Universally dispersible solid pigment preparations, their preparation and use

Abstract

To provide a solid pigment preparation that is universally applicable for different kinds of application media, and a process of producing the same.SOLUTION: The present disclosure relates to a solid pigment preparation, comprising at least one pigment in an aqueous solution comprising an amine-functional acrylic block copolymer and an amine-functional polymeric dispersant comprising a polyoxyalkylene moiety, as well as a process for producing the solid pigment preparations and their use in various coloring applications. The solid pigment preparations are particularly universally dispersible in both water- and solvent-based systems. Corresponding dispersions are accordingly also within the scope of the present disclosure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a solid pigment preparation, a method for producing the solid pigment preparation, and its use in various coloring applications. The solid pigment preparation is particularly universally dispersible in both water- and solvent-based systems. Corresponding dispersions and coloring materials are also within the scope of the present invention. [Background technology]

[0002] Pigments such as carbon black are widely used to impart color to materials, for example, in plastic materials, paints, inks, and coating compositions. Here, the pigment generally must be uniformly and finely dispersed throughout the host material. Therefore, it is common to use pigments in combination with dispersants, which facilitate the dispersion of pigment particles in an aqueous or organic carrier medium and / or stabilize the particles therein, for example, reducing the tendency for flocculation, settling, or agglomeration during storage. Such pigment preparations can be provided in liquid or solid form and typically contain additional additives such as stabilizers, defoamers, surfactants, rheology modifiers, and / or anti-settling agents.

[0003] Solid pigment preparations can be dispersed in liquid application media by stirring or shaking, and compared with liquid pigment preparations, they are easier to handle and have a higher active ingredient content, so they have attracted increasing interest.However, solid pigment preparations with comparable properties cannot be obtained by simply drying available liquid pigment preparations.Therefore, various different solid pigment preparations and dedicated processes for their production have been developed.

[0004] Thus, for example, EP 2234708 B1 relates to a method for producing a solid pigment preparation, which comprises the steps of atomizing a suspension, contacting the droplets formed by the atomization with a gas stream having a predetermined temperature to dry the droplets and obtain granules having a predetermined residual moisture content, and separating the granules from the gas stream. The suspension comprises a solvent, a pigment, and a surface-active additive.

[0005] EP 1 517 934 B2, for example, discloses granular solid pigment preparations containing from more than 10% to a maximum of 40% by weight of an anionic surface-active additive based on an acid phosphate, phosphonate, sulfate, and / or sulfonate ester of a polyalkylene oxide, or a reaction product of an alkylene oxide with an aliphatic alcohol, a phenol, a naphthol, an aliphatic amine, an aromatic amine, an aliphatic carboxylic acid, a carboxamide, or a salt thereof. Optionally, nonionic surface-active additives based on polyethers can also be used in these solid pigment preparations.

[0006] Furthermore, EP 1565531 B2 relates to solid pigment preparations containing a water-soluble anionic surfactant additive selected from the group consisting of homo- and copolymers of ethylenically unsaturated monocarboxylic and / or dicarboxylic acids, with or without vinyl monomers not containing acid functional groups, after partial or complete esterification with polyether alcohols or their single-end derivatives, and salts of these homo- and copolymers. A polyether-based nonionic surfactant additive is disclosed for optional use.

[0007] EP 1 913 095 B1 relates to solid pigment preparations which contain alkylene oxide group-containing and alkylene oxide group-free additives and water-soluble surface-active additives from the group of antioxidants.

[0008] EP 2350210 B9 describes a pigment and a compound of the general formula CH3-(CH2) n -CH2-O-[(CH2) p -O]m This describes pigment particles containing the compound -H (where n = 8-18, p = 1-4, m = 35-100).

[0009] However, the aforementioned solid pigment preparations available in the prior art are usually only sufficiently dispersible and / or stable in either aqueous or solvent-borne media. Good coloration depends on achieving a fine and uniform dispersion of pigment particles in the respective media. If the pigment particles are not optimally dispersed and stabilized in the application system, lineation, sedimentation, and so-called pigment spots, i.e., undispersed pigment aggregates, can occur, leading to undesirable changes in the viscosity of the application system, as well as hue changes and losses in color strength, hiding power, gloss, homogeneity, and brightness. Furthermore, even if the pigment preparations of the prior art can be used in both aqueous and solvent-borne systems, the imparted colorant properties, such as hue, shade, or color strength, generally change when the same pigment preparation is used to color different media. Therefore, the processing industry is required to use and store numerous different solid pigment preparations for different types of application media.

[0010] Therefore, there is a need for solid pigment preparations that are universally applicable to different types of application media. Thus, the pigment preparation must be easily and effectively dispersible with low energy input and / or shear in both aqueous and solvent-based application systems to produce stable dispersions and impart desirable color properties, such as high color strength, especially high jetness. Ideally, the color properties imparted to both aqueous and solvent-based application systems should be comparable. Solid pigment preparations must be economically obtainable, safe, and easy to handle. Summary of the Invention

[0011] Surprisingly, it has been found that a solid pigment preparation comprises: (a) at least one pigment; (b) an amine-functional acrylic block copolymer, and (c) Amine-functional polymeric dispersants containing polyoxyalkylene moieties. This provides such a universally applicable solid pigment preparation.

[0012] The present invention also relates to a method for preparing such a solid pigment preparation, which method comprises: (i) dispersing at least one pigment in an aqueous solution comprising an amine-functional acrylic block copolymer and an amine-functional polymeric dispersant comprising a polyoxyalkylene moiety; and (ii) drying the dispersion to form a solid pigment preparation.

[0013] Furthermore, the present invention also relates to a dispersion comprising (a) at least one pigment, (b) an amine-functional acrylic block copolymer, (c) an amine-functional polymeric dispersant comprising a polyoxyalkylene moiety, and (d) an aqueous or organic solvent-based liquid carrier medium. Such a dispersion can be obtained, for example, by the above-described method for producing a solid pigment preparation according to the present invention or by (re)dispersing the solid pigment preparation according to the present invention in an aqueous or organic solvent-based medium, prior to the drying step.

[0014] The present invention also relates to a method for coloring a material, which method comprises incorporating a solid pigment preparation or dispersion according to the invention into said material, as well as the colored material thereby obtained.

[0015] The present invention also generally relates to the use of a combination of (i) an amine-functional acrylic block copolymer and (ii) an amine-functional polymeric dispersant containing a polyoxyalkylene moiety for dispersing pigments.

[0016] Surprisingly, it has been found that the solid pigment preparations of the present invention provide good dispersion behavior in both aqueous and solvent-based systems, making them universally applicable. The solid pigment preparations of the present invention can be easily dispersed with relatively low shear and low energy input to obtain uniform dispersions with finely dispersed pigment particles, regardless of the application medium. The solid pigment preparations of the present invention provide high color strength and / or jetness in addition to good agitation dispersibility in water and organic solvents. The color properties imparted to aqueous and solvent-based systems are comparable. Thus, the same solid pigment preparation can be used to color both aqueous and solvent-based systems, eliminating the need to store multiple solid pigment preparations to coat different application media. Furthermore, the dispersions obtainable from the solid pigment preparations of the present invention are stable enough to exhibit no or only minimal tendency to form flocs, clumps, or other forms of disintegration. They can be easily and safely handled and measured by users and can be produced economically using established production techniques.

[0017] Without intending to be bound by any theory, it is believed that the chemical nature of the amine-functional acrylic block copolymer and the amine-functional polymeric dispersant containing a polyoxyalkylene moiety makes them not only individually suitable, but also complement each other and particularly effective when used in combination in dispersing and stabilizing pigments, such as carbon black pigments, in liquid media of different chemical compositions and polarities, including aqueous and organic solvent-based media. DETAILED DESCRIPTION OF THE INVENTION

[0018] The present invention will be described in more detail below. As used herein, the term "comprising" is understood to be open-ended and not to exclude the presence of additional, undescribed or unlisted elements, materials, components, or method steps. The terms "including," "containing," and similar terms are understood to be synonymous with "comprising." As used herein, the term "consisting of" is understood to exclude the presence of any unspecified elements, components, or method steps.

[0019] As noted above, the present invention relates to a solid pigment preparation comprising (a) at least one pigment, (b) an amine-functional acrylic block copolymer, and (c) an amine-functional polymeric dispersant comprising a polyoxyalkylene moiety.

[0020] Thus, the solid pigment preparation according to the invention characteristically comprises a combination of an amine-functional acrylic block copolymer and an amine-functional polymeric dispersant comprising a polyoxyalkylene moiety, which combination has been found to impart universally efficient dispersibility to the solid pigment preparation according to the invention in both aqueous and organic solvent-based liquid media, and to outperform the performance of these components when used individually.

[0021] As used herein, the term "amine-functional" refers to the presence of at least one amine functional group in each component, which here includes primary, secondary, and tertiary amine functional groups as well as quaternary ammonium groups.

[0022] The amine-functional acrylic block copolymer used to prepare and contained in the solid pigment preparation according to the present invention can be any type of block copolymer containing amine functionality in the sense described above, especially those made from acrylic monomers, i.e., acrylic acid, methacrylic acid (collectively referred to as (meth)acrylic acid), and their derivatives, such as esters of (meth)acrylic acid, such as alkyl (meth)acrylates. As used herein, the term "block copolymer" refers to a polymer containing two or more distinct (homo)polymeric subunits ("blocks") linked by covalent bonds. For example, the block copolymer can include a diblock copolymer in which a first block "A" derived from a first monomer or monomer mixture is bonded to a second block "B" derived from a second monomer or monomer mixture different from the first monomer or monomer mixture. Other non-limiting examples include triblock polymers of the ABA type. Typically, the amine-functional block copolymer used according to the present invention contains one or more blocks derived from amine-functional monomers and one or more blocks derived from non-amine-functional monomers, such as alkyl (meth)acrylates. The block copolymers used in accordance with the present invention may be obtained from appropriate monomers, for example by free radical polymerization, in accordance with art-recognized methods.

[0023] The amine-functional acrylic block copolymer used in accordance with the present invention may preferably be a copolymer of at least vinylpyridine and one or more (meth)acrylate monomers, preferably including butyl (meth)acrylate. The amine-functional acrylic block copolymer used in accordance with the present invention may preferably have an amine value of at least 20 mg KOH / g, preferably at least 30 mg KOH / g. The amine value can be measured according to DIN 16945. The amine-functional acrylic block copolymer may have a weight average molecular weight M of at least 15,000 g / mol, preferably at least 20,000 g / mol. wThe weight average molecular weight M w can be determined by gel permeation chromatography using polystyrene standards for calibration. Suitable amine-functional acrylic block copolymers that can be used in accordance with the present invention include Efka® PX4300, Efka® PX4310, Efka® PX4320, Efka® PX4330, Efka® PX4340, Efka® PX4700, Efka® PX4701, Efka® PX4702, and Efka® PX4711, available from BASF SE Formulation Additives.

[0024] As described above, according to the present invention, an amine-functional polymeric dispersant containing a polyoxyalkylene moiety is used in combination with an amine-functional acrylic block copolymer. The amine-functional polymeric dispersant containing a polyoxyalkylene moiety used to prepare the solid pigment preparation according to the present invention and contained therein can, in principle, include any polyoxyalkylene-based dispersant having amine functionality. The polyoxyalkylene moiety of the amine-functional polymeric dispersant can be obtained by polyaddition of alkylene oxide (preferably ethylene oxide, propylene oxide, or butylene oxide) to starter molecules (such as saturated or unsaturated aliphatic and aromatic alcohols, saturated or unsaturated aliphatic and aromatic amines, saturated or unsaturated aliphatic carboxylic acids, their anhydrides and carboxamides, and saturated or unsaturated aliphatic acyl chlorides). The alkylene oxide or starter molecule can have a substituent containing an amine functionality or a functional group that can be converted to an amine functionality. From 1 to 300 moles, preferably from 3 to 150 moles, of alkylene oxide are used per mole of starter molecule. Suitable aliphatic alcohols contain 6 to 26 carbon atoms, preferably 8 to 18 carbon atoms, and can have unbranched, branched, and cyclic structures. Suitable aromatic alcohols include alkyl, especially C1-C 12These include phenols and naphthols, which may be alkyl- and vinyl-substituted. Suitable aliphatic amines correspond to the amine analogs of the aforementioned aliphatic alcohols. An example of a suitable aromatic amine is aniline and its derivatives. Useful aliphatic carboxylic acids include, in particular, (meth)acrylic acid, saturated and unsaturated fatty acids, and polyfunctional carboxylic acids, such as dicarboxylic acids. Polymers bearing functional groups reactive with alkylene oxides, such as amino, carboxy, hydroxy, and / or thiol groups, can also be used as starting molecules. Such functionalized polymers can be obtained, for example, by radical polymerization from a mixture of ethylenically unsaturated monomers, including ethylenically unsaturated monomers bearing the respective functional groups (e.g., (meth)acrylic acid or hydroxyalkyl (meth)acrylates). However, it is also possible to use polyoxyalkylene-containing monomers, such as polyoxyalkylene (meth)acrylates, in the monomer mixture to obtain amine-functional polymeric dispersants containing polyoxyalkylene moieties. The polyoxyalkylene portion of the dispersant can include, inter alia, oxyethylene, oxypropylene, and / or oxybutylene units, preferably oxyethylene and / or oxypropylene units. The polyoxyalkylene portion of the amine-functional polymer dispersant can be selected from the group consisting of, for example, polyoxyethylene, polyoxypropylene, and polyoxybutylene. Preferably, the dispersant includes a polyoxyethylene portion, a polyoxypropylene portion, or a mixture or combination thereof. For example, an amine-functional polymer dispersant including a polyoxyalkylene portion can include a polyether-modified polymer, such as a polystyrene-based polyether-modified polymer. As used herein, the term "polystyrene-based polymer" refers to a polymer that primarily contains styrene-derived units, such as at least 70% by weight, based on the total weight of the polymer. The polyether component of such a polyether-modified polymer can comprise, for example, 10 to 90% by weight, e.g., 20 to 85% by weight, or 50 to 80% by weight, based on the total weight of the amine-functional polymer dispersant.Here, the polyether component preferably contains oxyethylene structural units and / or oxypropylene structural units, for example, a combination of oxyethylene structural units and oxypropylene structural units. When the polyether component contains multiple different oxyalkylene units, for example, a combination of oxyethylene structural units and oxypropylene structural units, the ratio thereof can vary. For example, the amine-functional polymeric dispersant can contain oxyethylene structural units and oxypropylene structural units in a weight ratio of 1:10 to 10:2, for example, 1:5 to 5:1, or 1:3 to 3:1, or 1:2 to 2:1. In certain variations, the amine-functional polymeric dispersant containing polyoxyalkylene moieties can mainly contain, for example, more than 50% by weight, or more than 60% by weight, or more than 70% by weight, or more than 80% by weight, or more than 90% by weight of oxyethylene structural units. At least one polyoxyalkylene moiety can be present in the polymer backbone or as a side chain in the amine-functional polymeric dispersant. Amine functionality can be introduced by the use of an amine-functional educt, such as an amine-functional alkylene oxide or polymer-containing starter molecule, or by post-modification. Amine functionality can be introduced, for example, by converting the terminal alcohol end groups of the pendant polyoxyalkylene moieties to amine-containing moieties by the addition of suitable compounds (e.g., carboxylic acids, anhydrides, and carboxamides) containing a functional group reactive with alcohol groups and a protectable amine functionality. The amine-functional polymeric dispersants used in accordance with the present invention can have an amine value of up to 30 mg KOH / g, or up to 20 mg KOH / g, for example, in the range of 5 to 20 mg KOH / g. The amine value can be determined as described above. The amine-functional polymeric dispersants containing polyoxyalkylene moieties have a weight average molecular weight M of at least 10,000 g / mol, preferably at least 15,000 g / mol. w The weight average molecular weight M wcan be determined by gel permeation chromatography using polystyrene standards for calibration. Suitable amine-functional polymeric polyoxyalkylene-functional dispersants that can be used in accordance with the present invention are, for example, BYKJET-9150, BYKJET-9151, and BYKJET-9152, commercially available from BYK-Chemie GmbH.

[0025] The total amount of the amine-functional acrylic block copolymer and the amine-functional polymer dispersant containing a polyoxyalkylene structure used can vary. For example, the amine-functional acrylic block copolymer and the amine-functional polymer dispersant containing a polyoxyalkylene structure can be used in a total amount of at least 10% by weight, for example, at least 15% by weight, for example, at least 20% by weight, for example, at least 30% by weight, at least 50% by weight, at least 55% by weight, at least 60% by weight, at least 65% by weight, at least 70% by weight, at least 75% by weight, at least 80% by weight, at least 85% by weight, or at least 90% by weight, based on the total weight of the pigment in the solid pigment preparation. The amine-functional acrylic block copolymer and the amine-functional polymer dispersant containing a polyoxyalkylene structure can be used in a total amount of up to 200% by weight, up to 150% by weight, up to 120% by weight, up to 115% by weight, up to 110% by weight, up to 105% by weight, or up to 100% by weight, based on the total weight of the pigment in the solid pigment preparation. Typically, the amine-functional acrylic block copolymer and the amine-functional polymeric dispersant comprising a polyoxyalkylene structure are used in a total amount ranging from 10 to 120 wt%, for example, 15 to 120 wt%, for example, 50 to 120 wt%, preferably 70 to 100 wt%, based on the total weight of the pigment in the solid pigment formulation. It will be understood that any range between any of the explicitly disclosed lower and upper limits is disclosed herein.

[0026] The weight ratio of the amine-functional acrylic block copolymer to the amine-functional polymeric dispersant containing a polyoxyalkylene moiety can vary, typically ranging from 1:99 to 80:20, such as 5:95 to 70:30, preferably 10:90 to 50:50, more preferably 10:90 to less than 30:70, such as 10:90 to 25:75. Further exemplary ranges of ratios of amine-functional acrylic block copolymers according to the present invention to amine-functional polymeric dispersants comprising polyoxyalkylene structures can be 10:90 to 35:65, 10:90 to 30:70, 10:90 to 25:75, 15:85 to 40:60, 15:85 to 30:70, 15:85 to 25:75, 20:80 to 40:60, 20:80 to 35:65, 20:80 to 25:75, 25:75 to 40:60, 25:75 to 35:65, or 25:75 to 30:70.

[0027] The pigments used in the solid pigment preparations of the present invention can include any type of organic or inorganic pigment known in the art. Mixtures of two or more pigments can also be used.

[0028] Inorganic pigments include, but are not limited to, white pigments such as titanium dioxide (CI Pigment White 6), zinc white, pigment-grade zinc oxide, zinc sulfide, and lithopone; black pigments such as iron oxide black (CI Pigment Black 11), iron manganese black, spinel black (CI Pigment Black 27), and carbon black; chromium oxide, chromium oxide hydrate green, chrome green (CI Pigment Green 48), cobalt green (CI Pigment Green 50), ultramarine green, cobalt blue (CI Pigment Blue 28 and 36; CI Pigment Blue 72), ultramarine blue, manganese blue, ultramarine violet, cobalt violet, manganese violet, red iron oxide (CI Pigment Red 101), cadmium sulfo selenide (CI Pigment Red 108), cerium sulfide (CI Pigment Red 265), molybdate red (CI Pigment Red 104), ultramarine red, brown acid Iron oxide (CI Pigment Brown 6 and 7), mixed browns, spinel phase, corundum phase (CI Pigment Brown 29, 31, 33, 34, 35, 37, 39 and 40), chrome titanium yellow (CI Pigment Brown 24), chrome orange, cerium sulfide (CI Pigment Orange 75), yellow iron oxide (CI Pigment Yellow 42), nickel titanium yellow (CI Pigment Yellow 53; CI Pigment Yellow 157, 158, 159, 160, 161, 162, 163, chromatic pigments such as cadmium sulfide, cadmium zinc sulfide (CI Pigment Yellow 37 and 35), chrome yellow (CI Pigment Yellow 34), bismuth vanadate (CI Pigment Yellow 184), and the like; as well as luster pigments such as aluminum platelets, aluminum platelets with one or more coatings (especially metal oxides), iron oxide platelets, and mica platelets can be used.

[0029] Examples of organic pigments that can be used include, but are not limited to, CI Pigment Brown 25, CI Pigment Orange 5, 13, 36, 38, 64, and 67, CI Pigment Red 1, 2, 3, 4, 5, 8, 9, 12, 17, 22, 23, 31, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 51:1, 52:1, 52:2, 53, 53:1, 53:3, 57:1, 58:2, 58:4, 63, 112, 146, 148, 170, 175, 184, 185, 187, 191:1, 208, Monoazo pigments such as CI Pigment Yellow 210, 245, 247 and 251, CI Pigment Yellow 1, 3, 62, 65, 73, 74, 97, 120, 151, 154, 168, 181, 183 and 191, CI Pigment Violet 32; diazo pigments such as CI Pigment Orange 16, 34, 44 and 72, CI Pigment Yellow 12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176, 180 and 188; CI Pigment Yellow 93, 95 and 128, CI Pigment Yellow 191, CI Pigment Yellow 201, CI Pigment Yellow 212, CI Pigment Yellow 221, CI Pigment Yellow 231, CI Pigment Yellow 241, CI Pigment Yellow 252, CI Pigment Yellow 261, CI Pigment Yellow 272, CI Pigment Yellow 281, CI Pigment Yellow 291, CI Pigment Yellow 301, CI Pigment Yellow 312, CI Pigment Yellow 323, CI Pigment Yellow 313, CI Pigment Yellow 314, CI Pigment Yellow 315, CI Pigment Yellow 316, CI Pigment Yellow 317, CI Pigment Yellow 318, CI Pigment Yellow 319, CI Pigment Yellow 326, CI Pigment Yellow 329, CI Pigment Yellow 326, CI Pigment Yellow 3 Diazo condensation pigments such as CI Pigment Red 144, 166, 214, 220, 221, 242, and 262, and CI Pigment Brown 23 and 41; anthanthrone pigments such as CI Pigment Red 168; anthraquinone pigments such as CI Pigment Yellow 147, 177, and 199, and CI Pigment Violet 31; anthrapyrimidine pigments such as CI Pigment Yellow 108; cinchona pigments such as CI Pigment Orange 48 and 49, CI Pigment Red 122, 202, 206, and 209, and CI Pigment Violet 19. Cridone pigments; quinophthalone pigments such as CI Pigment Yellow 138; diketopyrrolopyrrole pigments such as CI Pigment Orange 71, 73 and 81, CI Pigment Red 254, 255, 264, 270 and 272; dioxazine pigments such as CI Pigment Violet 23 and 37, CI Pigment Blue 80; flavanthrone pigments such as CI Pigment Yellow 24; indanthrone pigments such as CI Pigment Blue 60 and 64; CI Pigment Orange 61 and 69, CI Pigment Red 260, CIisoindoline pigments such as CI Pigment Yellow 139 and 185; isoindolinone pigments such as CI Pigment Yellow 109, 110, and 173; isoviolanthrone pigments such as CI Pigment Violet 31; metal complex pigments such as CI Pigment Red 257, CI Pigment Yellow 117, 129, 150, 153, and 177, and CI Pigment Green 8; perinone pigments such as CI Pigment Orange 43 and CI Pigment Red 194; perylene pigments such as CI Pigment Black 31 and 32, CI Pigment Red 123, 149, 178, 179, 190, and 224, and CI Pigment Violet 29; CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and 16, and CI Pigment Red 194. Examples of pigments include phthalocyanine pigments such as CI Pigment Green 7 and 36; pyranthrone pigments such as CI Pigment Orange 51 and CI Pigment Red 216; pyrazoloquinazolone pigments such as CI Pigment Orange 67 and CI Pigment Red 251; thioindigo pigments such as CI Pigment Red 88 and 181 and CI Pigment Violet 38; and triarylcarbonium pigments such as CI Pigment Blue 1, 61, and 62, CI Pigment Green 1, CI Pigment Red 81, 81:1, and 169, CI Pigment Violet 1, 2, 3, and 27, CI Pigment Black 1 (aniline black), CI Pigment Yellow 101 (aldazine yellow), and CI Pigment Brown 22.

[0030] According to the present invention, the pigment component used in the solid pigment preparation can particularly comprise a black pigment.Preferably, the pigment used according to the present invention comprises carbon black.The carbon black used can be any type of carbon black known in the art, such as furnace black, gas black, channel black, lamp black, thermal black, acetylene black, Si-containing black (for example, as known from WO 98 / 45361 or DE 19613796), inversion black (for example, as known from DE 19521565), metal-containing black (for example, as known from WO 98 / 42778), or light-arc black, as well as carbon black that is a by-product of chemical processes.

[0031] In particular, the pigment used in accordance with the present invention may comprise oxidized carbon black. As used herein, the term "oxidized carbon black" refers to carbon black that has undergone an oxidative treatment and is characterized by surface-bonded polar, ionic, or ionizable groups (such as alcohol groups, phenol groups, lactol groups, quinone groups, ketone groups, anhydride groups, lactone groups, peroxide groups, ether groups, and / or carboxylic acid groups). Exemplary oxidizing agents include oxygen gas; peroxides such as hydrogen peroxide; persulfates such as sodium persulfate and potassium persulfate; hypochlorites such as sodium hypochlorite; nitric acid; and transition metal-containing oxidizing agents such as permanganates, osmium tetroxide, chromium oxide, and cerium ammonium nitrate; and mixtures thereof.

[0032] The carbon black used as a pigment according to the invention is, for example, 500 m 2 / g or less, preferably 200 to 450m 2 / g, more preferably 350 to 400m 2The carbon black may have a statistical thickness surface area (STSA) in the range of 1 / 100g. STSA can be measured according to ASTM D6556 (2004). The carbon black may have an oil absorption (OAN) in the range of 50 to 150 mL / 100g, preferably in the range of 70 to 130 mL / 100g. The OAN of the carbon black can be measured according to ASTM D2414 (2000). The carbon black used in the present invention may have a volatile content of 25% or less, preferably in the range of 1 to 25%, more preferably in the range of 2 to 15%. The volatile content can be measured according to DIN 53552.

[0033] The solid pigment preparation according to the invention may, if desired, further comprise one or more common additives such as biocides, moistening agents, wetting agents, flow aids, rheology modifiers, anti-settling agents or anti-foaming agents, etc. If present, such additives are typically used in an amount ranging from 0% to 5% by weight, based on the total weight of the pigment in the solid pigment preparation.

[0034] The solid pigment preparation may contain one or more biocides, such as preservatives, insecticides, disinfectants and / or pesticides, including 5-chloro-2-methyl-2H-isothiazolin-3-one, 2-methyl-2H-isothiazolin-3-one, 1,2-benzothiazol-3-one, 2-n-octyl-4-isothiazolin-3-one, tetramethylolacetylenediurea, diiodomethyl-p-tolylsulfone, dodecylguanidine hydrochloride, 3-iodo-2-propynyl butylcarbamate, Acticide® (So-Chemie), PROXEL® GXL preservative (Lonza), PROXEL® LS preservative (Lonza), KORDEK TM (Dow Chemical Company). When used, biocides can be used in an amount of 0 to 5% by weight, preferably 0.1 to 3% by weight, based on the total weight of the pigment.

[0035] The solid pigment preparation may also contain a moisturizing agent. Suitable examples of moisturizing agents include polyalcohols such as glycerin, polyethylene glycol (PEG), and polypropylene glycol (PPG). The moisturizing agent can be used in an amount of 0 to 5% by weight, preferably 0.1 to 3% by weight, based on the total weight of the pigment.

[0036] The solid pigment preparation of the present invention may further comprise, for example, a wetting agent. Suitable examples of wetting agents include METOLAT® (Munsing-Chemie), DISPERBYK-190 (BYK-Chemie), ADDAPT® BioWet TM 25 (ADDAPT Chemicals), and Borchi® Gen 0650 (Borchers). The optional wetting agent can be used in an amount of 0% to 5% by weight, preferably 0.1% to 3% by weight, based on the total weight of the pigment.

[0037] The solid pigment preparation of the present invention can also contain an anti-settling agent, if necessary. Suitable examples of anti-settling agents include silicas such as AEROSIL® R972 (Evonik Resource Efficiency). The optional anti-settling agent can be used in an amount of 0 to 5% by weight, preferably 0.1 to 3% by weight, based on the total weight of the pigment.

[0038] The solid pigment preparation may also contain rheology modifiers. Suitable examples of rheology modifiers include polyalcohols, Rheovis® PU (BASF) and Coapur TM (Arkema Group), polyethers such as Rheovis PE (BASF), silicas such as SIPERNAT® (Evonik Resource Efficiency), and METHOCEL TM The optional rheology modifier can be used in an amount of 0 to 5% by weight, preferably 0.1 to 3% by weight, based on the total weight of the pigment.

[0039] The solid pigment preparation may optionally contain a defoamer. Suitable examples of defoamers include silicone-based defoamers such as TEGO® Foamex 8050 (Evonik Resource Efficiency) and TEGO® Foamex 810 (Evonik Resource Efficiency), silicone-free polymer defoamers such as TEGO® Foamex 830 (Evonik Resource Efficiency) and Surfynol® 104E (Evonik Resource Efficiency), star polymer-based defoamers such as FoamStar ST (BASF), and mineral oil defoamers such as BYK-030 (BYK-Chemie). The defoamer can be used in an amount of 0 to 5% by weight, preferably 0.1 to 3% by weight, based on the total weight of the pigment.

[0040] The solid pigment preparation according to the present invention can be prepared, for example, according to the process described above, which comprises dispersing at least one pigment in an aqueous solution comprising an amine-functional acrylic block copolymer, an amine-functional polymeric dispersant comprising a polyoxyalkylene moiety, and optionally one or more of the optional additional ingredients described above, and drying the dispersion to form the solid pigment preparation.

[0041] As used herein, the term "aqueous" means that the respective medium is based primarily on water, such as containing at least 50% by weight of water based on the total weight of the solvents used in the medium. For example, the aqueous solution may contain water as the solvent in an amount of at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 95% by weight, based on the total weight of the solvents in the aqueous solution. For example, water can be used as the only solvent, i.e., the solvent in the aqueous solution consists of water (100% by weight). Alternatively, the aqueous solution used in the method for preparing a solid pigment preparation according to the present invention may contain one or more organic solvents in addition to water. Suitable organic solvents are, for example, monohydric or polyhydric alcohols, glycols, ketones, esters, glycerin, or combinations thereof. The aqueous solution of the present invention may contain from 0% to less than 50% by weight, e.g., up to 40%, 30%, 20%, 10%, or 5% by weight of organic solvent, based on the total weight of the solvents (including water) in the aqueous solution. Preferably, the aqueous solution contains 0 to 5 wt %, for example 0.1 wt % to 3 wt %, of the organic solvent based on the total weight of the solvent (including water) of the aqueous solution.

[0042] The aqueous solution containing the amine-functional acrylic block copolymer, the amine-functional polymeric dispersant containing polyoxyalkylene moieties, and the optional components described above for use in the method of the present invention can be prepared in various ways. For example, the amine-functional acrylic block copolymer can be first dissolved in an aqueous carrier, followed by the addition of the amine-functional polymeric dispersant containing polyoxyalkylene moieties, or vice versa. Preferably, the amine-functional acrylic block copolymer is premixed with water (and any organic solvent, if used), and then added to the amine-functional polymeric dispersant containing polyoxyalkylene moieties to prepare an aqueous solution for dispersing the pigment. The optional additives described above, such as biocides, moistening agents, wetting agents, flow aids, rheology modifiers, anti-settling agents, and / or defoamers, can be added to the aqueous phase before or after the addition of the amine-functional acrylic block copolymer and / or the amine-functional polymeric dispersant containing polyoxyalkylene moieties. Preferably, the optional additives are added to the aqueous solution after the addition of the amine-functional acrylic block copolymer and the amine-functional polymeric dispersant containing polyoxyalkylene moieties.

[0043] One or more pigments are then dispersed in an aqueous solution containing the amine functional acrylic block copolymer, the amine functional polymeric dispersant containing polyoxyalkylene moieties, and any optional ingredients, if present.

[0044] The pigment is typically dispersed in the aqueous solution in an amount in the range of 10 to 70% by weight, for example 10 to 50% by weight, or 10 to 30% by weight, more preferably 12 to 28% by weight, even more preferably 15 to 25% by weight, most preferably 18 to 23% by weight, and especially 20 to 22% by weight, based on the total weight of the dispersion.

[0045] Dispersion can be carried out by any means known in the art, for example, using a bead mill, a planetary mill, ultrasound, stirring and mixing elements, a dissolver, a shaker mixer (e.g., a Skandex mixer), a rotor-stator dispersing assembly (e.g., an Ultra-Turrax), or a high-pressure homogenizer. Dispersion is generally carried out until the pigment components are uniformly dispersed in the aqueous solution.

[0046] Optionally, the pH of the dispersion can be adjusted. For example, the pH of the dispersion can be controlled to an alkaline range, such as 8 to 12 or 8.5 to 11.0, such as 8.5 to 10.5, 8.5 to 10.0, 8.5 to 9.8, 9.0 to 11.0, 9.0 to 10.0, 9.0 to 9.8, 9.5 to 11.0, 9.5 to 10.5, 9.3 to 9.8, 9.3 to 11.0, 9.3 to 10.5, or 9.3 to 10.0, or any range between any of the listed values. Controlling the pH in the preparation of the solid pigment preparation, for example, to one of the aforementioned ranges, can maintain an appropriate balance of the acid and base forms of the functional groups (such as amine groups and protonated amine groups) present on the dispersant.

[0047] It should be understood that the desired pH of the dispersion may already be achieved by the components used to prepare the aqueous solution and / or pigment. Alternatively, the pH may be adjusted to the desired value or range by adding an acid or base. The acid or base may be added at any stage before the drying step, for example, during or after the preparation of the aqueous solution containing the amine-functional acrylic block copolymer and the amine-functional polymeric dispersant containing a polyoxyalkylene moiety, during the dispersion of the pigment in the solution.

[0048] Any type of conventional acid or base can be used to adjust the pH. The pH of the dispersion can be adjusted, for example, by adding a volatile or non-volatile base. The term "volatile base" as used herein refers to a base that is easily vaporizable and has a vapor pressure of p≧0.01 kPa at 20°C, and the term "non-volatile base" as used herein refers to a base that is barely vaporizable and has a vapor pressure of p<0.01 kPa at 20°C. Suitable bases that can be used according to the present invention include, for example, amino alcohols such as 2-amino-2-methylpropanol, 2-dimethylaminoethanol, 2-dimethylamino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-(hydroxymethyl)-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, N-(3-aminopropyl)-N-methylethanolamine, 2-amino-1-butanol, dimethylethanolamine, diethylethanolamine, 2-(diisopropylamino)ethanol, and 2-(dibutylamino)ethanol; or amines such as triethylamine, diisopropylamine, N-aminopropylmorpholine, (poly)etheramines (such as Jeffamine M-600, Jeffamine D-230), or N,N-dimethyl-3-methoxypropylamine, or aqueous ammonia. Preferably, a non-volatile base is used, such as a base having a vapor pressure of 0.001 kPa or less, or 0.0005 kPa or less at 20° C. The pH of the dispersion can be measured, for example, with a pH meter such as a Metrohm 780 instrument.

[0049] As mentioned above, the pigment in aqueous solution dispersion is then dried to form a solid pigment preparation therefrom.

[0050] The dispersion may be dried using any known drying technique, such as, for example, spray drying, vacuum distillation, freeze drying, infrared drying, microwave drying, oven drying, drying using a rotary drum dryer, or any combination of the above. Preferably, the dispersion may be dried by spray drying.

[0051] Spray drying may be carried out in a spray dryer using nozzle atomization and parallel, semi-opposed (fountain atomization), or opposed gas path designs. Spray drying can be carried out, for example, as described in EP 2234708 B1. Optionally, flow additives can be used in the spray drying process to improve rheological properties. Suitable flow additives include, but are not limited to, silica and modified silicas commercially available from Evonik Industries (such as AEROSIL® and SIPERNAT® products).

[0052] The resulting dry solid pigment preparation may have a residual water content of 0 to 20% by weight, preferably 0.1 to 5% by weight, based on the total weight of the solid pigment preparation. The residual water content can be determined in accordance with DIN ISO 787-2.

[0053] The dried material can optionally be subjected to further processing such as grinding, crushing, milling, etc. The solid pigment preparation according to the invention can generally be provided in different physical forms, for example as a powder or granules. In particular, the solid pigment preparation according to the invention may be free-flowing, preferably a free-flowing granular composition. In this specification, the term "free-flowing granular composition" relates to a solid pigment preparation comprising pigment granules present in finely divided form.

[0054] Therefore, the pigment granules preferably have a mass-weighted median particle size in the range of 1 to 3000 μm. The mass-weighted median particle size of the pigment can be measured by laser diffraction spectroscopy according to ISO 13320-1. The measurement can be performed using a Sympatec HELOS laser diffraction spectrometer, dispersing the pigment granules at a dispersing air pressure of 1 bar and evaluating the particle size distribution according to the Fraunhofer theory.

[0055] As mentioned above, a distinctive advantage of the solid pigment preparations of the present invention is that they can be easily dispersed with relatively low shear and low energy input to obtain uniform dispersions with finely dispersed pigment particles in different application media. In particular, the solid pigment preparations of the present invention are dispersible in both aqueous and organic solvent-based media or resin media. They can be dispersed in, for example, water and organic solvents such as alcohols (e.g., ethanol), polymeric resins such as acrylic resins, hydrocarbons such as xylene, glycols, esters such as butyl acetate, and combinations of any of the above. Dispersion can be achieved, for example, by bead mills, ultrasonics, stirring and mixing elements, dissolvers, shaker mixers (e.g., Skandex mixers), rotor-stator dispersing assemblies (e.g., Ultra-Turrax), or high-pressure homogenizers. For example, the solid pigment preparations of the present invention can be dispersed in aqueous and / or organic solvent-based media, typically using a Pendraulik LR34 dissolver with a 40 mm diameter dispersing disc at 4000 rpm for less than 30 minutes, to obtain uniform dispersions with a milled fineness of less than 5 μm. The particle size of the resulting dispersion can be measured with a grindometer according to DIN EN ISO1524:2013.

[0056] Accordingly, the present invention also generally relates to the use of a combination of (i) an amine-functional acrylic block copolymer and (ii) an amine-functional polymeric dispersant containing a polyoxyalkylene moiety to disperse pigments.

[0057] In view of the foregoing, the present invention also relates to a dispersion comprising (a) at least one pigment, (b) an amine-functional acrylic block copolymer, (c) an amine-functional polymeric dispersant containing a polyoxyalkylene moiety, and (d) a liquid aqueous or organic solvent-based carrier medium. The pigment here is generally dispersed in the carrier medium, which forms the continuous phase. Such a dispersion can be obtained, for example, by the above-described method for producing a solid pigment preparation according to the present invention or by (re)dispersing the solid pigment preparation according to the present invention in an aqueous or organic solvent-based medium prior to the drying step.

[0058] It will be understood that the features described above for the solid pigment preparation, in particular the amine-functional acrylic block copolymer, the amine-functional polymeric dispersant containing polyoxyalkylene moieties, and the pigment, and the amounts of each thereof, apply analogously to the dispersion according to the invention. The dispersion according to the invention can likewise comprise any one of the optional components described above with reference to the solid pigment preparation according to the invention.

[0059] Dispersions according to the present invention are typically stable and do not show any appreciable deterioration such as flocculation, clumping, or adverse effects on their application properties over time, and typically exhibit good storage stability. As used herein, the term "storage stable" refers to dispersions that do not show significant deterioration even after accelerated storage conditions at 60°C for 16 hours.

[0060] The solid pigment preparations and associated dispersions of the present invention can in particular be used for coloring or tinting materials.

[0061] The present invention therefore also relates to a method for coloring a material, which comprises incorporating into said material a solid pigment preparation or dispersion according to the invention as described above.

[0062] The material to be colored is not particularly limited and may be any condensed phase material.Suitable materials that can be colored using the pigment preparation or dispersion according to the present invention include paints such as architectural exterior and architectural interior paints (for example, wood paints or emulsion paints); coating systems such as architectural coatings, industrial coatings, automotive coatings, and radiation-curable coatings; printing inks such as offset printing inks, flexographic printing inks, toluene gravure printing inks, textile printing inks, and radiation-curable printing inks; emulsion and varnish colors; adhesives; and plastics such as casein plastics, phenolic resins, urea resins, thiourea resins, melamine resins, acrylic resins, allyl resins, silicones, polyimides, polybenzimidazoles, polyamides, polycarbonates, polyesters, polyphenylene oxides, polysulfones, polyvinyl acetates, polyolefins, polyvinyl chlorides, polymethyl methacrylates, polyacrylonitriles, polystyrenes, or epoxy resins.

[0063] The incorporation of the pigment preparation or dispersion of the present invention into the material to be pigmented can be carried out according to any suitable known technique, for example by stirring, shaking, extruding (for example using a single or twin screw extruder), rolling, kneading, grinding, or any combination of the above.

[0064] Preferably, the material to be colored is fluid, and the pigment preparation can be incorporated by stirring in the fluid material. Stirring should be understood to mean any kind of mixing that uses minimal shear force (including, for example, shaking).In this specification, the term "fluid" refers to a liquid substance that can flow, does not have a fixed shape, and can move and change shape under pressure without separating.

[0065] Therefore, the present invention also relates to a coloring material obtained by the above-described method for coloring a material. The coloring material may be, in particular, a water-based, solvent-based, or 100% solids paint, coating, or ink composition. As used herein, the term "100% solids" refers to a composition that is substantially free of solvent, such as a powder coating composition. The term "waterborne" is used interchangeably with the term "aqueous" herein to mean that the material composition contains solids dissolved or dispersed in water and, optionally, one or more organic solvents or liquid carriers, with water comprising the majority (greater than 50% by weight) of the solvent in such a material composition. The term "solvent-borne" or "organic solvent-based" or the like, as used herein, refers to a medium or material containing one or more organic solvents and, optionally, water, with the organic solvent comprising the majority (greater than 50% by weight) of the solvent in such a medium or material composition. Non-limiting examples of organic solvents include monohydric or polyhydric alcohols, glycol ethers, ketones (e.g., methyl ethyl ketone), amides (e.g., N-methylpyrrolidone and dimethylformamide), esters (e.g., ethyl acetate, butyl acetate, and methoxypropyl acetate), or aromatic or aliphatic hydrocarbons (e.g., xylene), mineral oil, and mineral spirits.

[0066] It will be understood that the formulation of coloring materials may contain additional ingredients common in the art of compounding such materials for their respective purposes and uses. For example, the formulation of a paint, coating composition or ink may include the use of a grinding vehicle. The use of such additional ingredients is well known to those skilled in the art and therefore will not be described in greater detail herein.

[0067] The solid pigment preparations or dispersions according to the present invention can provide desirable color properties, such as high color strength and / or jetness, to the medium in which they are incorporated. Moreover, the color properties imparted by the same pigment preparation to different media, such as aqueous and solvent-based systems, are typically comparable. Thus, the dried film obtained from a coating system comprising the dispersed solid pigment preparation of the present invention, whether aqueous or organic solvent-based, can have a jetness M of, for example, 200 or more, preferably 220 or more, more preferably 260 or more, even more preferably 280 or more, and most preferably 300 or more. Y and / or have an undertone dM of 0 or greater, preferably greater than 0, for example 5 or greater or 10 or greater. Dried films obtained from identical dispersed solid pigment preparations of the present invention, for example from different coating systems, including aqueous and organic solvent-based coating systems, may have a ΔM Y The ΔM may exhibit equivalent color properties, such as having an equivalent jetness of less than 60, preferably less than 50, more preferably less than 40, even more preferably less than 30, and most preferably less than 20, and especially less than 15. Y is the jetness value M measured on films obtained from two different coating systems containing the same dispersed solid pigment preparation of the present invention. Y The above color characteristics can be measured using a spectrophotometer as described in the Examples. Jetness M Y , undertone dM and ΔM Y The aforementioned numerical values ​​of color properties such as can be determined in particular using reference aqueous and organic solvent-based coating systems with the solid pigment preparation according to the invention, as described in the examples below, which serve to illustrate the typical properties that can be obtained for the pigment preparation of the invention when used to color an aqueous medium or an organic solvent-based medium, respectively.

[0068] The dry film can be obtained from a water-based or solvent-based coating composition containing the dispersion of the pigment preparation according to the invention by any suitable film-forming technique known in the art. For example, the dispersion can be applied to the surface of a substrate such as a glass substrate using a film-drawing bar with uniform tension and pressure. Subsequently, the wet coating film on the substrate can be dried, for example, by flashing at room temperature (20 °C) for 5 to 120 minutes, preferably 10 to 60 minutes, more preferably 15 to 30 minutes, and / or by exposing the coated substrate to a high temperature such as 80 °C for 5 to 120 minutes, preferably 10 to 60 minutes, more preferably 15 to 30 minutes.

[0069] The present invention has been generally described above. However, further understanding can be obtained by referring to the following examples. These examples are provided herein for illustrative purposes only and are not intended to limit the present invention. Rather, the present invention should be given the full scope of the appended claims, including any equivalents thereof.

Examples

[0070] All parts and percentages shown through the examples refer to weight unless otherwise specified.

[0071] Materials Used

[0072] Pigments: <Color Black FW255> Furnace black oxide (STSA: about 370 m 2 / g, OAN: about 108 mL / 100 g, volatile matter: about 12.5 wt%) (commercially available from Orion Engineered Carbons) <Hostaperm® Yellow H4G> Benzimidazolone pigment (C.I. Pigment Yellow 151, commercially available from Clariant) <Titanium dioxide> Inorganic white pigment (commercially available from Kuncai) <Heliogen (Registered Trademark) Blue L7101F> Phthalocyanine pigment (C.I. Pigment Blue 15:4, commercially available from BASF)

[0073] Dispersant: <Dispersant A> Amine-functional acrylic block copolymer having an amine value of 40 mg KOH / g (commercially available from BASF as part of the Efka (Registered Trademark) PX product line.) <Dispersant B> Amine-functional polyoxyalkylene-containing dispersant having an amine value of 19 mg KOH / g (commercially available from BYK-Chemie as part of the BYKJET product line.) <Dispersant C> Ethoxylated C 16 -C 18 Alcohol (commercially available from KLK Oleo Europe) <Dispersant D> Concentrate of fatty acid derivatives without solvents and alkylphenol ethoxylate (APE), commercially available from Evonik Resource Efficiency as TEGO (Registered Trademark) Dispers652

[0074] Additive substances: <TEGO (Registered Trademark) Foamex830> Silicone-free defoamer containing organic polymer and fumed silica, commercially available from Evonik Resource Efficiency <Surfynol (Registered Trademark) 104E> Wetting agent and molecular defoamer, commercially available from Evonik Resource Efficiency <BYK (Registered Trademark)-024> Volatile organic (VOC)-free silicone-containing defoamer, commercially available from BYK-Chemie <AMP90 TM > 2-Amino-2-methylpropanol, commercially available from Angus Chemical <dmea> Dimethylethanolamine <TEGO® WET280> Liquid polyether siloxane copolymer (commercially available from Evonik Resource Efficiency GmbH) <ALBERDINGK® U9800> Solvent-free aliphatic polyester polyurethane dispersion (commercially available from Alberdingk Boley GmbH) <Degalan® VP4157L> Acrylic resin (commercially available from Evonik Resource Efficiency GmbH) <Vestanat® HB2640MX> Combination of aliphatic polyisocyanate and biuret of hexamethylene diisocyanate (75%) (commercially available from Evonik Resource Efficiency GmbH) <Baysilone® OL17> Polyether-modified polysiloxane (100%) (commercially available from OMG Borchers GmbH) <Setal® 189> Saturated polyester resin (commercially available from Alnex GmbH) <Setal® F310SN> Short oil alkyd resin based on saturated fatty acids (commercially available from Alnex GmbH) <Maprenal MF800 / 55IB> Isobutylated melamine formaldehyde resin (commercially available from Prefere Resins GmbH)

[0075] Preparation of solid pigment preparation

[0076] (A) Preparation of aqueous dispersion The aqueous dispersion was prepared as follows using the components shown in Table 1 in amounts corresponding to the predetermined weight percentages.

[0077] Table 1

Table 1

[0078] Example 1 (Comparative Example) Dispersant C was dissolved in water and mixed with Surfynol® 104E and AMP90 TM was added to this solution. Subsequently, pigment (Color Black FW255) was added, and the resulting mixture was stirred until the entire amount of pigment was wetted. A pre-dispersion was formed by dispersing this mixture in a Pendraulik LR34 disperser at 4000 rpm for 5 minutes using a 40 mm diameter dispersing disk. Subsequently, 540 g of 3 mm diameter steel beads were added to the pre-dispersion, and the pre-dispersion was milled for 60 minutes using a Skandex disperser BA-S20.

[0079] Example 2 (Comparative Example) Dispersant D was dissolved in water and TEGO® Foamex 830, Surfynol® 104E and AMP90 TM was added to this solution. Subsequently, pigment (Color Black FW255) was added, and the resulting mixture was stirred until the entire amount of pigment was wetted. A pre-dispersion was formed by dispersing this mixture in a Pendraulik LR34 disperser at 4000 rpm for 5 minutes using a 40 mm diameter dispersing disk. Subsequently, 540 g of 3 mm diameter steel beads were added to the pre-dispersion, and the pre-dispersion was milled for 60 minutes using a Skandex disperser BA-S20.

[0080] Example 3 (Comparative Example) Dispersant A was dissolved in water and TEGO® Foamex 830, Surfynol® 104E and AMP90 TM was added to this solution. Subsequently, pigment (Color Black FW255) was added, and the resulting mixture was stirred until the entire amount of pigment was wetted. A pre-dispersion was formed by dispersing this mixture in a Pendraulik LR34 disperser at 4000 rpm for 5 minutes using a 40 mm diameter dispersing disk. Subsequently, 540 g of 3 mm diameter steel beads were added to the pre-dispersion, and the pre-dispersion was milled for 60 minutes using a Skandex disperser BA-S20.

[0081] Example 4 (Comparative Example) The experimental procedure was the same as in Example 3, except that Dispersant B was used instead of Dispersant A.

[0082] The dispersion of Example 4 exhibited relatively fast settling.

[0083] Example 5 Dispersant A was premixed in water and added to Dispersant B. TEGO® Foamex 830, Surfynol® 104E, and AMP90 TM was added to this solution. Subsequently, pigment (Color Black FW255) was added, and the resulting mixture was stirred until the entire amount of pigment was wetted. A pre-dispersion was then formed by dispersing the mixture in a Pendraulik LR34 disperser at 4000 rpm for 5 minutes using a 40 mm diameter dispersing disk. Subsequently, 540 g of 3 mm diameter steel beads were added to the pre-dispersion, and the pre-dispersion was milled for 60 minutes using a Skandex BA-S20 disperser.

[0084] Examples 6-9 Dispersant A was premixed in water and added to Dispersant B in the relative amounts shown. Then, Surfynol® 104E and AMP90 TM was added to this solution. Subsequently, pigment (Color Black FW255) was added, and the resulting mixture was stirred until the entire amount of pigment was wetted. A pre-dispersion was then formed by dispersing the mixture in a Pendraulik LR34 disperser at 4000 rpm for 5 minutes using a 40 mm diameter dispersing disk. Subsequently, 540 g of 3 mm diameter steel beads were added to the pre-dispersion, and the pre-dispersion was milled for 60 minutes using a Skandex BA-S20 disperser.

[0085] (B) Spray drying The aqueous dispersions according to Examples 1 to 9 were spray dried using a Buchi B290 spray dryer. The dispersions were conveyed to the spray nozzle by a peristaltic pump and dried at an inlet temperature of 105-180° C. and an outlet temperature of about 68° C. The resulting solid pigment preparations were collected at the outlet via a cyclone.

[0086] Clogging or blockage at the spray nozzle was noted to subjectively assess spray dryability.

[0087] Evaluation of the prepared solid pigment preparations

[0088] Redispersibility in water The redispersibility in water of the spray-dried solid pigment preparations according to Examples 1 to 9 was investigated by dispersing them in water for 30 minutes at 4000 rpm in a Pendraulik LR34 dissolver using a 40 mm diameter dispersing disc and measuring the fineness of grind of the resulting dispersions. The ratio of deionized water to solid pigment preparation was chosen here to give a pigment concentration of 13 wt. %.

[0089] Redispersibility in organic solvents The redispersibility in organic solvents was investigated by dispersing the spray-dried solid pigment preparations according to Examples 1 to 9 in butyl acetate for 30 minutes at 4000 rpm using a Pendraulik LR34 dissolver with a 40 mm diameter dispersing disk and measuring the fineness of grind of the resulting dispersions. The ratio of organic solvent to solid pigment preparation was chosen here so that the concentration of pigment in the resulting solvent-based dispersion was 8.23 ​​wt. %.

[0090] The particle size of the dispersions thus obtained was measured with a grindometer according to the method of DIN EN ISO 1524:2013. When the fineness of grinding was less than 5 μm, the redispersibility in water or organic solvents, respectively, was evaluated as good. The results obtained are shown in Table 2 below.

[0091] Preparation of Aqueous Coating Compositions ("Reference Aqueous Coating System") (a) Preparation of aqueous dispersions from the solid pigment preparations of Examples 1 to 9: Deionized water is placed in a Skandex dispersion beaker (180 mL, 5.3 cm diameter, 12.5 cm height) and one of the solid pigment preparations 1 to 9 is stirred with a spatula. The mixture is then dispersed in a Pendraulik LR34 dissolver using a 40 mm diameter dispersion disk at 4000 rpm for 30 minutes. The ratio of deionized water to solid pigment preparation is selected so that the pigment concentration is 13% by weight.

[0092] (b) Preparation of reference lacquer A: Reference lacquer A is produced as follows. [Table 2]

[0093] ALBERDINGK® U9800 is added to a container and stirred using a Pendraulik LR34 dissolver. Butyl glycol, BYK®-024, TEGO® WET280, DMEA, and deionized water are premixed and added to the ALBERDINGK® U9800. This mixture is dispersed at 1000 rpm using a 40 mm diameter dispersion disk. The mixture is then homogenized at 1500 rpm for 5 minutes. After preparation of the reference lacquer, the reference lacquer is left overnight.

[0094] The quality of the reference lacquer A is controlled by applying it to a glass plate (130 x 90 x 1 mm) and stretching it with a film stretching bar having a slot height of 200 μm and uniform tension and pressure in the wet state. Taking care to ensure there are no air bubbles in the stripe of reference lacquer A, the film stretching bar is placed on the stripe of reference lacquer A and pulled uniformly across the plate. A stretched object approximately 10 cm long and 6 cm wide is produced.

[0095] After the drawing procedure, the wet coating on the glass plate is flashed off at room temperature (20°C) for 15 minutes, and then the coated glass plate is dried at 60°C for 15 minutes.

[0096] Coatings prepared from reference lacquer A are checked for defects such as craters, spots, and irregularities. If the number of defects is significant, the reference lacquer is prepared anew for use in formulating the coating composition described below.

[0097] (c) Preparation of the aqueous coating composition Aqueous coating compositions were prepared from aqueous dispersions prepared as described above from the solid pigment preparations according to Examples 1 to 9 and the reference lacquer A. [Table 3]

[0098] The dispersions prepared from each solid pigment preparation and reference lacquer A were weighed in the amounts indicated above into 80 mL beakers and vigorously homogenized with a spatula until uniform, yielding the corresponding aqueous coating compositions.

[0099] Preparation of Solvent-Borne Coating Compositions ("Reference Organic Solvent-Based Coating Systems") (a) Preparation of organic solvent-based dispersions from the solid pigment preparations of Examples 1 to 9: A Skandex dispersion beaker (180 mL, diameter 5.3 cm, height 12.5 cm) is filled with Degalan® VP4157L and butyl acetate in a weight ratio of 60.3:22.5, and one of the solid pigment preparations from Examples 1 to 9 is stirred in with a spatula. The mixture is then dispersed in a Pendraulik LR34 dissolver using a 40 mm diameter dispersion disk at 4000 rpm for 30 minutes. The ratio of organic solvent to solid pigment preparation is selected so that the pigment concentration in the resulting solvent-based dispersion is 8.23 ​​wt. %.

[0100] (b) Preparation of solvent-borne coating composition: Solvent-based coating compositions were prepared from the solvent-based dispersions thus obtained, which were prepared from the solid pigment preparations of Examples 1 to 9, according to the following formulations. [Table 4]

[0101] These components were weighed in the indicated amounts into an 80 mL beaker and vigorously homogenized with a spatula for 10 minutes to obtain the corresponding solvent-borne coating compositions.

[0102] Preparation of films from coating compositions Films were prepared from the aqueous coating compositions prepared from the solid pigment preparations of Examples 1-9, as well as from the solvent-borne coating compositions prepared from the solid pigment preparations of Examples 1-9, as follows.

[0103] Each coating composition was applied to a glass plate (130 x 90 x 1 mm) and stretched wet and with uniform tension and pressure using a film stretching bar with a slot height of 200 μm (for aqueous coating compositions) or 100 μm (for solvent-based coating compositions). Care was taken to ensure the absence of air bubbles in the coating composition stripe. The film stretching bar was placed over the coating composition stripe and stretched uniformly across the plate. A stretch approximately 10 cm long and 6 cm wide was produced.

[0104] After the drawing procedure, the resulting wet coating on the glass plate was flashed off at room temperature (20°C), and then the coated glass plate was dried at 80°C for 30 minutes (for solvent-based coating compositions) and at room temperature (20°C) for 15 minutes, followed by drying at 60°C for 15 minutes (for water-based coating compositions).

[0105] Color measurement The color properties of the resulting films prepared from the aqueous and solvent-based coating compositions were measured using a Pausch Q-Color 35 spectrophotometer (45° / 0° spectrophotometer) and BCSWIN software. Measurements were performed through glass after calibration with a white calibration tile and a black hollow body. The spectrometer averaged five individual measurements for each sample.

[0106] Hue-independent black value M Y and the hue-dependent black value, Mc, is calculated from the measurement-derived tristimulus (XYZ) data as follows:

[0107] Hue-independent black value M Y is calculated from the tristimulus component Y of the measurement (illuminant D65 / 10°) according to Equation 1:

number

number

[0108] The absolute hue contribution dM is the sum of the black values ​​Mc and M Y is calculated according to Equation 3.

number

[0109] The M thus obtained Y The color properties in terms of dM and dM are reported in Table 2 for films prepared from aqueous coating compositions prepared from solid pigment preparations according to Examples 1-9 above, as well as for films prepared from solvent-borne coating compositions.

[0110] The results in Table 2 show that only solid pigment preparations prepared according to the present invention are simultaneously spray-driable and easily redispersible in water and organic solvents, and exhibit comparable color properties with high jetness and similar undertone for films obtained from the corresponding aqueous or solvent-based coating compositions.

[0111] Table 2 [Table 5]

[0112] Preparation of further solid pigment preparations using different types of pigments (A) Preparation of aqueous dispersion Example 10 18 g of Dispersant A was premixed in 328 g of deionized water and added to 54 g of Dispersant B. Subsequently, 240 g of pigment (Hostaperm® Yellow H4G) was added, and the resulting mixture was stirred until the entire amount of pigment was wetted. A predispersion was then formed by dispersing the mixture in a Pendraulik LR34 dissolver at 4000 rpm for 10 minutes using an 80 mm diameter dispersing disc. The predispersion was then diluted by adding 160 g of deionized water, and glass beads with a diameter of 0.6-0.8 mm were added. The diluted predispersion was then milled at 4000 rpm for 60 minutes using a Dispermat CV with an 80 mm diameter Teflon disc.

[0113] Example 11 26.4 g of Dispersant A was premixed in 314.4 g of deionized water and added to 79.2 g of Dispersant B. 600 g of titanium dioxide pigment was then added, and the resulting mixture was stirred until the entire pigment was wet. A predispersion was then formed by dispersing the mixture in a Pendraulik LR34 disperser at 4000 rpm for 10 minutes using an 80 mm diameter dispersing disc. The predispersion was then diluted with 160 g of deionized water, glass beads with a diameter of 0.6-0.8 mm were added, and the diluted predispersion was milled at 4000 rpm for 90 minutes using a Dispermat CV with an 80 mm diameter Teflon disc.

[0114] Example 12 28 g of Dispersant A was premixed in 487 g of deionized water and added to 85 g of Dispersant B. Subsequently, 250 g of pigment (Heliogen® Blue L7101F) was added, and the resulting mixture was stirred until the entire amount of pigment was wetted. A predispersion was then formed by dispersing the mixture in a Pendraulik LR34 dissolver at 4000 rpm for 10 minutes using an 80 mm diameter dispersing disc. The predispersion was then diluted by adding 160 g of deionized water, and glass beads with a diameter of 0.6-0.8 mm were added. The diluted predispersion was then milled at 4000 rpm for 60 minutes using a Dispermat CV with an 80 mm diameter Teflon disc.

[0115] (B) Spray drying The aqueous dispersions according to Examples 10-12 were spray dried using a Buchi B290 spray dryer as described above for Examples 1-9. The resulting solid pigment preparations were collected at the outlet via a cyclone. Clogging or blockage at the spray nozzle was noted to subjectively assess spray dryability.

[0116] Evaluation of the prepared solid pigment preparations Storage stability To investigate their storage stability, the solid pigment preparations according to Examples 10 to 12 were stored for 10 days in an air atmosphere and in an oven (binder) at a temperature of 60° C., respectively.

[0117] Redispersibility in water The redispersibility in water of the freshly spray-dried and stored solid pigment preparations according to Examples 10 to 12 was investigated by dispersing each solid pigment preparation in water for 30 minutes at 4000 rpm in a Pendraulik LR34 dissolver using a 40 mm diameter dispersing disc and measuring the fineness of grind of the resulting dispersion. The ratio of deionized water to solid pigment preparation was chosen here to give a pigment concentration of 20 wt. %.

[0118] Redispersibility in organic solvents The redispersibility in organic solvents of freshly spray-dried and stored solid pigment preparations according to Examples 10 to 12 was investigated by dispersing each solid pigment preparation in a mixture of Setal® 189 and xylene according to Table 3 below in a Pendraulik LR34 dissolver using a 40 mm diameter dispersing disc for 30 minutes at 4000 rpm and measuring the fineness of grind of the resulting dispersions. The ratio of organic solvent to solid pigment preparation was chosen here so that the concentration of pigment in the resulting solvent-based dispersions was 10 to 20 wt. %.

[0119] Table 3 [Table 6]

[0120] The particle size of the dispersions thus obtained was measured with a grindometer according to the method of DIN EN ISO 1524: 2013. When the fineness of grinding was less than 6 μm, the redispersibility in water or organic solvents, respectively, was rated as good.

[0121] Preparation of Aqueous Coating Compositions ("Reference Aqueous Coating System") (a) Preparation of aqueous dispersions from the solid pigment preparations of Examples 10 to 12: A Skandex dispersion beaker (180 mL, 5.3 cm diameter, 12.5 cm height) is filled with deionized water and one of the solid pigment preparations 10-12 ((a) freshly spray-dried or (b) stored at 60 °C for 10 days as described above) is stirred with a spatula. The mixture is then dispersed in a Pendraulik LR34 dissolver using a 40 mm diameter dispersion disk at 4000 rpm for 30 minutes. The ratio of deionized water to solid pigment preparation is selected so that the pigment concentration is 20 wt. %.

[0122] (b) Preparation of reference lacquer A: The same reference lacquer A was used as in Examples 1-9.

[0123] (c) Preparation of the aqueous coating composition Aqueous coating compositions were prepared from aqueous dispersions prepared as described above from solid pigment preparations according to Examples 10 and 12 ((a) freshly spray-dried or (b) stored at a temperature of 60°C for 10 days) and reference lacquer A. [Table 7]

[0124] The dispersions prepared from each solid pigment preparation and reference lacquer A were weighed in the amounts indicated above into 80 mL beakers and vigorously homogenized with a spatula until uniform, yielding the corresponding aqueous coating compositions.

[0125] Preparation of Solvent-Borne Coating Compositions ("Reference Organic Solvent-Based Coating Systems") (a) Preparation of organic solvent-based dispersions from the solid pigment preparations of Examples 10 to 12: A Skandex dispersion beaker (180 mL, diameter 5.3 cm, height 12.5 cm) is filled with Setal® 189 and xylene in the weight ratio according to Table 4 below, and one of the solid pigment preparations from Examples 10 to 12 ((a) freshly spray-dried or (b) stored at 60°C for 10 days as described above) is stirred in with a spatula. The mixture is then dispersed in a Pendraulik LR34 dissolver using a 40 mm diameter dispersion disk at 4000 rpm for 30 minutes. The ratio of organic solvent to solid pigment preparation is selected so that the resulting solvent-based dispersion has a pigment concentration of 10 to 20% by weight. Table 4 [Table 8]

[0126] (b) Preparation of solvent-borne coating composition: Solvent-based coating compositions were prepared from the solvent-based dispersions thus obtained from the solid pigment preparations of Examples 10 and 12 ((a) freshly spray-dried or (b) stored at a temperature of 60°C for 10 days) according to the following formula: [Table 9]

[0127] These components were weighed in the indicated amounts into an 80 mL beaker and vigorously homogenized with a spatula for 10 minutes to obtain the corresponding solvent-borne coating compositions.

[0128] Preparation of films from coating compositions Films were prepared from aqueous coating compositions prepared from the solid pigment preparations of Examples 10 and 12 ((a) freshly spray-dried or (b) stored at a temperature of 60°C for 10 days) and solvent-borne coating compositions prepared from the solid pigment preparations of Examples 10 and 12 ((a) freshly spray-dried or (b) stored at a temperature of 60°C for 10 days) as follows:

[0129] Each coating composition was applied to a glass plate (130 x 90 x 1 mm) and stretched wet and with uniform tension and pressure using a film stretching bar with a slot height of 200 μm (for aqueous coating compositions) or 100 μm (for solvent-based coating compositions). Care was taken to ensure the absence of air bubbles in the coating composition stripe. The film stretching bar was placed over the coating composition stripe and stretched uniformly across the plate. A stretch approximately 10 cm long and 6 cm wide was produced.

[0130] After the drawing procedure, the resulting wet coating on the glass plate was flashed off at room temperature (20°C) for 15 minutes, and then the coated glass plate was dried at 130°C for 15 minutes (for solvent-based coating compositions) and at room temperature (20°C) for 15 minutes, and then at 60°C for 15 minutes (for water-based coating compositions).

[0131] Color measurement The color properties of the films prepared from the aqueous and solvent-based coating compositions thus obtained were measured using a Byk mac i and BASF ColorCare software. The color was measured using a 45° measurement angle only. The measuring instrument was on the painted side after calibration with a white calibration tile and a black hollow body. The spectrometer averaged five individual measurements for each sample. Color value through glass L * a * b * was measured.

[0132] result The aqueous pigment dispersions of Examples 10 to 12 were all sprayable. The resulting solid pigment dispersions of Examples 10 to 12 all exhibited good redispersibility in water as well as in organic solvents, even after storage at high temperatures. Films prepared from the aqueous and solvent-based coating compositions incorporating such solid pigment dispersions exhibited similar color properties for each system before and after storage at high temperatures. [Table 10]

[0133] This demonstrates that for different types of pigments other than carbon black, stable solid pigment preparations can be obtained according to the present invention that have good dispersibility in both water-based and solvent-based systems, imparting desirable color properties to both water-based and solvent-based systems.< / dmea>

Claims

1. (a) at least one pigment; (b) an amine-functional acrylic block copolymer of at least vinylpyridine and one or more (meth)acrylate monomers; (c) an amine-functional polymeric dispersant that is a polyether-modified polymer based on polystyrene, comprising a polyoxyalkylene structure containing oxyethylene and / or oxypropylene units; and (d) an aqueous or organic solvent-based liquid carrier medium; A dispersion comprising:

2. The amine functional acrylic block copolymer (b) is - a copolymer of at least vinylpyridine and one or more acrylate monomers, including butyl (meth)acrylate; and / or - have an amine number of at least 20 mg KOH / g, and / or a weight average molecular weight M of at least 15,000 g / mol w having The dispersion of claim 1.

3. The amine functional polymeric dispersant (c) is - have an amine value of up to 30 mg KOH / g, and / or a weight average molecular weight M of at least 10,000 g / mol w having The dispersion according to claim 1 or 2.

4. 4. The dispersion of claim 1, comprising the amine-functional acrylic block copolymer (b) and the amine-functional polymer dispersant (c) comprising a polyoxyalkylene structure in a total amount ranging from 10 to 200 wt %, based on the total weight of the pigment (a).

5. 5. The dispersion of any one of claims 1 to 4, comprising the amine-functional acrylic block copolymer (b) and the amine-functional polymeric dispersant comprising a polyoxyalkylene moiety (c) in a weight ratio of from 5:95 to 70:

30.

6. The pigment (a) comprises carbon black; The carbon black has one, or more than one, or all of the following: (a) 500m 2 / g or less statistical thickness surface area (STSA), (b) Oil absorption amount (OAN) of 50 to 150 mL / 100 g, (c) a volatile content of 25% or less; The dispersion according to any one of claims 1 to 5.

7. The dispersion of any one of claims 1 to 6, wherein the pH of the dispersion is in the range of 8.5 to 11.

0.

8. A method for coloring a material, the method comprising incorporating a dispersion according to any one of claims 1 to 7 into said material.

9. The method of claim 8 , wherein the material is a fluid and the incorporating comprises stirring the dispersion in the fluid material.

10. A coloring material obtainable by the method according to claim 8 or 9.

11. The colorant of claim 10, wherein the colorant is a water-based or solvent-based paint, coating or ink composition.

12. 1. Use of a combination of (i) an amine-functional acrylic block copolymer of at least vinylpyridine and one or more (meth)acrylate monomers and (ii) an amine-functional polymeric dispersant that is a polystyrene-based polyether-modified polymer containing a polyoxyalkylene moiety containing oxyethylene and / or oxypropylene building blocks to disperse pigments.

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