they have versatility of use; that is, they can be used with a variety of polymers, for example, at least three different polymers. Exemplary polymers include, but are not limited to, polyethylene-based polymers, polystyrene, SAN, HIPS, ABS, ASA, vinyl chloride polymers, polyacrylates, polyamides, polycarbonates, polyesters, polyurethanes, and thermoplastic elastomers. When uniformly mixed with a polymer such that the pigment filler loading is 0.5-1% by weight, the resulting tinting composition preferably exhibits a tinting strength at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, for example 20-50%, stronger than a mixture having the same composition but prepared by adding each component separately to a mixing apparatus and combining the components (e.g., pigment filler, dispersing and wetting agent, polymer). Preferably, the pigment formulation imparts this improvement in tinting strength to at least three different polymers.

[0033] In one aspect, the present invention relates to a final pigment formulation in which at least one pigment additive has a particle diameter D50 (by quantity) in the range of 0.5-3.5 μm, and comprises at least 60% by weight of the at least one pigment additive relative to the total weight of the pigment formulation. The particle size of the pigment additive in the final pigment formulation indicates the degree of dispersion of the pigment additive in the pigment formulation. Prior to milling, the pigment additive powder is in the form of agglomerated and / or aggregated particles, typically having a particle size greater than 7 micrometers, for example, 7-10 micrometers. For organic pigments, the aggregates comprise multiple pigment crystals (crystallites) grown together on their surface. The pigment crystals and aggregates connect at their edges and corners to form agglomerates. The milling process, with the aid of a dispersing wetting agent, separates the aggregates of organic pigments from each other and also reduces the size of the aggregates; moreover, the dispersing wetting agent prevents the milled individual particles (which may include monocrystalline or primary particles) from re-attaching (agglomerating) or flocculating. In contrast, carbon black is an aggregate of primary particles whose structure resembles a bunch of grapes. The primary particles adhere to each other through covalent interactions, and typically, grinding does not break the individual aggregates into primary particles. 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 dispersing wetting agent prevents the carbon black aggregates from re-agglomerating.

[0034] The pigment formulations of the present invention can be obtained as free-flowing powders or as microgranules, both of which can be measured by sieving (e.g., using a Filtra Vibration digital electromagnetic sieve shaker, model FTL 0200).

[0035] In a preferred embodiment of the microparticles, the particle size of all microparticles in the pigment formulation is in the range of 60-500 μm, more preferably 80-350 μm (measured, for example, using a Filtra Vibration model FTL 0200 digital electromagnetic sieve). Preferably, the microparticles are ready-to-use microparticles that contain all additives and all active ingredients (desired for use in the masterbatch composition) for use as a ready-to-use pigment formulation.

[0036] When the term "pigment additive" is used in this invention, it means any pigment additive selected from inorganic pigments, organic pigments, carbon black, and dyes.

[0037] Unless otherwise stated, when referring to the particle diameters D10, D50, and D90 of pigment additives in this invention, they refer to the particle diameter (in terms of quantity) of at least one pigment additive in the final pigment formulation, determined by dispersing the final pigment formulation in a solvent and analyzing the dispersion using a laser particle size analyzer (e.g., a laser Beckman Coulter particle size analyzer, optical model Fraunhofer .rf780z). The particle size of the pigment additives in the final pigment formulation can be obtained by dispersing the pigment formulation in a suitable solvent carrier (e.g., butyl acetate). The dispersant-wetting agent is completely dissolved under the test conditions, and therefore, the apparatus measures only the size of the milled pigment dispersed in the solvent. D10 is greater than or equal to the diameter of 10% of the particles in a given group; D50 is greater than or equal to the diameter of 50% of the particles in said group; and D90 is greater than or equal to the diameter of 90% of the particles in said group.

[0038] When the particle size of particulate matter or powder is mentioned in this invention, it means the particle diameter measured using a suitable filter.

[0039] When the term "free-flowing powder" is used in this invention, it means that the final pigment formulation has particles with a particle size of less than 50 μm.

[0040] The pigment formulations of the present invention are preferably in the form of free-flowing powders or particulates. Alternatively or additionally, the pigment formulations are in the form of: a) free-flowing powders having a D20 of at least 0.8 micrometers and a D90 of up to 5 micrometers when measured in a dry state by a laser particle size analyzer (e.g., a Malvern Mastersizer 2000 particle size analyzer equipped with a Scirocco 2000 dry powder sample introduction accessory) at a pressure of 3.5 bar; or b) particulates having a D20 of at least 10 micrometers and a D90 of up to 1000 micrometers when measured in a dry state by a laser particle size analyzer at a pressure of 3.5 bar.

[0041] The components of all embodiments of pigment formulations as particulate matter preferably have a particle size in the range of 60-500 μm, more preferably 80-350 μm.

[0042] In all embodiments of the invention, at least one pigment additive in the final pigment formulation preferably also has a particle diameter D90 (in terms of quantity) in the range of 0.9-4 μm.

[0043] In all embodiments of the invention, at least one pigment additive in the final pigment formulation preferably also has a particle diameter D10 (in terms of quantity) in the range of 0.5-1 μm.

[0044] In another aspect, the present invention relates to a method for preparing the pigment formulation of the present invention, wherein the components are processed using an apparatus capable of imparting at least one pigment additive with a particle diameter D50 (in terms of quantity) in the range of 0.5-3.5 μm.

[0045] In a preferred aspect, the present invention relates to pigment formulations according to the invention, wherein the pigment formulations can be obtained from a pigment composition via a method comprising the following steps:

[0046] 1) Introducing a pigment composition into a grinding apparatus (preferably a dry grinding apparatus), said pigment composition comprising, substantially comprising, or comprising the following substances:

[0047] - At least one dispersing and wetting agent selected from wax-based powdered processing additives having pigment-affinity groups, acid polyester-based additives having pigment-affinity groups, modified polyethers with highly pigment-affinity groups, copolymers of styrene and polyethers, amides of maleic acid, amphiphilic copolymers, modified polyacrylates with highly pigment-affinity groups, polyester-based block copolymers, high molecular weight polyurethane polymers, polyester-polyamine-polyolefin terpolymers, and modified polysiloxanes having epoxy or urethane groups, wherein the at least one dispersing and wetting agent has a melting point in the range of 50-150°C; and

[0048] - At least one pigment additive selected from inorganic pigments, organic pigments, carbon black, and dyes; and

[0049] -Optional additives,

[0050] 2) The pigment composition from step 1) is mixed and ground;

[0051] 3) The pigment formulation thus obtained is unloaded as a free-flowing powder or particulate material.

[0052] Preferably, in step 1), additional additives may be added, such as antistatic agents, fillers, etc., which have been discussed elsewhere in this document.

[0053] The dispersing and wetting agent preferably has a number average molecular weight of 5000-35000 g / mol. Since the pigment additive is preferably added to the mill as a solid, the resulting pigment formulation preferably has a low content of water or other solvents, for example, less than 3% by weight, less than 2.5%, or less than 2%. For example, the pigment formulation may have less than 3% by weight, less than 2.5%, or less than 2% water.

[0054] Unbound by any theory, and as will become clear from the detailed description and examples, the method of the present invention results in excellent grinding and deaggregation of the primary particles of the pigment, and therefore their excellent homogenization and dispersion. The method of the present invention allows for the attainment of uniform grinding and fineness (comparable to those obtained via conventional extrusion processes) and very fine particle dispersion, thereby overcoming the disadvantages of prior art pigment formulations.

[0055] The method of the present invention allows obtaining a pigment formulation as a free-flowing powder or particulate in step 3), wherein at least one pigment additive in the pigment formulation has a particle diameter D50 (by number) in the range of 0.5-3.5 μm, a particle diameter D90 (by number) in the range of 0.9-4 μm, and a particle diameter D10 (by number) in the range of 0.5-1 μm, which are dispersed in a solvent and then measured by a laser particle size analyzer, for example, using a laser Beckman Coulter particle size analyzer with optical model Fraunhofer .rf780z.

[0056] Advantageously, the particulate material of the present invention is a ready-to-use product.

[0057] Therefore, the particulate pigment formulation of the present invention is versatile and has a high pigment concentration and narrow particle size (60-500 μm).

[0058] In another aspect, the present invention relates to a universal dyeing system suitable for preparing plastic and rubber articles with a variety of hues (color shades), comprising a limited number of basic pigments corresponding to a limited set of pigment formulations. The pigment formulations of the present invention allow for the preparation of hues by simply dry-blending the monochromatic (single-pigment) basic pigment formulations of the present invention (e.g., about 16-22 types) without the need for custom processing of the pigment mixture via an extrusion process.

[0059] Therefore, the present invention also relates to a dyeing system comprising a series of pigment formulations having a desired color (RAL, NCS, BS, etc.) that can be obtained simply by dry mixing two or more pigment formulations according to the present invention.

[0060] Therefore, in another aspect, the present invention relates to the use of pigment formulations according to the invention for coloring all kinds of plastic materials (e.g., polyethylene-based polymers, polystyrene, SAN, HIPS, ABS, ASA, vinyl chloride polymers, polyacrylates, polyamides, polycarbonates, polyesters, polyurethanes, and thermoplastic elastomers). Preferably, when the colored plastic composition includes 0.5-1% by weight of pigment additive, it exhibits a coloring power at least 20%, for example, 20-50%, stronger than a mixture having the same composition but prepared by individually adding each component to a mixing apparatus and combining the components into a homogeneous mixture.

[0061] Preferably, the given pigment formulation is suitable for coloring at least three plastic materials, such as at least three selected from polyethylene-based polymers, polystyrene, SAN, HIPS, ABS, ASA, vinyl chloride polymers, polyacrylates, polyamides, polycarbonates, polyesters, polyurethanes, and thermoplastic elastomers. Preferably, the pigment formulation is uniformly mixed with the first, second, and third polymers respectively in a first, second, and third manner such that the resulting mixture containing 0.5-1% by weight of the pigment exhibits a tinting strength at least 20% (e.g., 20-50%) stronger than a mixture with the same composition prepared by individually adding each component to a mixing apparatus and combining the components into a homogeneous mixture.

[0062] Plastic materials are selected from, for example, the following: polyethylene products (e.g., HDPE (high-density polyethylene), LDPE (low-density polyethylene), LLDPE (linear low-density polyethylene), MDPE (medium-density polyethylene), EVA (ethylene-vinyl acetate), EVOH (ethylene-vinyl alcohol)); polypropylene products (e.g., PP (polypropylene), PP copolymers, EPR (ethylene propylene diene monomer rubber), EPDM (ethylene propylene diene monomer rubber (M grade))); and styrene products (e.g., PS (polystyrene), SAN (styrene-acrylonitrile copolymer), HIPS (high-impact polystyrene), ABS (acrylonitrile-butadiene-styrene), ASA (acrylic-styrene-acrylonitrile copolymer)). Polyvinyl chloride polymers (e.g., PVC (polyvinyl chloride), unplasticized and plasticized); acrylic polymers (e.g., PMMA (poly(methyl methacrylate)), polyacrylates); polyamides (e.g., PA6, PA6,6, PA11, PA12, and copolymers thereof); polycarbonates and their blends (e.g., PC / ABS (polycarbonate / acrylonitrile-butadiene-styrene), PC / polyester); polyesters (e.g., PET (polyethylene terephthalate), PBT (polybutylene terephthalate), copolyesters); polyurethanes (e.g., TPU (thermoplastic polyurethane)); thermoplastic elastomers (e.g., TPO (thermoplastic olefin), TPV (thermoplastic vulcanizate)). The polyethylene and polypropylene articles may be obtained using metallocene catalysts or other polymerization methods known to those skilled in the art.

[0063] Furthermore, and surprisingly, the pigment formulations of the present invention allow for the improvement of the technical and mechanical properties of the final colored plastic articles, as will become clear from the experimental section of the present invention.

[0064] Specifically, MFR data demonstrate the processability and good dispersion of the colored samples (without significant difference compared to uncolored samples). Izod testing (impact strength) shows significantly higher results (+77%) for the colored samples compared to the uncolored samples (using the pigment formulation of this invention), as confirmed by examination of the fractured area, which exhibits uniform bleaching and a well-developed deformation process. Rockwell hardness testing highlights significantly higher values ​​(+37%) for samples colored with the pigment formulation of this invention before xenon lamp aging, and values ​​showing opposite behavior between the colored and uncolored samples after 1000 hours of xenon lamp aging. While the colored samples almost retained their original values, showing only moderate changes, the uncolored samples suffered a strong reduction. This phenomenon confirms the increased brittleness of the uncolored samples (as confirmed by the impact test results). For the colored samples, the colorfastness test results measured after 1000 hours of xenon lamp exposure are impressive. No fading was observed in colorimetric analysis or in grayscale analysis. In short, the colored sample behaved significantly better than the uncolored sample.

[0065] Specifically, the present invention includes:

[0066] 1. Pigment formulations, comprising:

[0067] At least one dispersing and wetting agent selected from wax-based powdered processing additives having pigment-affinity groups, acid polyester-based additives having pigment-affinity groups, polyethers modified with highly pigment-affinity groups, copolymers of styrene and polyethers, maleic acid amides, amphiphilic copolymers, modified polyacrylates with highly pigment-affinity groups, polyester-based block copolymers, high molecular weight polyurethane polymers, polyester-polyamine-polyolefin terpolymers, and modified polysiloxanes having epoxy or urethane groups, wherein the at least one dispersing and wetting agent has a melting point in the range of 50-150°C; and

[0068] At least one pigment additive selected from inorganic pigments, organic pigments, carbon black, and dyes.

[0069] The particle diameter D50 (by quantity) of the at least one pigment additive in the pigment formulation ranges from 0.5 to 3.5 μm, and

[0070] The pigment formulation comprises at least 60% by weight of the at least one pigment additive relative to the total weight of the pigment formulation.

[0071] 2. The pigment formulation of item 1, wherein the pigment formulation comprises less than 3% water.

[0072] 3. The pigment formulation of any one of items 1 and 2, wherein the dispersing and wetting agent has a number average molecular weight of 5,000-35,000.

[0073] 4. A pigment formulation of any one of items 1-3, wherein said pigment formulation has the following form:

[0074] a) Free-flowing powder having particles having a D20 of at least 0.8 micrometers and a D90 of up to 5 micrometers when measured by a laser particle size analyzer in a dry state at a pressure of 3.5 bar; or

[0075] b) Particles having a D20 of at least 10 micrometers and a D90 of up to 1000 micrometers when measured in a laser particle size analyzer in a dry state under a pressure of 3.5 bar.

[0076] 5. The pigment formulation of item 4, wherein the particulate matter has a particle size in the range of 60-500 μm, preferably 80-350 μm.

[0077] 6. A pigment formulation of any one of items 1-5, wherein the average particle diameter D90 (in terms of quantity) of the at least one pigment additive in the pigment formulation ranges from 0.9 to 4 μm.

[0078] 7. A pigment formulation of any one of items 1-6, wherein the average particle diameter D10 of the at least one pigment additive in the pigment formulation is in the range of 0.5-1 μm.

[0079] 8. A pigment formulation of any one of items 1-7, wherein the pigment formulation comprises at least 70% by weight of the at least one pigment additive relative to the total weight of the pigment formulation.

[0080] 9. A pigment formulation of any one of items 1-8, wherein the pigment formulation comprises at least 85% by weight of the at least one pigment additive relative to the total weight of the pigment formulation.

[0081] 10. A pigment formulation of any one of items 1-9, further comprising at least one additive selected from heat stabilizers, antioxidants, light stabilizers, antistatic agents, thermally conductive additives, anti-blocking additives, anti-collapse additives, UV stabilizers, fillers, anti-fibrillating agents, processing aids, swelling agents, drying additives, compatibilizers, lubricants, nucleating additives, clarifying additives, flame retardants, optical brighteners, tracer additives, and slip additives.

[0082] 11. The pigment formulation of item 10, wherein the filler comprises at least one selected from: calcium carbonate, kaolin, barium sulfate, talc, wollastonite, silica, pyrolytic silica, mica, and any mixture thereof.

[0083] 12. A pigment formulation of any one of items 1-11, wherein the pigment formulation is miscible with at least three polymers selected from: polyethylene-based polymers, polystyrene, SAN, HIPS, ABS, ASA, vinyl chloride polymers, polyacrylates, polyamides, polycarbonates, polyesters, polyurethanes, and thermoplastic elastomers.

[0084] 13. A pigment formulation of any one of items 1-12, wherein the pigment formulation is manufactured by a method comprising:

[0085] The dispersing wetting agent and the pigment additive are introduced into a grinding apparatus having at least two rotors;

[0086] Mixing and grinding the dispersing wetting agent and the pigment additive to disperse the pigment additive with the dispersing wetting agent; and

[0087] Pigment formulations obtained as free-flowing powders or as particulates.

[0088] 14. The pigment formulation of Item 13, wherein the average circumferential velocity (VPE) of the at least two rotors during mixing and grinding is in the range of 5-50 m / s.

[0089] 15. Pigment formulations of Item 13 or 14, wherein the duration of the entire process is 10 to 90 minutes and the temperature is 50 to 150°C.

[0090] 16. A pigment formulation of any one of items 13-15, wherein the grinding apparatus comprises at least two rotors, wherein at least one rotor is a blade rotor.

[0091] 17. The pigment formulation of any one of items 13-16, wherein the grinding apparatus is a dry grinding apparatus.

[0092] 18. A pigment formulation of any one of items 1-17, wherein the pigment formulation comprising 0.5-1% by weight of the pigment additive exhibits at least 20% stronger tinting strength than a mixture of polymers selected from polyethylene-based polymers, polystyrene, SAN, HIPS, ABS, ASA, vinyl chloride polymers, polyacrylates, polyamides, polycarbonates, polyesters, polyurethanes, and thermoplastic elastomers prepared by individually adding each component to a mixing apparatus and combining the components.

[0093] 19. A dyeing system comprising a variety of pigment formulations for desired hues, which can be obtained by dry mixing two or more pigment formulations according to any one of items 1-18.

[0094] 20. The use of a pigment formulation according to any one of items 1-18 for coloring plastic materials.

[0095] 21. A coloring composition comprising a plastic material and a pigment formulation of any one of items 1-18.

[0096] 22. The colored composition of item 21, wherein the plastic material is selected from polyethylene articles, polypropylene articles and copolymers, polystyrene and polystyrene copolymers, vinyl chloride polymers, acrylics, polyacrylates, polyamide homopolymers and copolymers, polycarbonates and polycarbonate blends, polyester homopolymers and copolymers, polyurethanes, and thermoplastic elastomers.

[0097] 23. The colored composition of item 21 or 22, wherein the plastic material is selected from: HDPE, LDPE, LLDPE, MDPE, EVA, EVOH, polyethylene articles obtained from metallocene catalyst systems, PP, polypropylene articles obtained from metallocene, 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.

[0098] 24. A coloring composition of any one of items 21-23, wherein the coloring composition comprises 0.5-1% by weight of a pigment additive and exhibits at least 20% stronger coloring power than a mixture having the same composition but prepared by individually adding the components to a mixing apparatus and combining the components into a homogeneous mixture.

[0099] 25. Pigment formulations, comprising:

[0100] At least one dispersing and wetting agent selected from wax-based powdered processing additives having pigment-affinity groups, acid polyester-based additives having pigment-affinity groups, polyethers modified with highly pigment-affinity groups, copolymers of styrene and polyethers, maleic acid amides, amphiphilic copolymers, modified polyacrylates with highly pigment-affinity groups, polyester-based block copolymers, high molecular weight polyurethane polymers, polyester-polyamine-polyolefin terpolymers, and modified polysiloxanes having epoxy or urethane groups, wherein the at least one dispersing and wetting agent has a melting point in the range of 50-150°C; and

[0101] At least one pigment additive selected from inorganic pigments, organic pigments, carbon black, and dyes.

[0102] The pigment formulation comprises at least 60% by weight of the at least one pigment additive relative to the total weight of the pigment formulation, and

[0103] The first, second, and third homogeneous mixtures of the pigment formulation and the first, second, and third polymers each contain 0.5-1% by weight of the at least one pigment additive. The resulting first, second, and third mixtures exhibit at least 20% stronger tinting strength than mixtures with the same composition prepared by individually adding each component to a mixing device and combining the components into a homogeneous mixture. The first, second, and third polymers are selected from three different polymers: polyethylene-based polymers, polystyrene, SAN, HIPS, ABS, ASA, vinyl chloride polymers, polyacrylates, polyamides, polycarbonates, polyesters, polyurethanes, and thermoplastic elastomers.

[0104] 26. A method for manufacturing pigment formulations, comprising:

[0105] At least one dispersing and wetting agent and at least one pigment additive are introduced into a grinding apparatus. The at least one dispersing and wetting agent is selected from wax-based powdered processing additives having pigment-affinity groups, acid polyester-based additives having pigment-affinity groups, modified polyethers with high pigment-affinity groups, copolymers of styrene and polyethers, maleic acid amides, amphiphilic copolymers, modified polyacrylates with high pigment-affinity groups, polyester-based block copolymers, high molecular weight polyurethanes, polyester-polyamine-polyolefin terpolymers, and modified polysiloxanes with epoxy or urethane groups. The dispersing and wetting agent has a melting point in the range of 50-150°C. The at least one pigment additive is selected from inorganic pigments, organic pigments, carbon black, and dyes. The grinding apparatus comprises at least two rotors.

[0106] The dispersing and wetting agent is mixed with and ground with the at least one pigment additive to form a pigment formulation, wherein the average circumferential speed of the grinding device is 5-50 m / s; and

[0107] The pigment formulation is collected, the pigment formulation comprising at least 60% by weight of the at least one pigment additive.

[0108] 27. The method of Item 26, wherein the mixing and grinding are performed for 10-90 minutes.

[0109] 28. The method of Item 26 or 27, wherein the maximum temperature reached during mixing and grinding of the mixture of dispersing wetting agent and pigment additive is 50-150°C.

[0110] 29. The method of any one of items 26-28, wherein the particle diameter D90 (in terms of quantity) of the at least one pigment additive in the collected pigment formulation is in the range of 0.9-4 µm.

[0111] 30. The method of any one of items 26-29, wherein the particle diameter D10 (in terms of quantity) of the at least one pigment additive in the collected pigment formulation is in the range of 0.5-1 µm.

[0112] 31. The method of any one of items 26-30, wherein the particle diameter D50 (in quantity) of the at least one pigment additive in the collected pigment formulation is in the range of 0.5-3.5 μm.

[0113] 32. The method of any one of items 26-31, wherein the grinding apparatus is a dry grinding apparatus.

[0114] 33. The method of any one of items 26-32, wherein at least one of the rotors is a blade rotor.

[0115] 34. The method of any one of items 26-33, wherein the dispersing wetting agent has a number average molecular weight of 5,000-35,000.

[0116] 35. The method of any one of items 26-34, wherein the pigment formulation received has the following form:

[0117] a) Free-flowing powder having a d20 of at least 0.8 micrometers and a d90 of up to 5 micrometers when measured by a laser particle size analyzer in a dry state under a pressure of 3.5 bar; or

[0118] b) Particles having a d20 of at least 10 micrometers and a d90 of up to 1000 micrometers when measured by a laser particle size analyzer in a dry state under a pressure of 3.5 bar.

[0119] 36. The method of any one of items 26-35, wherein the pigment formulation received is in the form of microparticles having a particle size in the range of 60-500 μm, preferably 80-350 μm.

[0120] 37. The method of any one of items 26-36, wherein the pigment formulation received is in the form of a free-flowing powder having a particle size of less than 50 μm.

[0121] 38. The method of any one of items 26-37, wherein the introduction further includes introducing at least one additive selected from: heat stabilizers, antioxidants, light stabilizers, antistatic agents, thermally conductive additives, anti-blocking additives, anti-collapse additives, UV stabilizers, fillers, anti-fibrillating agents, processing aids, swelling agents, drying additives, compatibilizers, lubricants, nucleating additives, clarifying additives, flame retardants, optical brighteners, tracer additives, and slip additives. Attached Figure Description

[0122] Figure 1 This is a graph showing the size values ​​of the pigment additives in the final pigment formulation of Example 1; and

[0123] Figure 2 This is a graph showing the size values ​​of the pigment additives in the final pigment formulation of Example 6. Detailed Implementation

[0124] Therefore, in one aspect, the present invention relates to pigment formulations comprising, substantially composed of, or composed of the following substances:

[0125] - At least one dispersing and wetting agent selected from wax-based powdered processing additives having pigment-affinity groups, acid polyester-based additives having pigment-affinity groups, modified polyethers with highly pigment-affinity groups, copolymers of styrene and polyethers, maleic acid amides, amphiphilic copolymers, modified polyacrylates with highly pigment-affinity groups, polyester-based block copolymers, high molecular weight polyurethane polymers, polyester-polyamine-polyolefin terpolymers, and modified polysiloxanes having epoxy or urethane groups, wherein the at least one dispersing and wetting agent has a melting point in the range of 50-150°C; and

[0126] - At least one pigment additive selected from inorganic pigments, organic pigments, carbon black, and dyes, and

[0127] -Optional additives,

[0128] Wherein, the particle diameter D50 (by quantity) of at least one pigment additive in the pigment formulation ranges from 0.5 to 3.5 μm, and

[0129] The pigment formulation contains at least 60% by weight of the at least one pigment additive relative to the total weight of the pigment formulation.

[0130] As described above, when the term "pigment additive" is used in this invention, it means a pigment additive selected from inorganic pigments, organic pigments, carbon black, and dyes. The term "high molecular weight" preferably refers to a number-average molecular weight of 5000-35000 g / mol. An amphiphilic copolymer is a copolymer comprising both hydrophilic and hydrophobic polymers (mers) arranged randomly in a block form, or arranged in some other arrangement (e.g., a gradient).

[0131] For example, pigment additives may be one or more of the following compounds:

[0132]

[0133] The pigment formulations of the present invention are in the form of free-flowing powders or in the form of particulate matter.

[0134] Relative to the total weight of the pigment formulation of the present invention, the pigment formulation contains at least 60% by weight, more preferably 70% by weight, and even more preferably 85% by weight (e.g., up to 95% by weight) of at least one pigment additive.

[0135] Pigment formulations in particulate form have a component particle size in the range of 60-500 μm, more preferably 80-350 μm, as measured using, for example, a digital electromagnetic sieve shaker (model FTL 0200) from Filtra Vibration.

[0136] At least one pigment additive in the final pigment formulation of the present invention also has a particle diameter D90 (by quantity) in the range of 0.9-4 μm.

[0137] At least one pigment additive in the final pigment formulation of the present invention also has a particle diameter D10 (in terms of quantity) in the range of 0.5-1 μm.

[0138] The pigment composition used to obtain the pigment formulation of the present invention further comprises other optional additives selected from: heat stabilizers, oxygen stabilizers (antioxidants), and light stabilizers; charge transporters (antistatics) and heat transporters; thermal additives; anti-blocking additives; anti-collapse additives; antioxidant additives; antistatic additives; UV stabilizer additives; fillers; anti-fibrillating agents; processing aids; swelling agents; drying / compensating additives; lubricants; nucleating / clarifying additives; flame retardants; optical brighteners / tracers; and slip additives. Among the heat stabilizers, organophosphites and phenolic antioxidants may be mentioned.

[0139] Among heat transfer agents, thermally conductive plastics, graphite, aluminum nitride, and boron nitride can be mentioned.

[0140] Among the anti-blocking additives, silica, talc, calcium carbonate, alumina-silicate ceramics, mica, diamides, primary and secondary amides, organic and metal stearates, silicone resins, and polytetrafluoroethylene may be mentioned.

[0141] Among antistatic additives, conductive fillers, glyceryl monostearate, ethoxylated fatty acid amines, diethanolamine, and polyether block amides may be mentioned.

[0142] Among UV stabilizers, oxaloyl aniline, benzophenone, benzotriazole and hydroxyphenyltriazine may be mentioned.

[0143] Among the fillers, calcium carbonate, kaolin, barium sulfate, talc, wollastonite, silicon dioxide and its derivatives (e.g., pyrolytic silicon dioxide), and mica may be mentioned.

[0144] Among the antigen-reducing agents, calcium carbonate, talc, and natural and synthetic rubbers may be mentioned.

[0145] Among processing aids, fluoropolymers, precipitated calcium carbonate, and metal stearates may be mentioned.

[0146] Among the expanding agents, aliphatic hydrocarbons, unstable nitrogen compounds, and mixtures of sodium carbonate or sodium bicarbonate with citric acid may be mentioned.

[0147] Among compatibilizing additives, stearic acid, benzoic acid, styrene-maleic anhydride, and styrene-acrylonitrile copolymers may be mentioned.

[0148] Molybdenum sulfide and graphite are mentioned in lubricants.

[0149] Among the nucleating / clarifying additives, the following may be mentioned: isophthalic acid and terephthalic acid; blends of organic diacids with group II oxides, hydroxides or acids; talc; sodium benzoate; and ionomers.

[0150] Halogenated organic compounds can be mentioned in flame retardants.

[0151] Among optical brighteners, bisbenzo[a] can be mentioned. Azole derivatives, such as benzotriazole phenylcoumarin, naphthotriazole phenylcoumarin, and triazine phenylcoumarin.

[0152] Among the lubricating additives, unsaturated fatty acid amides, secondary amides, and waxes can be mentioned.

[0153] Among antioxidants, hindered phenols, phosphites, phosphonites, and secondary aromatic amines can be listed.

[0154] Among light stabilizers, examples include hindered amines (HALS (hindered amine light stabilizer) or HAS (hindered amine stabilizer)), benzophenone, and benzotriazole.

[0155] In another aspect, the present invention relates to a method for preparing the pigment formulation of the present invention, wherein the components are processed using an apparatus capable of imparting at least one pigment additive with a particle diameter D50 (in terms of quantity) in the range of 0.5-3.5 μm, and reaching an amount of at least one pigment additive of 60% by weight relative to the total weight of the pigment formulation. The amount of the at least one pigment additive is at least 60%, preferably 70%, and more preferably 85% relative to the total weight of the pigment formulation.

[0156] According to the present invention, the pigment formulation can preferably be obtained from a pigment composition.

[0157] More preferably, the pigment formulation can be obtained by a method including the following steps:

[0158] 1) Introducing the pigment composition according to the invention into a dry grinding apparatus, said pigment composition comprising, substantially comprising, or comprising:

[0159] - At least one dispersing and wetting agent selected from wax-based powdered processing additives having pigment-affinity groups, acid polyester-based additives having pigment-affinity groups, modified polyethers with highly pigment-affinity groups, copolymers of styrene and polyethers, maleic acid amides, amphiphilic copolymers, modified polyacrylates with highly pigment-affinity groups, polyester-based block copolymers, high molecular weight polyurethane polymers, polyester-polyamine-polyolefin terpolymers, and modified polysiloxanes having epoxy or urethane groups, wherein the at least one dispersing and wetting agent has a melting point in the range of 50-150°C, and

[0160] - At least one pigment additive selected from inorganic pigments, organic pigments, carbon black, and dyes.

[0161] 2) Mix and dry grind the components from step 1), and

[0162] 3) The pigment formulation thus obtained is unloaded as a free-flowing powder or particulate material.

[0163] In this invention, a dry grinding apparatus is preferred over jet grinding apparatuses and wet grinding apparatuses. Dry grinding apparatuses allow for appropriate grinding forces, while known jet grinding apparatuses are excessively energetic, thus impairing the post-processing of dispersed pigment particles and consequently the stability of the final color. On the other hand, wet grinding apparatuses typically cannot disperse pigment particles to a particle size of <15 micrometers, and require a further drying step, making the entire process more expensive.

[0164] In the above methods, all known organic pigments, inorganic pigments, carbon black and dyes are suitable for use in the preparation of pigment formulations.

[0165] Examples of pigment additives are listed above.

[0166] The preferred dry grinding apparatus used in the method of the present invention may have at least two rotors and may be discontinuous or continuous.

[0167] In a preferred embodiment, the pigment formulation can be obtained by a method comprising the following steps:

[0168] 1) Introduce the aforementioned pigment composition into a grinding apparatus equipped with at least two rotors (preferably, at least one rotor is a blade rotor).

[0169] 2) Mix and grind the pigment composition;

[0170] 3) Unload the pigment formulation thus obtained.

[0171] Both the continuous and non-continuous apparatuses used in the preceding methods allow for obtaining a pigment formulation as a free-flowing powder or particulate material in step 3), and the pigment formulation has at least one pigment additive with a particle diameter D50 (in terms of quantity) in the range of 0.5-3.5 μm.

[0172] The discontinuous dry grinding device comprises 2-7 rotors, for example, 3, 4, 5 or 6 rotors, preferably 4.

[0173] When using a discontinuous mixing device, the average circumferential speed VPE is contained in the range of 5-50 m / s, and the mixing and dry grinding step 2) is preferably carried out for 10-90 minutes, for example, 15-90 minutes or 20-90 minutes, until a temperature of 50-150°C is reached.

[0174] Unbound by any theory, the inventors of this invention believe that the final diameter of at least one pigment additive particle and the fineness of the pigment formulation grinding are necessary for the final performance (dispersibility and tinting strength) of the product.

[0175] All devices that allow for a large number of repeated collisions between the particles and components of the device (e.g., rotors), and thereby allow for the impact (shock) of the constituent particles of the present invention, are suitable for use in the present invention.

[0176] The fineness of pigment additives in pigment formulations is related to the number of impacts experienced by pigment particles during collisions with each other, with the rotor, and with the inner sheath of the grinding chamber. Unbound by any theory, it is believed that, over a prolonged period (e.g., 10–90 minutes), the grinding action of a dry mill will disperse the wetting agent evenly between the pigment additive particles without the use of water or other solvents.

[0177] Based on the characteristics of the components (preferably at least one additive selected from inorganic pigments, organic pigments, carbon black and dyes) (i.e., density, oil absorption capacity, specific surface area, etc.), preferred conditions (aspects) for VPE, time and final temperature can be established.

[0178] The article thus obtained in step 3) is unloaded and, advantageously, packaged.

[0179] Preferably, the dust-free particulate matter has a particle diameter in the range of 80-350µm.

[0180] If some grinding devices are non-continuous, then granulation equipment may also be provided when the product of step c) is a free-flowing powder. Alternatively, the non-continuous device allows for the production of dust-free particulate matter with a particle size in the range of 60-500 μm, more preferably 80-350 μm, as measured (e.g., using a digital electromagnetic sieve of Filtra Vibration model FTL 0200).

[0181] Preferably, the granulation step is performed via a rotary screw feeder, which forces the product, already at a preferred temperature range of 60°C-140°C, to rotate in a regular vortex motion (pivot), resulting in the formation of very uniform spherical granules. The circumferential velocity (VPE) of the screw feeder is preferably between 15-50 m / s. After approximately five minutes, uniform microparticles are formed. Preferably, the temperature is kept below 50°C, thereby causing complete re-solidification of the carrier and stabilizing the spherical granules.

[0182] The obtained product (i.e., dust-free microparticles) is in the form of uniform microparticles with a narrow particle size profile, wherein the particle size is in the range of 60-500 μm, more preferably 80-350 μm, as measured (e.g., using a digital electromagnetic sieve of FiltraVibration model FTL 0200).

[0183] The performance of the pigment formulations of the present invention (i.e., excellent deagglomeration and / or disaggregation of pigment particles, uniform dispersion, and dispersibility and tinting strength) is comparable to, and in some cases even superior to, that achievable using conventional extrusion processes, as shown in the experimental section. A surprising feature of these pigment formulations is that, when the percentage of the at least one pigment additive relative to the total weight of the pigment formulation is at least 60% by weight, more preferably 70% by weight, even more preferably 85% by weight, and most preferably up to 95% by weight, the final pigment formulation retains these properties.

[0184] As shown in the experimental section below, the fineness of the milled particles of at least one pigment additive in the final pigment formulation of the present invention is represented by an advantageous limited range.

[0185] The final pigment formulation of the present invention has excellent uniformity, that is, the calculated particle size D90 of the ground pigment particles is at most 4 micrometers, with very few particles having a size greater than 5 micrometers.

[0186] As described above, the general-purpose pigment formulation comprises at least 60% by weight, more preferably 70% by weight, of at least one pigment additive relative to the total weight of the pigment formulation, preferably 85% of organic pigment, and preferably up to 95% of inorganic pigment.

[0187] On the other hand, since the pigment formulations of the present invention are versatile and have high pigment concentrations, the present invention relates to a general-purpose dyeing system suitable for preparing plastic and rubber articles with a variety of hues, having a limited number of basic colors corresponding to a limited set of pigment formulations. The pigment formulations of the present invention allow for the preparation of hues by simply dry-mixing the monochromatic basic pigment formulations of the present invention (e.g., about 16-22 types) without the need for custom processing of the pigment mixture via an extrusion process.

[0188] Therefore, the present invention also relates to a dyeing system comprising a series of pigment formulations having desired color (RAL, NCS, BS, etc.) chromaticity, which can be obtained by dry mixing two or more pigment formulations according to the present invention.

[0189] The dyeing system can be used with any plastic material. Preferably, any given dyeing system can be used with at least three plastic materials.

[0190] Therefore, in another aspect, the present invention relates to the use of pigment formulations according to the invention for coloring all kinds of plastic materials.

[0191] Plastic materials are selected from, for example, the following: polyethylene products (e.g., HDPE, LDPE, LLDPE, MDPE, EVA, EVOH, even those derived from metallocene catalyst systems); polypropylene products (e.g., PP (even those derived from metallocene), PP copolymers, EPR, EPDM); styrene products (e.g., PS, SAN, HIPS, ABS, ASA); vinyl chloride polymers (e.g., PVC, unplasticized and plasticized); acrylics (e.g., PMMA, polyacrylates); polyamides (e.g., PA6, PA6,6, PA11, PA12, and their copolymers); polycarbonates and their blends (e.g., PC / ABS, PC / polyester); polyesters (e.g., PET, PBT, copolyesters); polyurethanes (e.g., TPU); thermoplastic elastomers (e.g., TPO, TPV).

[0192] The present invention will now be described through some embodiments, which are exemplary and do not limit the invention.

[0193] Experimental Section

[0194] The formulation of the present invention

[0195] All pigments used are referred to below by the names of the color indexes, which are commonly used for pigment identification.

[0196] Example 1

[0197] Preparation of pigment formulation XP303-C (pigment concentration = 85%)

[0198] Mix and grind 6800g of Pigment Red 254 (available as SR2P from Cinic) with 1200g of Disperplast 1018 (supplied by BYK).

[0199] The dry grinding device is a non-continuous device equipped with four rotors.

[0200] Process parameters: 1 minute at a circumferential speed of 6 m / s, 14 minutes at a circumferential speed of 15 m / s, and then 6 minutes at a circumferential speed of 25 m / s; temperature reaches 72℃.

[0201] The pigment formulation thus obtained corresponds to the microparticles.

[0202] The particle size values ​​of the pigment additives in the pigment formulation are as follows (analyzed in butyl acetate dispersion using a laser Beckman Coulter particle size analyzer):

[0203] D10 = 0.571 μm

[0204] D50 = 0.790 μm

[0205] D90 = 1.034 μm

[0206] The particle size of the microparticles is in the range of 80-350µm.

[0207] Example 2

[0208] Preparation of pigment formulation XP901 (pigment concentration = 80%)

[0209] 6400 g of carbon black pigment PBL-7 (Orion's Carbon Black Special Black 100) and 1600 g of dispersant Disperplast 1018 (BYK) were mixed and ground using a discontinuous dry grinding apparatus equipped with four rotors. Process parameters: 1 minute at a circumferential speed of 6 m / s, 14 minutes at a circumferential speed of 15 m / s, and then 6 minutes at a circumferential speed of 25 m / s; temperature reached 132°C. The resulting composition was in the form of dust-free particulate matter.

[0210] The D50 of the pigment additive in the pigment formulation (measured as in Example 1) is 1.5 μm.

[0211] The particle size of the microparticles is 80-350 μm.

[0212] Example 3

[0213] Preparation of pigment formulation XP307C (pigment concentration = 90%)

[0214] 5400g of Pigment Red 101 (Lanxess's Bayferrox 130 M) and 600g of Disperplast 1018 (BYK) were mixed and ground using a discontinuous dry grinding device equipped with four rotors.

[0215] Process parameters: 1 minute at a circular speed of 6 m / s, and 14 minutes at a circular speed of 25 m / s. Temperature reaches 50℃.

[0216] The obtained composition is in the form of a free-flowing powder.

[0217] The D50 of the pigment additive in the pigment formulation (measured as in Example 1) is 1.2 μm.

[0218] The particle size of the powder is <50μm.

[0219] Example 4

[0220] Preparation of pigment formulation XP001 PW6 (pigment concentration = 90%)

[0221] 5400g of PW6 101 pigment (Tronox CR-826) and 600g of dispersant Disperplast 1018 (BYK) were mixed and ground using a discontinuous dry grinding device equipped with four rotors.

[0222] Process parameters: 1 minute at a circumferential speed of 6 m / s, 14 minutes at a circumferential speed of 25 m / s, and then 6 minutes at a circumferential speed of 30 m / s.

[0223] The resulting composition is in the form of particulate matter.

[0224] The D50 of the pigment additive in the pigment formulation (measured as in Example 1) is 0.7 μm.

[0225] Particle size: 80-350μm

[0226] Example 5

[0227] Preparation of pigment formulation XP105-C (pigment concentration = 80%)

[0228] 4800g of PY139 pigment (BASF's Paliotol L2140) and 1200g of dispersant Disperplast 1018 (BYK) were mixed and ground using a discontinuous dry grinding device equipped with four rotors.

[0229] Process parameters: 1 minute at a circular speed of 6 m / s, and 14 minutes at a circular speed of 15 m / s. Temperature reaches 52℃.

[0230] The resulting formulation is in the form of a free-flowing powder.

[0231] The D50 of the pigment additive in the pigment formulation (measured as in Example 1) is 1.6 μm.

[0232] The particle size of the powder is <50μm.

[0233] Example 6

[0234] Preparation of pigment formulation XP502-C (pigment concentration = 80%)

[0235] Using a dry grinding discontinuous apparatus equipped with four rotors, 4800g of pigment blue Phtalo PB 15:1 (Clariant's MP PV Blu Solido a 4R) was mixed with 1200g of dispersant Disperplast 1018 (BYK) and ground.

[0236] The process parameters are: 1 minute at a circumferential speed of 6 m / s and 14 minutes at a circumferential speed of 15 m / s.

[0237] The resulting formulation was in the form of a free-flowing powder and analyzed in a butyl acetate dispersion using a Fraunhofer RF780Z laser Beckman Coulter particle size analyzer. The particle size of the pigment additives in the pigment formulation was:

[0238] D10 = 0.746 μm

[0239] D50 = 1.526 μm

[0240] D90=3.269μm

[0241] The particle size of the powder is <50μm, as measured using a Filtra Vibration digital electromagnetic sieve model FTL 0200.

[0242] Example 7

[0243] Preparation of green hue in the dyeing system of the present invention

[0244] To obtain a green hue, the following three articles of the present invention were dried and blended using a mixer (time = 2 minutes): Article XP001 PW6 prepared in Example 4 (dosage = 75% of the white article of Example 4, which has a pigment concentration of 90%) + Article XP502-C PB 15:1 prepared in Example 6 (dosage = 39% of the article of Example 6, which has a pigment concentration of 80%) + Article XP105-C PY139 prepared in Example 5 as a yellow substance (dosage = 1.63% of the article of Example 5, which has a pigment concentration of 80%). A green hue was obtained. The green hue was completely uniform upon visual inspection.

[0245] Example 8

[0246] Preparation of deep blue hue in the mixing system used in this invention

[0247] To obtain a deep blue hue, the following three products of the present invention were dry-blended using a conventional mixer (time = 2 minutes): Product XP901 PBL-7 of Example 2 (30% of the black product of Example 2, having 80% pigment concentration) + Product XP001 PW6 of Example 4 (70% of the white product of Example 4, having 90% pigment concentration) + Product XP502-C PB 15:1 of Example 6 (16.25% of the blue product of Example 6, having 80% pigment concentration). Dry-blending the formulations of the present invention yields a deep blue color. A deep blue hue of quality completely equivalent to that obtainable using known masterbatches processed by conventional extrusion processes was obtained.

[0248] Example 9

[0249] Evaluation of samples colored with the pigment formulation of the present invention

[0250] ABS / SAN sheets are prepared by coloring using the following method.

[0251] Sample 1: Board material colored with XP303-C

[0252] In the ES-65 extruder of CDM ENGINEERING srl, ABS+SAN (50-50%) was introduced together with the formulation of Example 1 (XP303-C), the latter in an amount of 0.70 by weight.

[0253] The extrusion temperature is:

[0254] Barrel 1: 200℃, Barrel 2: 210℃, Barrel 3: 230℃, Cil. Deg. 4: 240℃, Barrel 5: 235℃, Plate: 230℃, Machine Head: 230℃.

[0255] Then, the extruded parts are printed using an IMEX ITALY SM 50T press. The molding temperatures are: Zone 1: 220°C, Zone 2: 230°C, Zone 3: 240°C, Nozzle: 230°C.

[0256] Sample 2: ABS-SAN sheet colored with XP307C

[0257] Sample 2 was prepared in 0.60% by weight of formulation XP307C of Example 3, using the same equipment as Sample 1, following the procedure described.

[0258] Sample 3: Uncolored ABS-SAN sheet

[0259] Sample 3 was prepared using the same procedure as that for Sample 1, with an uncolored ABS-SAN blend.

[0260] The three samples thus prepared were subjected to the following tests (conducted by POLYTECHNIC OF MILAN, DEPARTMENT OF CHEMICAL MATERIALS AND CHEMICAL ENGINEERING "Giulio Natta" Polytechnic Polymer Testing Laboratory): color fastness (before and after xenon lamp testing); melt flow rate (MFR); thermogravimetric analysis; Rockwell hardness; IZOD notched impact strength; migration; and chemical resistance (ESC).

[0261] Aging test (xenon lamp test) – According to ISO 4892-2:2006 (AMF2009), using a Solarbox 3000e device and exposed to xenon gas, irradiance: 550W / m². 2 Lamp: 2500W; intensity measured on sample surface, air-cooled; Filter: UV OUTDOOR filter (280nm) installed between lamp and test chamber; Thermometer: BST (black mark thermometer); Temperature: 65±3℃ (with lamp on); Cycle: continuous radiation.

[0262] The following tests were performed on the samples before and after aging (xenon lamp test):

[0263] Colorfastness: According to the method of UNI EN 20105 / A02:1996, the grayscale of the sample has a color change between 1 and 5 (1 = maximum change; 5 = no change);

[0264] Melt flow rate: according to ASTM D1238:2013 method (load = 5 kg; test temperature = 230 °C)

[0265] Rockwell hardness: determined by UNI EN ISO 2039-2:2001 method

[0266] Izod impact test: according to UNI EN ISO 180:2009 method.

[0267] Color change (UNI EN 20105 / A02:1996): Initial and subsequent xenon lamp tests

[0268] Overall migration in water: color migration, according to the Italian Ministry of Health's DM 74 method of April 6, 2004, by placing freshly prepared samples 1-3 in contact with water at approximately 40°C for 24 hours.

[0269] The results shown in Table 1 were obtained.

[0270] Table 1

[0271]

[0272] The MFR data shown in Table 1 demonstrate the processability and good dispersion of the colored samples, with no relevant difference when compared to uncolored samples. For the uncolored sample (Sample 3) and the two samples colored with the formulation of the present invention (Samples 1 and 2), the results of the xenon lamp test all show minimal changes. In any case, the observed changes (about 1-2 units) are lower than the range of known colored samples that have undergone 1000 hours of aging in the xenon lamp test.

[0273] The Izod test (impact strength) shows much higher results (+77%) for the samples colored with the pigment formulation of the present invention than for the uncolored samples. As confirmed by examining the fractured regions, this indicates uniform whitening and a well-evolved deformation process. Conversely, the fracture surface of uncolored Sample 3 is less uniform and shows regions with irregular depressions.

[0274] With respect to uncolored Sample 3, a large decrease in the initial value was detected after 1000 hours of xenon lamp aging testing.

[0275] Rockwell hardness testing highlights: a) significantly higher values (+37%) for samples colored with the pigment formulation of the present invention before xenon lamp aging testing; b) after 1000 hours of xenon lamp aging testing, the values show opposite behavior between colored and uncolored samples. While the colored samples almost retain their original values, only showing a moderate change, the uncolored samples have suffered a strong decrease. This phenomenon confirms the increased brittleness of the uncolored samples, as corroborated by the results of the impact test.

[0276] For the colored samples, the color fastness test results measured after 1000 hours of exposure in the xenon lamp test are remarkable. No discoloration was observed in colorimetric analysis or with respect to the gray scale. In short, the behavior of the colored samples is significantly superior to that of the uncolored samples.

[0277] In all samples, under the specific test conditions, the total migration was found to be below the detection limit.

[0278] All samples are qualified for contact with food.

[0279] Example 10

[0280] Evaluation of samples colored with the pigment formulation of the present invention

[0281] The pigment formulation (XP303 C) of Example 1 was compared with pure pigment by coloring polypropylene.

[0282] Use the following instruments to perform the test:

[0283] Analytical balance (accuracy: 0.001g), precision balance (accuracy: 0.01g), mixer (model: CY-37, speed: 0-55 rpm, timer: 0.1 seconds-99.99 hours, engine power: 90-180W, inner barrel diameter: 50mm, depth: 60mm), twin-screw extruder (model: CTE 20, speed: 600 rpm, engine power: 4KW, L / D=56, diameter: 21.7mm), injection molding machine (model: HTF58X1, screw model: A-D26, closing force: 580KN, injection volume: 66cm³). 3 ); Spectrophotometer (model: Konica-MinoltaCM-2600d).

[0284] Polypropylene samples were tested at pigment contents of 0.5% or 0.1%.

[0285] The procedure involves manually mixing polypropylene resin and pigment powder or the pigment formulation XP303 C of Example 1 of this invention, along with silicone oil, until a homogeneous mixture is obtained. The mixture thus obtained is then injection molded to form chips.

[0286] The samples (comparative and the present invention) all exhibited good dispersibility.

[0287] No visible spots were detected.

[0288] The method of this invention significantly improves its FPV (filter value), measured using DIN EN13900-5.

[0289] Filtration pressure values ​​used: Pure pigment = 5.250 bar / g; XP303 C = 2.420 bar / g.

[0290] At a dilution ratio of 1:10, the formulation XP303 C according to the present invention has high coloring power.

[0291] At a pigment content of 0.5% or an equivalent formulation content (correspondingly, a 15% reduction in pigment), the formulation XP303 C of this invention exhibits 130% higher tinting strength than pure pigment. Dispersibility clearly demonstrates the superior dispersibility of the formulation XP303 C of this invention, as also confirmed by measurements of filtration pressure values.

[0292] Example 11

[0293] Evaluation of samples HP 714 and HP 729 (pigment concentration = 90%) colored with the pigment formulation of the present invention.

[0294] HP 714: 4,500 g of Pigment Brown 24 (Heucodur Yellow G 9239 from Heubach) and 500 g of Disperplast 1018 (from BYK) are mixed and ground using a discontinuous dry grinding device equipped with three rotors.

[0295] Process parameters: The temperature reaches 110℃ after 1 minute at a circumferential speed of 6 m / s and 29 minutes at a circumferential speed of 30 m / s.

[0296] The obtained composition is in granular form.

[0297] The particle size is <500μm.

[0298] HP 729: 4,500 g of Pigment Brown 24 (Heucodur Yellow G 9239 from Heubach) and 500 g of Dispersant P 4100 (liquid at room temperature) (by BYK) are mixed and ground using a discontinuous dry grinding device equipped with three rotors.

[0299] Process parameters: The temperature reaches 110℃ after 1 minute at a circumferential speed of 6 m / s and 29 minutes at a circumferential speed of 30 m / s.

[0300] The obtained composition is in granular form.

[0301] The particle size of the granules is <500μm.

[0302] Pigment formulations (HP 714 and HP 729) were compared by coloring with ABS and tested according to DIN EN ISO 294-1.

[0303] Use the following instruments to perform the test:

[0304] Precision balance (accuracy: 0.002g), twin-screw extruder (model: Leistritz, ZSE 18HP-35D, speed: 125 rpm, engine power: 9.4kW, L / D=35, diameter: 18mm), injection molding machine (model: Arburg, 300C 500-170, screw model: 30 L 873 SW, injection volume: 13.5cm³). 3 ); Spectrophotometer (Model: Datacolor, Spectraflash SF 300).

[0305] Tinting strength measurement: Relative tinting strength is calculated by the decrease relative to the standard according to DIN EN ISO 787-24.

[0306] Acrylonitrile-butadiene-styrene (ABS) samples were tested at a dilution ratio of 1:10 with a pigment content of 0.1%.

[0307] Formulation HP 714 exhibits significantly superior dispersibility compared to HP 729. This is evidenced by the difference in tinting strength; HP 714 has 37% higher tinting strength than HP 729.

[0308]

[0309] Another indicator of better dispersibility is the quality of the prepared batch. Prior to injection molding, each color formulation is premixed with the carrier material (ABS) using a twin-screw extruder. In contrast to HP 714, the produced HP 729 batch is non-uniform, containing particles with significantly varying tinting strength.

[0310] Given that the only difference between the two formulations is the dispersant used, dispersant P 4100 is not suitable for coloring ABS.

[0311] Example 12

[0312] Comparative Example

[0313] Preparation of pigment formulations (pigment concentration = 80%)

[0314] 1760g of Monarch 1100 carbon black (available from Cabot Corporation) was mixed and ground with 440g of dispersant Atmer 116 (liquid at room temperature) (supplied by CRODA Corporation).

[0315] The dry grinding device is a non-continuous device equipped with three rotors.

[0316] Process parameters: 1 minute at a circumferential speed of 6.1 m / s and then 39 minutes at a circumferential speed of 31 m / s; temperature reaches 66℃.

[0317] The pigment formulation thus obtained is in powder form.

[0318] A 1.644L Banbury mixer from Farrel Corporation was used to obtain a masterbatch containing 30% carbon black by combining pigment formulations with a styrene-acrylonitrile polymer (Kostill B755). The following process conditions were applied: chamber temperature 40°C; rotor temperature 40°C; mixing time after flux 90 seconds; flushing pressure 4.2 bar; and rotor speed 182 RPM. The product was processed at 190°C. o The product is discharged at C. It is then cooled and ground into coarse particles using a Pallman PS3 mill with three rotating blades.

[0319] Then, the masterbatch is diluted (30=>5% carbon black in GP22 acrylonitrile-butadiene-styrene polymer) by extrusion on a single screw (LabTec-30mm, 30L / D, die-to-hopper temperature: 220-220-220-210-200℃) and cut into granules by a granulation system.

[0320] The granules were dried overnight at 70°C.

[0321] During the injection molding process for plaque and impact test bar, ABS GP22 was used again to dilute the resulting product from 5% carbon black to 0.75% carbon black. The molding temperatures were: Zone 1: 200℃, Zone 2: 220℃, Zone 3: 240℃, and nozzle: 230℃.

[0322] Using the same method described above for pigment formulations, a comparative masterbatch for styrene-acrylonitrile polymers was prepared using Black Pearls 1100 carbon black (Cabot Corporation), which is a carbon black with the same surface area as Monarch 1100 carbon black but prepared in granular form. The masterbatch (30% carbon black by weight) was diluted and shaped into plates and impact test bars as described previously.

[0323] The color Cie L of the board was analyzed using UltraScan Vis from Hunterlab. a b .

[0324] IZOD impact resistance of notched specimens was measured using a CEAST Pendulum impact testing machine in accordance with ISO 180 / A:2000.

[0325] result:

[0326]

[0327] The data above show that, compared with plastics prepared using pigment formulations, plastics prepared using pure pigments are disadvantageous in terms of both color performance and impact strength when using Atmer 116 dispersant (which is liquid at room temperature) to form pigment formulations.

Claims

1. Dry-milled pigment formulations, comprising: At least one dispersing and wetting agent selected from wax-based powdered processing additives having pigment-affinity groups, acid polyester-based additives having pigment-affinity groups, polyethers modified with highly pigment-affinity groups, copolymers of styrene and polyethers, maleic acid amides, amphiphilic copolymers, modified polyacrylates with highly pigment-affinity groups, polyester-based block copolymers, high molecular weight polyurethane polymers, polyester-polyamine-polyolefin terpolymers, and modified polysiloxanes having epoxy or urethane groups, wherein the at least one dispersing and wetting agent has a melting point in the range of 50-150°C; and At least one pigment additive selected from inorganic pigments, organic pigments, carbon black, and dyes. The particle diameter D50 (by quantity) of the at least one pigment additive in the pigment formulation ranges from 0.5 to 3.5 μm, and The pigment formulation comprises at least 60% by weight of the at least one pigment additive relative to the total weight of the pigment formulation, and The pigment formulation described herein has the following forms: a) Free-flowing powder having particles having a D20 of at least 0.8 micrometers and a D90 of up to 5 micrometers when measured by a laser particle size analyzer in a dry state at a pressure of 3.5 bar; or b) Particles having a D20 of at least 10 micrometers and a D90 of up to 1000 micrometers when measured in a laser particle size analyzer in a dry state under a pressure of 3.5 bar.

2. The dry-milled pigment formulation of claim 1, wherein the pigment formulation comprises less than 3% water.

3. The dry-milled pigment formulation of claim 1 or 2, wherein the dispersing and wetting agent has a number average molecular weight of 5,000-35,000.

4. The dry-milled pigment formulation of claim 1, wherein the particulate material has a particle size in the range of 60-500 μm, preferably 80-350 μm.

5. The dry-milled pigment formulation of claim 1, wherein the average particle diameter D90 (in terms of quantity) of the at least one pigment additive in the pigment formulation ranges from 0.9 to 4 μm.

6. The dry-milled pigment formulation of claim 1, wherein, The average particle diameter D10 of the at least one pigment additive in the pigment formulation is in the range of 0.5-1 μm.

7. The dry-milled pigment formulation of claim 1, wherein the pigment formulation comprises at least 70% by weight of the at least one pigment additive relative to the total weight of the pigment formulation.

8. The dry-milled pigment formulation of claim 1, wherein the pigment formulation comprises at least 85% by weight of the at least one pigment additive relative to the total weight of the pigment formulation.

9. The dry-milled pigment formulation of claim 1, further comprising at least one additive selected from heat stabilizers, antioxidants, light stabilizers, antistatic agents, thermally conductive additives, anti-blocking additives, anti-collapse additives, UV stabilizers, fillers, anti-fibrillating agents, processing aids, swelling agents, drying additives, compatibilizers, lubricants, nucleating additives, clarifying additives, flame retardants, optical brighteners, tracer additives, and slip additives.

10. The dry-milled pigment formulation of claim 9, wherein the filler comprises at least one selected from: calcium carbonate, kaolin, barium sulfate, talc, wollastonite, silica, pyrolytic silica, mica, and any mixture thereof.

11. The dry-milled pigment formulation of claim 1, wherein the pigment formulation is miscible with at least three polymers selected from: polyethylene-based polymers, polystyrene, SAN, HIPS, ABS, ASA, vinyl chloride polymers, polyacrylates, polyamides, polycarbonates, polyesters, polyurethanes, and thermoplastic elastomers.

12. The dry-milled pigment formulation of claim 1, wherein the pigment formulation is manufactured by a method comprising: The dispersing wetting agent and the pigment additive are introduced into a grinding apparatus having at least two rotors; Mixing and grinding the dispersing wetting agent and the pigment additive to disperse the pigment additive with the dispersing wetting agent; and Pigment formulations obtained as free-flowing powders or as particulates.

13. The dry-milled pigment formulation of claim 12, wherein the average circumferential speed (VPE) of the at least two rotors during mixing and milling is in the range of 5-50 m / s.

14. The dry-milled pigment formulation of claim 12 or 13, wherein the duration of the entire process is 10 to 90 minutes and the temperature is 50 to 150°C.

15. The dry-milled pigment formulation of claim 12, wherein the milling apparatus comprises at least two rotors, wherein at least one rotor is a blade rotor.

16. The dry-milled pigment formulation of claim 12, wherein the milling apparatus is a dry milling apparatus.

17. The dry-milled pigment formulation of claim 1, wherein the pigment formulation comprising 0.5-1% by weight of the pigment additive exhibits at least 20% stronger tinting strength than a mixture of polymers selected from polyethylene-based polymers, polystyrene, SAN, HIPS, ABS, ASA, vinyl chloride polymers, polyacrylates, polyamides, polycarbonates, polyesters, polyurethanes, and thermoplastic elastomers prepared by individually adding each component to a mixing apparatus and combining the components.

18. A dyeing system comprising a plurality of dry-milled pigment formulations of desired hues, which can be obtained by dry mixing two or more pigment formulations according to claim 1.

19. Use of the dry-milled pigment formulation according to claim 1 for coloring plastic materials.

20. A coloring composition comprising a plastic material and the dry-milled pigment formulation of claim 1.

21. The colored composition of claim 20, wherein the plastic material is selected from polyethylene articles, polypropylene articles and copolymers, polystyrene and polystyrene copolymers, vinyl chloride polymers, acrylics, polyacrylates, polyamide homopolymers and copolymers, polycarbonates and polycarbonate blends, polyester homopolymers and copolymers, polyurethanes, and thermoplastic elastomers.

22. The colored composition of claim 20 or 21, wherein the plastic material is selected from: HDPE, LDPE, LLDPE, MDPE, EVA, EVOH, polyethylene articles obtained from metallocene catalyst systems, PP, polypropylene articles obtained from metallocene, 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.

23. The coloring composition of claim 20, wherein the coloring composition comprises 0.5-1% by weight of pigment additive and exhibits at least 20% stronger coloring power than a mixture having the same composition but prepared by individually adding each component to a mixing apparatus and combining the components into a homogeneous mixture.

24. Dry-milled pigment formulations, comprising: At least one dispersing and wetting agent selected from wax-based powdered processing additives having pigment-affinity groups, acid polyester-based additives having pigment-affinity groups, polyethers modified with highly pigment-affinity groups, copolymers of styrene and polyethers, maleic acid amides, amphiphilic copolymers, modified polyacrylates with highly pigment-affinity groups, polyester-based block copolymers, high molecular weight polyurethane polymers, polyester-polyamine-polyolefin terpolymers, and modified polysiloxanes having epoxy or urethane groups, wherein the at least one dispersing and wetting agent has a melting point in the range of 50-150°C; and At least one pigment additive selected from inorganic pigments, organic pigments, carbon black, and dyes. The pigment formulation comprises at least 60% by weight of the at least one pigment additive relative to the total weight of the pigment formulation. The particle diameter D50 (by quantity) of the at least one pigment additive in the pigment formulation ranges from 0.5 to 3.5 μm. and The first, second, and third homogeneous mixtures of the pigment formulation and the first, second, and third polymers each contain 0.5-1% by weight of the at least one pigment additive. The resulting first, second, and third mixtures exhibit at least 20% stronger tinting strength than mixtures with the same composition prepared by individually adding each component to a mixing device and combining the components into a homogeneous mixture. The first, second, and third polymers are selected from three different polymers: polyethylene-based polymers, polystyrene, SAN, HIPS, ABS, ASA, vinyl chloride polymers, polyacrylates, polyamides, polycarbonates, polyesters, polyurethanes, and thermoplastic elastomers.

25. A method for manufacturing pigment formulations, including: At least one dispersing and wetting agent and at least one pigment additive are introduced into a grinding apparatus. The at least one dispersing and wetting agent is selected from wax-based powdered processing additives having pigment-affinity groups, acid polyester-based additives having pigment-affinity groups, modified polyethers with high pigment-affinity groups, copolymers of styrene and polyethers, maleic acid amides, amphiphilic copolymers, modified polyacrylates with high pigment-affinity groups, polyester-based block copolymers, high molecular weight polyurethanes, polyester-polyamine-polyolefin terpolymers, and modified polysiloxanes with epoxy or urethane groups. The at least one dispersing and wetting agent has a melting point in the range of 50-150°C. The at least one pigment additive is selected from inorganic pigments, organic pigments, carbon black, and dyes. The grinding apparatus comprises at least two rotors. The dispersing and wetting agent is mixed with and ground with the at least one pigment additive to form a pigment formulation, wherein the average circumferential speed of the grinding device is 5-50 m / s; and The pigment formulation is collected, the pigment formulation comprising at least 60% by weight of the at least one pigment additive. The particle diameter D50 (by quantity) of the at least one pigment additive in the pigment formulation ranges from 0.5 to 3.5 μm, and The pigment formulations received are in the following forms: a) Free-flowing powder having a d20 of at least 0.8 micrometers and a d90 of up to 5 micrometers when measured by a laser particle size analyzer in a dry state under a pressure of 3.5 bar; or b) Particles having a d20 of at least 10 micrometers and a d90 of up to 1000 micrometers when measured by a laser particle size analyzer in a dry state under a pressure of 3.5 bar.

26. The method of claim 25, wherein the mixing and grinding are performed for 10-90 minutes.

27. The method of claim 25 or 26, wherein the maximum temperature reached during mixing and grinding of the mixture of dispersing wetting agent and pigment additive is 50-150°C.

28. The method of claim 25, wherein the particle diameter D90 (in terms of quantity) of the at least one pigment additive in the collected pigment formulation is in the range of 0.9-4 µm.

29. The method of claim 25, wherein the particle diameter D10 (in terms of quantity) of the at least one pigment additive in the collected pigment formulation is in the range of 0.5-1 µm.

30. The method of claim 25, wherein the grinding apparatus is a dry grinding apparatus.

31. The method of claim 25, wherein at least one of the rotors is a blade rotor.

32. The method of claim 25, wherein the dispersing and wetting agent has a number average molecular weight of 5,000-35,000.

33. The method of claim 25, wherein the collected pigment formulation is in the form of microparticles having a particle size in the range of 60-500 μm, preferably 80-350 μm.

34. The method of claim 25, wherein the collected pigment formulation is in the form of a free-flowing powder having a particle size of less than 50 μm.

35. The method of claim 25, wherein the introduction further comprises introducing at least one additive selected from the group consisting of: heat stabilizers, antioxidants, light stabilizers, antistatic agents, thermally conductive additives, anti-blocking additives, anti-collapse additives, UV stabilizers, fillers, anti-fibrillating agents, processing aids, swelling agents, drying additives, compatibilizers, lubricants, nucleating additives, clarifying additives, flame retardants, optical brighteners, tracer additives, and slip additives.

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