WO2023208924A1 - Mixed crystal composition of quinacridones with diketopyrrolopyrroles and manufacturing process - Google Patents

Mixed crystal composition of quinacridones with diketopyrrolopyrroles and manufacturing process Download PDF

Info

Publication number
WO2023208924A1
WO2023208924A1 PCT/EP2023/060793 EP2023060793W WO2023208924A1 WO 2023208924 A1 WO2023208924 A1 WO 2023208924A1 EP 2023060793 W EP2023060793 W EP 2023060793W WO 2023208924 A1 WO2023208924 A1 WO 2023208924A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
pigment
quinacridone
quinacridone pigment
mixed crystal
Prior art date
Application number
PCT/EP2023/060793
Other languages
French (fr)
Inventor
Markus Hecht
Paul Pascal ROQUETTE
Stephane Biry
Original Assignee
Sun Chemical Corporation
Sun Chemical B.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sun Chemical Corporation, Sun Chemical B.V. filed Critical Sun Chemical Corporation
Publication of WO2023208924A1 publication Critical patent/WO2023208924A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0025—Crystal modifications; Special X-ray patterns
    • C09B67/0027—Crystal modifications; Special X-ray patterns of quinacridones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C09B67/0034—Mixtures of two or more pigments or dyes of the same type
    • C09B67/0036—Mixtures of quinacridones

Definitions

  • references do not refer to the composition of the products of the present application and do not refer to the targeted properties (hue, color strength, transparency). Furthermore, the references do not refer to the use of solvent-salt- kneading for the manufacturing of the mixed crystal as well as the overall composition.
  • PV 19 is 5, 12-dihydroquinolino[2,3-b]acridine-7, 14-dione (C.l. PV 19, CAS 1047-16-1).
  • PR 122 is 2, 9-dimethyl-5,12-dihydroquinolino[2,3-b]acridine-7, 14-dione (C.l. PR 122, CAS 980-26-7). It is known that PV 19 and PR 122 can form a mixed crystal in ratios of 85:15 to 60:40 by synthesis through co-cyclization reaction of a diarylaminoterephthalic acid and a dialkylarylaminoterephthalic acid in pholyphosphoric acid. The co-synthesis, however, only produces crude pigment and requires an additional finishing step to produce a useful pigment (e.g. EP3778784A1). This approach provides a magenta that is low in color strength and/or too bluish in hue.
  • PR 264 is 3, 6-bis-biphenyl-4-yl-2,5-dihydropyrrolo[3,4-c]pyrrole-1 , 4-dione (C.l. PR 264, CAS 88949-33-1).
  • PR 272 is 3,6-bis(4-methylphenyl)-2,5-dihydropyrrolo[3,4-c]pyrrole- 1 ,4-dione (C.l. PR 272, CAS 84632-66-6).
  • quinacridones can form solid solutions or mixed crystals by cosynthesis in the polyphosphoric acid process or by wet milling.
  • the co-synthesis only produces crude pigment and an additional finishing step is necessary to produce a useful pigment.
  • particle size and morphology are difficult to control.
  • the co-synthesis approach is already implemented at the nucleophilic substitution of a dialkyl succinyl succinate with an aniline derivate as in US2005011403A1 , the unsymmetric QA (quinacridone) is formed prompting the necessity of cumbersome global registration of C.l. PR 282.
  • producing the solid solution or mixed crystal by co-synthesis makes the control of the specific ratio of the individual components difficult as the yields of the individual syntheses differ.
  • the process of the present invention is advantageous in that the mixed crystal can be formed from crude pigment of the individual components (PV 19 and PR 122) by solvent-salt-kneading.
  • Solvent-salt-kneading aids as a comminution technology to reduce particle size and simultaneously enables re-growth of the crystals in a suitable solvent system.
  • the intense intermixing of the individual components facilitates the formation of solid solutions I mixed crystals.
  • the parameters influencing the particle size during the solvent-salt-kneading-process are known to persons skilled in the art and can be readily adjusted to tune the particle size and, therefore, the properties of the resulting pigment.
  • the crude pigment of the individual components comprises the pigment of the individual components (PV 19 and PR 122) as obtained from the synthesis of the individual components (PV 19 and PR 122), preferably as obtained from the synthesis without a finishing step, wherein the finishing step preferably comprises a modification selected from the group consisting of a particle size modification and a surface modification.
  • solid solutions may be defined as a crystalline material, which consists of a host compound and one or more guest compounds that are incorporated in the crystal lattice of the host. Therefore, the solid solution is characterized by the crystal lattice of the host.
  • mixed crystals may be defined as a crystalline material, which consists of two or more compounds and exhibits a crystal lattice that is different from the crystal lattices of the individual components.
  • a solid solution and a mixed crystal can be characterized, for example, by powder X-ray diffractometry.
  • a mixed crystal can be viewed as a type of solid solution.
  • the crude materials used in the solvent-salt-kneading process to form a mixed crystal can be synthesized separately; therefore, no co-synthesis is necessary.
  • solvent-salt- kneading simultaneously acts as comminution and re-growth process, no pre-milling of the material is necessary, and crude large-particle material can be utilized.
  • Another advantage is the ease of adding further components into the product (PR 264, PR 272 or any QA (quinacridone) synergist, DPP (d i keto pyrro Io pyrrole) synergist, resin or additive) by introducing the material into the solvent-salt-kneading process either before and/or during and/or after the formation of the QA (quinacridone) mixed-crystal.
  • the added material can be readily incorporated into the product and helps to adjust the coloristic properties and secondary properties (e.g. rheology, durability) of the product. Therefore, the invented approach acts as a one-step process compared to conventional methods that include several processes (milling, solvent finish, blending, etc.)
  • the crude materials used in the solvent-salt-kneading process comprise the materials as obtained from the synthesis of the individual material, preferably as obtained from the synthesis without a finishing step, wherein the finishing step preferably comprises a modification selected from the group consisting of a particle size modification and a surface modification.
  • the crude large-particle materials comprise materials as obtained from the synthesis of the individual components, preferably as obtained from the synthesis without a finishing step, wherein the finishing step preferably comprises a modification selected from the group consisting of a particle size modification and a surface modification.
  • Solvent-salt-kneading is a highly versatile method to produce solid solutions or mixed crystals as it can be easily adapted to different chemistries without the necessity of cosynthesis.
  • Solvent-salt-kneading simultaneously facilitates the formation of a solid solution or mixed crystal and finishes the material by comminution and re-growth into optimized particle sizes and distributions. Therefore, solvent-salt-kneading is a one-step process (formation of mixed crystal + finishing) compared to state-of-the-art multi-step processes requiring formation of mixed crystal followed by milling, finishing, blending steps.
  • a pigment finished in such a one-step procedure exhibits more homogeneous particle size for both the mixed crystal and the physical mixture components, and therefore exhibits equal or very similar dispersion properties for each of its components. This is highly advantageous for color matching compared to paints I inks that are prepared with several components blended in a mill base (e.g. EP3480264B1).
  • the present composition differentiates itself from industry standards, as it is a halogen- free, yellowish magenta with excellent color strength and transparency. No other commercially available pigment matches these properties.
  • the present application describes a one-step solvent-salt-kneading process for making a magenta pigment consisting of a mixed crystal of two quinacridones (PV 19 and PR 122).
  • the magenta pigment would further comprise in the ratio of 60:40 to 85:15 or 60:40 to 75:25 in a physical mixture with at least one diketopyrrolopyrrole (Pigment Red 264 and Pigment Red 272) contributing 1-15wt% or 4-10wt% the total composition.
  • the composition can furthermore optionally include 0- 15% of a quinacridone synergist, for example a monosulfonic acid metal salt derivative of PV 19.
  • the composition is advantageously manufactured in a one-step process by solvent-salt-kneading.
  • Yellow-shade magenta (“process red” colors) mostly constitute azo-pigments (e.g. PR 57:1 ; PR 48:2; PR 146, PR 269) that are known to not be able to match the excellent properties of high-performance pigments such as quinacridones or diketopyrrolopyrroles. Furthermore, among the mentioned azo-pigments, only PR 57:1 is chlorine-free.
  • composition of the present application formed by a solvent-salt-kneading process, offers a unique chlorine-free, high-performance alternative to azo-pigments in the field of “process red” colors for printing applications.
  • Quinacridone-based magentas such as PV 19 or a mixed crystal of PV 19 and PR 122 are chlorine-free and considered high-performance pigments, but cannot meet the requirements regarding hue, transparency and color strength.
  • the quinacridone mixed crystal indicates a quinacridone mixed crystal, which contains PV 19 and PR 122 as essential components; more specifically, a quinacridone solid solution in which a mixed crystal phase of PR 122 and PV 19 is formed. Accordingly, this mixed crystal has inherent peaks at 5.9° ⁇ 0.2° 20 and 11 .9° ⁇ 0.2° of the diffraction angle as measured by powder X-ray diffraction, which are not present in any of the single crystal of PV 19 and the single crystal of PR 122. Therefore, it is possible to easily check by crystal X-ray diffraction whether the quinacridone pigment is a mixed crystal or merely a mixture of the single crystals.
  • composition of the present application further contains either PR 264 or PR 272 as well as possibly a quinacridone synergist, e.g. a monosulfonic acid metal salt derivative of PV 19 in a physical mixture with the mixed crystal described above.
  • a quinacridone synergist e.g. a monosulfonic acid metal salt derivative of PV 19 in a physical mixture with the mixed crystal described above.
  • the presence of either can be found, for example, by mass spectrometry.
  • composition of the present invention may advantageously be prepared by solvent- salt-kneading, which facilitates the formation of the quinacridone mixed crystal by intense intermixing in the continuous comminution and re-growth during the process.
  • Solvent-salt-kneading is carried out with an organic solvent, for example one or more of ethylene glycol, diethylene glycol, diacetone alcohol, dimethylformamide, glycerine, triethylene glycol, dipropylene glycol, ethylene glycol monobutyl ether, methyl ethyl ketone, cyclohexanone, dimethylacetamide, N-methylpyrrolidone, butyl acetate, glycerol triacetate, sulfolane, xylene, tetrahydrofuran, butanol, water and dimethyl sulfoxide.
  • the at least one solvent comprises one or more of diethylene glycol, diacetone alcohol, and glycerine.
  • the at least one solvent is diethylene glycol.
  • quinacridone synergists for example sulfonic acid derivatives and/or salts of quinacridone; formaldehyde reaction products with 5,12-dihydroquino[2,3-b]acridine- 7, 14-dione and 3,5-dimethyl-1 H-pyrazole; formaldehyde reaction products with 5,12- dihydroquino[2,3-b]acridine-7, 14-dione and 3, 5-dimethyl-1 H-pyrazole, sulfonated or 2- [(1 ,3-Dihydro-1 , 3-d ioxo-2H-isoindol-2-yl)methyl]-5,12-dihydroquino[2,3-b]acridine-7, 14- dione.
  • quinacridone synergists for example sulfonic acid derivatives and/or salts of quinacridone
  • synergists for example a natural or synthetic resin comprising esters and salts of abietic acid; hydrated or partially hydrogenated or dimerized rosin; a polysorbate-type nonionic surfactant comprising an ester or a mixture of esters formed from fatty acids, such as lauric or sebacic acid; and polyols, such as like sorbitic monolaureate or dibutylsebacate.
  • the synergist may be added either before and/or during and/or after kneading and/or grinding.
  • the mixed crystal of PR 122 and PV 19 exhibits two signals at 5.9° ⁇ 0.2° 20 and 11 .9° ⁇ 0.2° 20 that are both not present in the diffractograms of the individual components, nor in the lattice of a typical commercial PR 122 solid solution, such as Hostaperm Pink E (Heubach). These signals are well separated from other signals in the diffractograms and are, therefore, ideal to characterize the mixed crystal.
  • the successful formation of the mixed crystal can be evaluated by the intensity ratio of the two signals.
  • Intensity ratio (Diffraction peak intensity at a diffraction angle 20 of around 5.9°) I (Diffraction peak intensity at a diffraction angle 20 of around 11 .9°) > 3.
  • Solvent-salt-kneading uses an inorganic salt as grinding medium, for example sodium chloride, sodium sulfate or anhydrous aluminium sulfate or a mixture thereof.
  • the pigment to salt ratio is between 1 :3 and 1 :18.
  • Solvent-salt- kneading is advantageously performed at temperatures between 25°C and 120°C, such as between 40°C and 100°C, or between 60°C and 80°C.
  • Solvent-salt-kneading is typically carried out for 4 hours to 48 hours, such as 6 hours to 24 hours, or 8 hours to 18 hours.
  • the pigment is formed as crystalline particles with particle sizes Dv(50) ⁇ 150 nm.
  • the pigment has a particle size distribution Dv(50) in the rage of from 10 to 145 nm, more preferably 20 to 140 nm, more preferably from 25 to 130 nm, more preferably from 30 to 120 nm.
  • the individual crude components can be of significantly larger particle size and still result in product with excellent coloristic properties.
  • the mixed crystal quinacridone pigment composition has a particle size distribution of Dv(50) ⁇ 150 nm, preferably the mixed crystal quinacridone pigment composition has a particle size distribution of Dv(50) in the range of from 10 to 145 nm, more preferably from 20 to 140 nm, more preferably from 25 to 130 nm, more preferably from 30 to 120 nm, determined according to reference example 5.
  • the method further comprises grinding the crude quinacridone pigment in the presence of a diketopyrrolopyrrole selected from the group consisting of PR 264, PR 272 and a mixture thereof.
  • PV 19 is 5,12-dihydroquinolino[2,3- b]acridine-7, 14-dione and/or PR 122 is 2,9-dimethyl-5,12-dihydroquinolino[2,3- b]acridine-7, 14-dione and/or PR 264 is 3,6-bis-biphenyl-4-yl-2,5-dihydropyrrolo[3,4- c]pyrrole-1 , 4-dione and/or PR 272 is 3,6-bis(4-methylphenyl)-2,5-dihydropyrrolo[3,4- c]pyrrole-1 , 4-dione.
  • the 1-step solvent-salt-kneading process is a solvent-salt-kneading process.
  • the crude quinacridone pigment comprises the pigment as obtained from the synthesis of the quinacridone pigment, preferably as obtained from the synthesis without a finishing step, wherein the finishing step preferably comprises a modification selected from the group consisting of a particle size modification and a surface modification.
  • the temperature is ranging from 60 to 90°C, preferably from 40 to 90°C, more preferably from 80 to 90 °C or the temperature is ranging from 45 to 100 °C, preferably from 50 to 90 °C.
  • the inorganic salt is selected from the group consisting of alkali metal halide, alkali metal sulfate, alkaline earth metal halide, alkaline earth metal sulfate, and a mixture of two or more thereof, preferably wherein the inorganic salt is selected from the group consisting of sodium chloride, sodium sulfate, anhydrous aluminium sulfate, and a mixture of two or more thereof, more preferably wherein the inorganic salt is sodium chloride.
  • the solubility of the crude quinacridone pigment and the salt in the organic liquid is in the range of from 0 to 10 g/L, preferably from 0.0001 to 9.5 g/L, more preferably from 0.0005 to 9 g/L, at a temperature in the range of from 20 to 25 °C.
  • the salt comprises an inorganic salt.
  • the mixed crystal quinacridone pigment composition comprises a quinacridone synergist, wherein from 0 to 10 wt% of the mixed crystal quinacridone pigment composition consist of the quinacridone synergist.
  • the particle size distribution Dv(50) is determined according to reference example 5.
  • the quinacridone pigment has a particle size distribution of Dv(50) in the range of from 10 to 145 nm, preferably from 20 to 140 nm, more preferably from 25 to 130 nm, more preferably from 30 to 120 nm, determined according to reference example 5.
  • the organic liquid comprises a solvent.
  • the crude components comprise the components as obtained in the synthesis of the individual component, preferably as obtained from the synthesis without a finishing step, wherein the finishing step preferably comprises a modification selected from the group consisting of a particle size modification and a surface modification.
  • the finishing step preferably comprises a modification selected from the group consisting of a particle size modification and a surface modification.
  • a method of making a mixed crystal quinacridone pigment composition comprising a 1-step solvent-salt-kneading process, comprising the steps of:
  • step (b) discharging the crude quinacridone pigment from step (a) into water; thereby attaining a water pigment mixture;
  • composition comprises a combination of PV 19 and PR 122, preferably wherein the composition is a combination of PV 19 and PR 122.
  • the mixed crystal quinacridone pigment composition has a particle size distribution of Dv(50) ⁇ 150 nm, preferably the mixed crystal quinacridone pigment composition has a particle size distribution of Dv(50) in the range of from 10 to 145 nm, more preferably from 20 to 140 nm, more preferably from 25 to 130 nm, more preferably from 30 to 120 nm, determined according to reference example 5.
  • PV 19 is 5,12- dihydroquinolino[2,3-b]acridine-7, 14-dione and/or PR 122 is 2,9-dimethyl-5,12- dihydroquinolino[2,3-b]acridine-7, 14-dione and/or PR 264 is 3,6-bis-biphenyl-4-yl-
  • 2.5-dihydropyrrolo[3,4-c]pyrrole-1 , 4-dione and/or PR 272 is 3,6-bis(4-methylphenyl)-
  • the crude quinacridone pigment comprises the pigment as obtained from the synthesis of the quinacridone pigment, preferably as obtained from the synthesis without a finishing step, wherein the finishing step preferably comprises a modification selected from the group consisting of a particle size modification and a surface modification.
  • the temperature is ranging from 60 to 90°C, preferably from 40 to 90°C, more preferably from 80 to 90 °C or the temperature is ranging from 45 to 100 °C, preferably from 50 to 90 °C.
  • the inorganic salt is selected from the group consisting of alkali metal halide, alkali metal sulfate, alkaline earth metal halide, alkaline earth metal sulfate, and a mixture of two or more thereof, preferably wherein the inorganic salt is selected from the group consisting of sodium chloride, sodium sulfate, anhydrous aluminium sulfate, and a mixture of two or more thereof, more preferably wherein the inorganic salt is sodium chloride.
  • the solubility of the crude quinacridone pigment and the salt in the organic liquid is in the range of from 0 to 10 g/L, preferably from 0.0001 to 9.5 g/L, more preferably from 0.0005 to 9 g/L, at a temperature in the range of from 20 to 25 °C.
  • the mixed crystal quinacridone pigment composition comprises a quinacridone synergist, wherein from 0 to 10 wt% of the mixed crystal quinacridone pigment composition consist of the quinacridone synergist.
  • the quinacridone pigment has a particle size distribution of Dv(50) in the range of from 10 to 145 nm, preferably from 20 to 140 nm, more preferably from 25 to 130 nm, more preferably from 30 to 120 nm, determined according to reference example 5.
  • any preceding paragraph comprising a solvent selected from the group consisting of ethylene glycol, diethylene glycol, diacetone alcohol, dimethylformamide, glycerine, triethylene glycol, dipropylene glycol, ethylene glycol monobutyl ether, methyl ethyl ketone, cyclohexanone, dimethylacetamide, N- methylpyrrolidone, butyl acetate, glycerol triacetate, sulfolane, xylene, tetrahydrofuran, butanol, water, dimethyl sulfoxide and blends thereof, preferably the solvent is selected from the group consisting of ethylene glycol, diethylene glycol, diacetone alcohol, dimethylformamide, glycerine, triethylene glycol, dipropylene glycol, ethylene glycol monobutyl ether, methyl ethyl ketone, cyclohexanone, dimethylacetamide, N-methylpyrrolidone
  • At least one solvent comprises one or more of diethylene glycol, diacetone alcohol, and glycerine, preferably the solvent is diethylene glycol.
  • the synergist is a quinacridone derivative selected from the group consisting of quinacridone sulfonic acids and salts thereof, phthalimidoalkyl-quinacridones, imidazolylalkyl-quinacridones, pyrazolylalkyl-quinacridones, sulfonic acids and salts of pyrazolylalkyl-quinacridones, and dialkylaminoalkylsulfonamide derivatives of quinacridones.
  • quinacridone derivative selected from the group consisting of quinacridone sulfonic acids and salts thereof, phthalimidoalkyl-quinacridones, imidazolylalkyl-quinacridones, pyrazolylalkyl-quinacridones, sulfonic acids and salts of pyrazolylalkyl-quinacridones, and dialkylaminoalkylsulfonamide derivatives of quinacridones.
  • synergist is selected from the group consisting of sulfonic acid derivatives and/or salts of quinacridone; quino[2,3- b]acridine-2-sulfonic acid, 5,7,12,14-tetrahydro-7,14-dioxo-, and its metal salt; formaldehyde reaction products with 5, 12-dihydroquino[2,3-b]acridine-7, 14-dione and 3,5-dimethyl-1 H-pyrazole; formaldehyde reaction products with 5,12- dihydroquino[2,3-b]acridine-7, 14-dione and 3,5-dimethyl-1 H-pyrazole, sulfonated or 2-[(1 ,3-dihydro-1 ,3-dioxo-2H-isoindol-2-yl)methyl]-5,12-dihydroquino[2,3-b]acridine- 7, 14-dione
  • synergist is present in the amount of 1-10 wt% relative to the crude quinacridone pigment, preferably the synergist in (a)(iii) is present in the amount of 1-10 wt% relative to the crude quinacridone pigment in (a).
  • synergist is present in the amount of 1-5 wt% relative to the crude quinacridone pigment, preferably the synergist in (a)(iii) is present in the amount of 1-5 wt% relative to the crude quinacridone pigment in (a).
  • synergist is present in a range of about 0.001 to about 0.1 parts by weight, relative to the crude quinacridone pigment, preferably the synergist in (a)(iii) is present in a range of about 0.001 to about 0.1 parts by weight, relative to the crude quinacridone pigment in (a).
  • a narrow particle size distribution obtained with Dv(50) is ⁇ 150 nm, preferably the narrow particle size distribution obtained with Dv(50) is in the rage of from 10 to 145 nm, more preferably from 20 to 140 nm, more preferably from 25 to 130 nm, more preferably from 30 to 120 nm, determined according to reference example 5.
  • the composition is characterised by powder X-ray diffractometry signals at the diffraction angles 20 at about 5.9° ⁇ 0.2° and 11.9° ⁇ 0.2°.
  • composition is further characterised by powder X-ray diffractometry signals at the diffraction angles of 8.0° ⁇ 0.2° 20 and 17.9° ⁇ 0.2° 20 after adding PR 264.
  • composition is further characterised by powder X-ray diffractometry signals at the diffraction angles of 7.7° ⁇ 0.2° 20 and 15.7° ⁇ 0.2° 20 after adding PR 272.
  • a mixed crystal quinacridone pigment composition resulting from the method of any one or more of paragraphs 1-28.
  • the pigment composition of paragraphs 29 or 30, wherein the amount of quinacridone pigment derivative contained is from 0.1 to 10 parts by mass, relative to 100 parts by mass of pigment, preferably the amount of quinacridone pigment derivative contained in (a)(iii) is from 0.1 to 10 parts by mass, relative to 100 parts by mass of the mixed crystal quinacridone pigment composition.
  • the pigment composition of paragraphs 29 or 30, wherein the amount of quinacridone pigment derivative contained is from 0.5 to 3 parts by mass, preferably from 1 to 3 parts by mass, relative to 100 parts by mass of pigment, preferably the amount of quinacridone pigment derivative contained in (a)(iii) is from 0.5 to 3 parts by mass, preferably from 1 to 3 parts by mass, relative to 100 parts by mass of the mixed crystal quinacridone pigment composition.
  • a printing ink or coating or plastic composition comprising the pigment composition of any one or more of paragraphs 29-35.
  • composition of paragraph 37, wherein the composition is suitable for use as a digital printing ink, inkjet ink, electrophotographic toner, aqueous ink, UV- curable ink, solvent-based ink or oil-based ink.
  • a printed or coated article comprising the printing ink or coating composition of any one or more of paragraphs 35-38.
  • a plastic article comprising the pigment composition of any one or more of paragraphs 29-35.
  • the present invention relates to a method for making a mixed crystal quinacridone pigment composition, the method comprising
  • an organic liquid selected from the group consisting of ethylene glycol, diethylene glycol, diacetone alcohol, dimethylformamide, glycerine, triethylene glycol, dipropylene glycol, ethylene glycol monobutyl ether, methyl ethyl ketone, cyclohexanone, dimethylacetamide, N-methylpyrrolidone, butyl acetate, glycerol triacetate, sulfolane, xylene, tetra hydrofuran, dimethyl sulfoxide and a mixture of two or more thereof; and (iii) 0 to 10 wt% of a synergist, based on the mixed crystal quinacridone pigment composition;
  • step (b) discharging the ground at least two quinacridone pigments from step (a) into water;
  • step (c) isolating the ground at least two quinacridone pigments from step (b); wherein the ground at least two quinacridone pigments have a particle size distribution of Dv(50) is in the range of from 10 to 145 nm.
  • the mixed crystal quinacridone pigment composition comprises PV 19 and PR 122.
  • the at least two quinacridone pigments comprise PV 19 and PR 122.
  • PV 19 and PR 122 are present in the ratio of 60:40 to 85:15 or 60:40 to 75:25.
  • PV 19 is 5, 12-dihydroquinolino[2,3-b]acridine-7, 14-dione and/or PR 122 is 2,9-dimethyl-5,12-dihydroquinolino[2,3-b]acridine-7, 14-dione.
  • the method further comprises a diketopyrrolopyrrole selected from the group consisting of PR 264, PR 272 and a mixture thereof, wherein preferably PR 264 is 3, 6-bis-biphenyl-4-yl-2,5-dihydropyrrolo[3,4-c]pyrrole-1 ,4-dione and PR 272 is 3,6-bis(4- methylphenyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1 , 4-dione.
  • PR 264 is 3, 6-bis-biphenyl-4-yl-2,5-dihydropyrrolo[3,4-c]pyrrole-1 ,4-dione
  • PR 272 is 3,6-bis(4- methylphenyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1 , 4-dione.
  • the amount of the diketopyrrolopyrrole is in the range of from 0.1 to 15 wt%, preferably from 1 to 15 wt%, more preferably from 5 to 10 wt% based on the mixed crystal quinacridone pigment composition.
  • the at least two quinacridone pigments comprise at least two crude quinacridone pigments, wherein the at least two crude pigments comprise at least two quinacridone pigments as obtained from the synthesis of the at least two quinacridone pigments, preferably as obtained from the synthesis without a finishing step, wherein the finishing step preferably comprises a modification selected from the group consisting of a particle size modification and a surface modification.
  • the temperature is in the range of from 60 to 90°C, preferably from 40 to 90°C, more preferably from 80 to 90 °C or the temperature is in the range of from 45 to 100 °C, preferably from 50 to 90 °C.
  • the inorganic salt is selected from the group consisting of alkali metal halide, alkali metal sulfate, alkaline earth metal halide, alkaline earth metal sulfate, and a mixture of two or more thereof, preferably wherein the inorganic salt is selected from the group consisting of sodium chloride, sodium sulfate, anhydrous aluminium sulfate, and a mixture of two or more thereof, more preferably wherein the inorganic salt is sodium chloride.
  • the at least two quinacridone pigments and the inorganic salt are substantially insoluble in the organic liquid, preferably wherein the solubility of the at least two quinacridone pigments and the inorganic salt in the organic liquid is in the range of from 0 to 10 g/L, preferably from 0.0001 to 9.5 g/L, more preferably from 0.0005 to 9 g/L, at a temperature in the range of from 20 to 25 °C.
  • the solubility of the at least two quinacridone pigments is determined by methods known to a skilled person.
  • particle size distribution of Dv(50) is determined according to reference example 5.
  • the ground at least two quinacridone pigments have a particle size distribution of Dv(50) in the range of from, 20 to 140 nm, preferably from 25 to 130 nm, more preferably from 30 to 120 nm, determined according to reference example 5.
  • the mixed crystal quinacridone pigment composition has a particle size distribution of Dv(50) ⁇ 150 nm, preferably the mixed crystal quinacridone pigment composition has a particle size distribution of Dv(50) in the range of from 10 to 145 nm, more preferably from 20 to 140 nm, more preferably from 25 to 130 nm, more preferably from 30 to 120 nm, determined according to reference example 5.
  • (a) further comprises grinding the crude quinacridone pigment in the presence of a diketopyrrolopyrrole selected from the group consisting of PR 264, PR 272 and a mixture thereof.
  • the organic liquid is selected from the group consisting of diethylene glycol, glycerine, diacetone alcohol, and a mixture of two or more thereof, preferably the organic liquid is diethylene glycol.
  • the synergist in (a)(iii) is a quinacridone derivative selected from the group consisting of quinacridone sulfonic acids and salts thereof, phthalimidoalkyl- quinacridones, imidazolylalkyl-quinacridones, pyrazolylalkyl-quinacridones, sulfonic acids and salts of pyrazolylalkyl-quinacridones, dialkylaminoalkylsulfonamide derivatives of quinacridones, and a mixture of two or more thereof.
  • the synergist in (a)(iii) is a quinacridone derivative
  • the quinacridone derivative is selected from the group consisting of sulfonic acid derivatives and/or salts of quinacridone; quino[2,3-b]acridine-2-sulfonic acid, 5,7,12,14-tetrahydro-7,14-dioxo-, and its metal salt; formaldehyde reaction products with 5,12-dihydroquino[2,3-b]acridine- 7, 14-dione and 3,5-dimethyl-1 H-pyrazole; formaldehyde reaction products with 5,12- dihydroquino[2,3-b]acridine-7, 14-dione and 3, 5-dimethyl-1 H-pyrazole, sulfonated or 2- [(1 ,3-dihydro-1 ,3-dioxo-2H-isoindol-2-yl)methyl]-5,12-dihydroquino[2,3
  • the synergist in (a)(iii) is selected from the group consisting of a natural or synthetic resin comprising esters and salts of abietic acid; a hydrated or partially hydrogenated or dimerized rosin; a polysorbate-type nonionic surfactant comprising an ester or a mixture of esters formed from fatty acids, preferably from lauric or sebacic acid; polyols, preferably sorbitan monolaureate and dibutylsebacate; and a mixture of two or more thereof.
  • synergist in (a)(iii) is present in an amount of 1-10 wt% based on the at least two quinacridone pigments in (a), preferably in an amount of 1-5 wt% based on the at least two quinacridone pigments in (a).
  • synergist in (a)(iii) is present in a range of 0.001 to 0.1 parts by weight, based on the at least two quinacridone pigments in (a).
  • the mixed crystal quinacridone pigment composition comprising the at least two quinacridone pigments has a particle size distribution of Dv(50) in the rage of from 10 to 145 nm, preferably from 20 to 140 nm, more preferably from 25 to 130 nm, more preferably from 30 to 120 nm, determined according to reference example 5.
  • the mixed crystal quinacridone pigment composition is characterised by powder X-ray diffractometry signals at the diffraction angles 20 at 5.9° ⁇ 0.2° and 11.9° ⁇ 0.2°.
  • the mixed crystal quinacridone pigment composition is further characterised by powder X-ray diffractometry signals at the diffraction angles 20 at 8.0° ⁇ 0.2° and 17.9° ⁇ 0.2° after adding PR 264.
  • the mixed crystal quinacridone pigment composition is further characterised by powder X-ray diffractometry signals at the diffraction angles 20 at 7.7° ⁇ 0.2° and 15.7° ⁇ 0.2° after adding PR 272.
  • the method comprises a 1-step solvent-salt-kneading process.
  • the present invention also relates to a mixed crystal quinacridone pigment composition, obtainable or obtained according to the method of any one of the particular and preferred embodiments of the present invention for the production of a mixed crystal quinacridone pigment composition.
  • the mixed crystal quinacridone pigment composition has a ratio of a diffraction peak intensity at a diffraction angle 20 of 5.9 ⁇ 0.2° to a diffraction peak intensity at a diffraction angle of 20 of 11 .9 ⁇ 0.2°C is 3 or higher, preferably the ratio of a diffraction peak intensity at a diffraction angle 20 of 5.9 ⁇ 0.2° to a diffraction peak intensity at a diffraction angle of 20 of 11 .9 ⁇ 0.2°C is in the range of from 3 to 20, more preferably from 6 to 10, as measured by powder X-ray diffractometry, preferably the ratio of the diffraction peak intensity is measured according to reference example 4, described therein.
  • the amount of the synergist of the mixed crystal quinacridone pigment composition is in the range of from 0.1 to 10 parts by mass, preferably from 0.5 to 3 parts by mass or from 1 to 5 parts by mass, relative to 100 parts by mass of the mixed crystal quinacridone pigment composition.
  • the particle size distribution of Dv(50) the mixed crystal quinacridone pigment composition is in the rage of from 10 to 145 nm, preferably from 20 to 140 nm, more preferably from 25 to 130 nm, more preferably from 30 to 120 nm, determined according to reference example 5 described therein.
  • the mixed crystal quinacridone pigment composition is chlorine-free.
  • the present invention also relates to a printing ink or coating or plastic composition comprising the mixed crystal quinacridone pigment composition of any one of the particular and preferred embodiments of the present invention. It is preferred that the printing ink or coating composition of the present invention is suitable for use as printing ink, automotive coating, architectural coating or industrial coating. It is preferred that the printing ink composition of of the present invention is suitable for use as a digital printing ink, inkjet ink, electrophotographic toner, aqueous ink, UV-curable ink, solvent-based ink or oil-based ink.
  • the present invention also relates to a printed or coated article comprising the printing ink or coating composition of any one of the particular and preferred embodiments of the present invention.lt is preferred that the printed article is a plastic article.
  • the present invention also relates to a plastic article comprising the mixed crystal quinacridone pigment composition of any one of the particular and preferred embodiments of the present invention.
  • the present invention is further illustrated by the following set of embodiments and combinations of embodiments resulting from the dependencies and back-references as indicated.
  • every embodiment in this range is meant to be explicitly disclosed for the skilled person, i.e. the wording of this term is to be understood by the skilled person as being synonymous to "The method of any one of embodiments 1 , 2, 3 and 4".
  • the following set of embodiments represents a suitably structured part of the general description directed to preferred aspects of the present invention, and, thus, suitably supports, but does not represent the claims of the present invention.
  • a method for making a mixed crystal quinacridone pigment composition comprising
  • an organic liquid selected from the group consisting of ethylene glycol, diethylene glycol, diacetone alcohol, dimethylformamide, glycerine, triethylene glycol, dipropylene glycol, ethylene glycol monobutyl ether, methyl ethyl ketone, cyclohexanone, dimethylacetamide, N-methylpyrrolidone, butyl acetate, glycerol triacetate, sulfolane, xylene, tetrahydrofuran, dimethyl sulfoxide and a mixture of two or more thereof; and (iii) 0 to 10 wt% of a synergist, based on the mixed crystal quinacridone pigment composition;
  • step (b) discharging the ground at least two quinacridone pigments from step (a) into water;
  • step (c) isolating the ground at least two quinacridone pigments from step (b); wherein the ground at least two quinacridone pigments have a particle size distribution of Dv(50) is in the range of from 10 to 145 nm.
  • the at least two quinacridone pigments comprise at least two crude quinacridone pigments, wherein the at least two crude pigments comprise at least two quinacridone pigments as obtained from the synthesis of the at least two quinacridone pigments, preferably as obtained from the synthesis without a finishing step, wherein the finishing step preferably comprises a modification selected from the group consisting of a particle size modification and a surface modification.
  • the temperature is in the range of from 60 to 90°C, preferably from 40 to 90°C, more preferably from 80 to 90 °C or the temperature is in the range of from 45 to 100 °C, preferably from 50 to 90 °C.
  • the inorganic salt is selected from the group consisting of alkali metal halide, alkali metal sulfate, alkaline earth metal halide, alkaline earth metal sulfate, and a mixture of two or more thereof, preferably wherein the inorganic salt is selected from the group consisting of sodium chloride, sodium sulfate, anhydrous aluminium sulfate, and a mixture of two or more thereof, more preferably wherein the inorganic salt is sodium chloride.
  • the mixed crystal quinacridone pigment composition has a particle size distribution of Dv(50) ⁇ 150 nm, preferably the mixed crystal quinacridone pigment composition has a particle size distribution of Dv(50) in the range of from 10 to 145 nm, more preferably from 20 to 140 nm, more preferably from 25 to 130 nm, more preferably from 30 to 120 nm, determined according to reference example 5.
  • (a) further comprises grinding the crude quinacridone pigment in the presence of a diketopyrrolopyrrole selected from the group consisting of PR 264, PR 272 and a mixture thereof.
  • the organic liquid is selected from the group consisting of diethylene glycol, glycerine, diacetone alcohol, and a mixture of two or more thereof, preferably the organic liquid is diethylene glycol.
  • the synergist in (a)(iii) is a quinacridone derivative selected from the group consisting of quinacridone sulfonic acids and salts thereof, phthalimidoalkyl-quinacridones, imidazolylalkyl- quinacridones, pyrazolylalkyl-quinacridones, sulfonic acids and salts of pyrazolylalkyl-quinacridones, dialkylaminoalkylsulfonamide derivatives of quinacridones, and a mixture of two or more thereof.
  • the quinacridone derivative is selected from the group consisting of sulfonic acid derivatives and/or salts of quinacridone; quino[2,3-b]acridine-2-sulfonic acid, 5,7,12,14-tetrahydro-7,14-dioxo-, and its metal salt; formaldehyde reaction products with 5, 12-dihydroquino[2,3-b]acridine-7, 14- dione and 3,5-dimethyl-1 H-pyrazole; formaldehyde reaction products with 5,12- dihydroquino[2,3-b]acridine-7, 14-dione and 3, 5-dimethyl-1 H-pyrazole, sulfonated or 2-[(1 ,3-dihydro-1 ,3-dioxo-2H-isoindol-2-yl)methyl]-5,12-dihydroquino[2,3-b]acridine- 7,14-dione, and a mixture of two
  • synergist in (a)(iii) is selected from the group consisting of a natural or synthetic resin comprising esters and salts of abietic acid; a hydrated or partially hydrogenated or dimerized rosin; a polysorbate-type nonionic surfactant comprising an ester or a mixture of esters formed from fatty acids, preferably from lauric or sebacic acid; polyols, preferably sorbitan monolaureate and dibutylsebacate; and a mixture of two or more thereof.
  • the mixed crystal quinacridone pigment composition comprising the at least two quinacridone pigments has a particle size distribution of Dv(50) in the rage of from 10 to 145 nm, preferably from 20 to 140 nm, more preferably from 25 to 130 nm, more preferably from 30 to 120 nm, determined according to reference example 5.
  • the mixed crystal quinacridone pigment composition is characterised by powder X-ray diffractometry signals at the diffraction angles 20 at 5.9° ⁇ 0.2° and 11 .9° ⁇ 0.2°.
  • the mixed crystal quinacridone pigment composition is further characterised by powder X-ray diffractometry signals at the diffraction angles 20 at 8.0° ⁇ 0.2° and 17.9° ⁇ 0.2° after adding PR 264.
  • the method of embodiment 23, wherein the mixed crystal quinacridone pigment composition is further characterised by powder X-ray diffractometry signals at the diffraction angles 20 at 7.7° ⁇ 0.2° and 15.7° ⁇ 0.2° after adding PR 272. 26.
  • a mixed crystal quinacridone pigment composition obtainable or obtained by the method of any one of embodiments 1 to 26.
  • a printing ink or coating or plastic composition comprising the mixed crystal quinacridone pigment composition of any one of embodiments 27 to 31 .
  • 33. The printing ink or coating composition of embodiment 32, wherein the composition is suitable for use as printing ink, automotive coating, architectural coating or industrial coating.
  • a printed or coated article comprising the printing ink or coating composition of any one of embodiments 32 to 34.
  • a plastic article comprising the mixed crystal quinacridone pigment composition of any one of embodiments 27 to 31 .
  • a kneading apparatus (duplex-blade kneader) with a capacity of 0.6 litre was charged with 20.0 g of crude y-PV 19 and 11.1 g of PR 122. 214.3 g of sodium chloride and 45.0 g of diethylene glycol (DEG) were added to the kneader. The walls of the apparatus were thermostated at 80°C. After 12 h of kneading, 3.6 g of PR 264 and 1.1 g of a monosulfonic acid metal salt derivative of PV 19 was added and kneading was continued for 12 h with the walls thermostated at 80 °C.
  • DEG diethylene glycol
  • the yield of the obtained pigment was 34.1 g and comprised 56% PV 19 and 31 % PR 122 in a mixed crystal as a physical mixture with 10% PR 264 and 3% of a monosulfonic acid metal salt derivative of PV 19.
  • the pigment was pulverized in a mill to obtain a magenta powder.
  • a kneading apparatus (duplex-blade kneader) with a capacity of 0.6 litre was charged with 21.7 g of crude y-PV 19 and 9.3 g of PR 122. 214.3 g of sodium chloride and 45.0 g of diethylene glycol (DEG) were added to the kneader. The walls of the apparatus were thermostated at 80°C. After 12 h of kneading, 3.6 g of PR 272 and 1.1 g of a monosulfonic acid metal salt derivative of PV 19 was added and kneading was continued for 12 h with the walls thermostated at 80°C.
  • DEG diethylene glycol
  • the kneading was stopped and 1 .6 L water was added to the kneading mass and stirred for 3 h.
  • the mixture was filtered and the pigment was washed with water until the conductivity of the filtrate was below 100 pS/cm.
  • the wet presscake was dried in an oven at 80°C for 24 h.
  • the yield of the obtained pigment was 34.5 g and comprised 61 % PV 19 and 26% PR 122 in a mixed crystal as a physical mixture with 10% PR 272 and 3% of a monosulfonic acid metal salt derivative of PV 19.
  • the pigment was pulverized in a mill to obtain a magenta powder.
  • a kneading apparatus (duplex-blade kneader) with a capacity of 0.6 litre was charged with 24.5 g of crude y-PV 19 and 8.2 g of PR 122. 214.3 g of sodium chloride and 45.0 g of diethylene glycol (DEG) were added to the kneader. The walls of the apparatus were thermostated at 80°C. After 6 h of kneading, 1.8 g of PR 272 and 1.1 g of a monosulfonic acid metal salt derivative of PV 19 was added and kneading was continued for 6 h with the walls thermostated at 80°C.
  • DEG diethylene glycol
  • the kneading was stopped and 1 .6 L water was added to the kneading mass and stirred for 3 h.
  • the mixture was filtered and the pigment was washed with water until the conductivity of the filtrate was below 100 pS/cm.
  • the wet presscake was dried in an oven at 80°C for 24 h.
  • the yield of the obtained pigment was 34.5 g and comprised 69% PV 19 and 23% PR 122 in a mixed crystal as a physical mixture with 5% PR 272 and 3% of a monosulfonic acid metal salt derivative of PV 19.
  • the pigment was pulverized in a mill to obtain a magenta powder.
  • a kneading apparatus (duplex-blade kneader) with a capacity of 0.6 litre was charged with 20.7 g of crude y-PV 19 and 11.4 g of PR 122. 214.3 g of sodium chloride and 45.0 g of diethylene glycol (DEG) were added to the kneader. The walls of the apparatus were thermostated at 80°C. After 12 h of kneading, 3.6 g of PR 272 was added and kneading was continued for 12 h with the walls thermostated at 75-80°C.
  • DEG diethylene glycol
  • the kneading was stopped and 1 .6 L water was added to the kneading mass and stirred for 3 h.
  • the mixture was filtered and the pigment was washed with water until the conductivity of the filtrate was below 100 pS/cm.
  • the wet presscake was dried in an oven at 80°C for 24 h.
  • the yield of the obtained pigment was 34.5 g and comprised 58% PV 19 and 32% PR 122 in a mixed crystal as a physical mixture with 10% PR 272.
  • the pigment was pulverized in a mill to obtain a magenta powder.
  • a kneading apparatus (duplex-blade kneader) with a capacity of 0.6 litre was charged with 20.7 g of crude y-PV 19 and 11.4 g of PR 122. 214.3 g of sodium chloride and 45.0 g of diethylene glycol (DEG) were added to the kneader. The walls of the apparatus were thermostated at 76-80°C. After 12 h of kneading, 3.6 g of PR 264 was added and kneading was continued for 12 h with the walls thermostated at 76 °C.
  • DEG diethylene glycol
  • the kneading was stopped and 1 .6 L water was added to the kneading mass and stirred for 3 h.
  • the mixture was filtered and the pigment was washed with water until the conductivity of the filtrate was below 100 pS/cm.
  • the wet presscake was dried in an oven at 80 °C for 24 h.
  • the yield of the obtained pigment was 34.9 g and comprised 58% PV 19 and 32% PR 122 in a mixed crystal as a physical mixture with 10% PR 264.
  • the pigment was pulverized in a mill to obtain a magenta powder.
  • a kneading apparatus (duplex-blade kneader) with a capacity of 0.6 litre was charged with 25.1 g of crude y-PV 19 and 8.4 g of PR 122. 214.3 g of sodium chloride and 45.0 g of diethylene glycol (DEG) were added to the kneader. The walls of the apparatus were thermostated at 80°C. After 6 h of kneading, 1.8 g of PR 264 and 0.4 g of a monosulfonic acid metal salt derivative of PV 19 was added and kneading was continued for 6 h with the walls thermostated at 80°C.
  • DEG diethylene glycol
  • the yield of the obtained pigment was 34.9 g and comprised 70% PV 19 and 24% PR 122 in a mixed crystal as a physical mixture with 5% PR 272 and 1 % of a monosulfonic acid metal salt derivative of PV 19.
  • the pigment was pulverized in a mill to obtain a magenta powder.
  • a kneading apparatus (duplex-blade kneader) with a capacity of 0.6 litre was charged with 18.8g of crude y-PV 19 and 12.9g of PR 122. 214.3 g of sodium chloride and 45.0 g of diethylene glycol (DEG) were added to the kneader. The walls of the apparatus were thermostated at 75°C. After 12 h of kneading, 3.6 g of PR 272 and 0.4 g of a monosulfonic acid metal salt derivative of PV 19 was added and kneading was continued for 12 h with the walls thermostated at 75°C.
  • DEG diethylene glycol
  • the kneading was stopped and 1 .6 L water and 45 mL of 20% hydrochloric acid (aq) was added to the kneading mass and stirred for 2 h at 70 °C.
  • the mixture was filtered and the pigment was washed with water until the conductivity of the filtrate was below 100 pS/cm and the pH above 6.
  • the wet presscake was dried in an oven at 80 °C for 24 h.
  • the yield of the obtained pigment was 34.6 g and comprised 53% PV 19 and 36% PR 122 in a mixed crystal as a physical mixture with 10% PR 272 and 1% of a monosulfonic acid metal salt derivative of PV 19.
  • the pigment was pulverized in a mill to obtain a magenta powder.
  • a kneading apparatus (duplex-blade kneader) with a capacity of 0.6 litre was charged with 20.2g of crude y-PV 19 and 10.9g of PR 122. 214.3 g of sodium chloride and 45.0 g of diethylene glycol (DEG) were added to the kneader. The walls of the apparatus were thermostated at 80°C. After 12 h of kneading, 3.6 g of PR 272 and 1.1 g of a monosulfonic acid metal salt derivative of PV 19 was added and kneading was continued for 12 h with the walls thermostated at 78 °C.
  • DEG diethylene glycol
  • the yield of the obtained pigment was 34.5 g and comprised 57% PV 19 and 30% PR 122 in a mixed crystal as a physical mixture with 10% PR 272 and 3% of a monosulfonic acid metal salt derivative of PV 19.
  • the pigment was pulverized in a mill to obtain a magenta powder.
  • a kneading apparatus (sigma-blade kneader) with a capacity of 10 litres was charged with 367.5 g of crude y-PV 19 and 157.5 g of PR 122. 3300 g of sodium chloride and 650 g of diethylene glycol (DEG) were added to the kneader. The walls of the apparatus were thermostated at 50 °C. After 6 h of kneading, 22.1 g of PR 264 and 5.5 g of a monosulfonic acid metal salt derivative of PV 19 was added and kneading was continued for 4 h with the walls thermostated at 50°C to ensure an internal temperature of 70°C.
  • DEG diethylene glycol
  • the kneading was stopped and 5 L water was added to the kneading mass.
  • the mixture was stirred for 3 h at room temperature.
  • 7 L of water and 140 g of 20% HOI (aq) were added and stirring was continued at 80 °C for 2 h.
  • the mixture was filtered and the pigment was washed with water until the conductivity of the filtrate was below 100 pS/cm.
  • the wet presscake was dried in an oven at 80 °C for 20 h.
  • the yield of the obtained pigment was 500 g and comprised 67% PV 19 and 28% PR 122 in a mixed crystal as a physical mixture with 4% PR 264 and 1 % of a monosulfonic acid metal salt derivative of PV 19.
  • the pigment was pulverized in a mill to obtain a magenta powder.
  • a kneading apparatus (duplex-blade kneader) with a capacity of 0.6 litre was charged with 26.8 g of crude y-PV 19 and 8.9 g of PR 122. 214.3 g of sodium chloride and 45.0 g of diethylene glycol (DEG) were added to the kneader. The walls of the apparatus were thermostated at 80°C and the mixture was kneaded for 12h. Afterwards, 1.6L of water were added, the mixture was stirred for 3 h and then filtered. The pigment was washed with water until the conductivity of the filtrate was below 100 pS/cm. The wet presscake was dried in an oven at 80°C for 24 h. The yield of the obtained pigment was 35.0 g and comprised 75% PV 19 and 25% PR 122 in a mixed crystal. The pigment was pulverized in a mill to obtain a magenta powder.
  • DEG diethylene glycol
  • a kneading apparatus (duplex-blade kneader) with a capacity of 0.6 litre was charged with 25.9 g of crude y-PV 19 and 8.7 g of PR 122. 214.3 g of sodium chloride and 45.0 g of diethylene glycol (DEG) were added to the kneader. The walls of the apparatus were thermostated at 80-83°C and the mixture was kneaded for 6h. Then, 1.1 g of a monosulfonic acid metal salt derivative of PV 19 was added and kneading was continued for 6 h with the walls thermostated at 83 °C.
  • DEG diethylene glycol
  • the pigment was washed with water until the conductivity of the filtrate was below 100 pS/cm.
  • the wet presscake was dried in an oven at 80°C for 24 h.
  • the yield of the obtained pigment was 33.2 g and comprised of 73% PV 19 and 24% PR 122 in a mixed crystal as a physical mixture with 3% of a monosulfonic acid metal salt derivative of PV 19.
  • the pigment was pulverized in a mill to obtain a magenta powder.
  • a 5 wt% pigment millbase was prepared by combining 5 wt% of the pigment with 95 wt% of a stoving-alkyd based solvent borne binder test system in a sealable container.
  • Dispersion media e.g. glass beads 0 3mm
  • Dispersion media were added to the container in the weight ratio 1 :1.5 millbase components:beads and the container loaded into a Skandex disperser and the millbase components dispersed for 4 hrs.
  • a 45 wt% white millbase was prepared by combining 45 wt% of Titanium Dioxide pigment (e.g. Kronos 2310 supplied by Kronos International Inc.) with 55 wt% of a stoving-alkyd based solvent borne binder test system in a sealable container. Dispersion media (e.g. glass beads 0 3mm) were added to the container in the weight ratio 1 :1.5 millbase components:beads and the container loaded into a Skandex disperser and the millbase components dispersed for 1 hr.
  • Titanium Dioxide pigment e.g. Kronos 2310 supplied by Kronos International Inc.
  • Dispersion media e.g. glass beads 0 3mm
  • Preparation 1 50 wt% of the 5 wt% pigment millbase (Preparation 1) and 50 wt% of the 45 wt% pigment titanium dioxide millbase (Preparation 2) are mixed for 60s with a speed mixer (e.g. Hauschild series DAC 800 FVZ) at 2000 min -1 to provide a 10:90 pigment:Titanium Dioxide white reduction.
  • a speed mixer e.g. Hauschild series DAC 800 FVZ
  • the 5 wt% pigment millbase (Preparation 1) is drawn-down manually on a black and white contrast board (e.g. Leneta 2A-3) using a 150 pm spiral applicator. The coating is left to dry for 20 minutes at room temperature and then baked for 30 min at 130°C.
  • a black and white contrast board e.g. Leneta 2A-3
  • the white reduction (Preparation 3) is drawn-down manually on a black and white contrast board (e.g. Leneta 2A-3) using a 150 pm spiral applicator.
  • the coating is left to dry for 20 minutes at room temperature and then baked for 30 min at 130°C.
  • Colorimetric evaluation is carried out according to the spectral method (ISO 18314-1 (2015)) with d/8° or 87d geometry with the specular component excluded.
  • mass tone panels prepared according to Preparation 4
  • the transparency is determined on the basis of DIN 55988 using the colorimetric parameter scattering-dE.
  • the difference between the transparency of any of the Examples 1 through 8 or Comparative Examples 1 and 2 and the reference material Cinquasia Magenta D 4570 is given as ddE.
  • Cinquasia Magenta D 4570 was set as reference as its hue is close to the target hue of the discussed invention and aids to judge the performance of the invention compared to state-of-the-art PV 19/PR 122 mixed crystals (Comparative Examples)
  • H means the hue in the L*C*H color space (also referred to as CIELAB) specified by the Commission Internationale de I’Eclairage.
  • dH expresses the difference in hue between two samples. Cinquasia Magenta D 4570 was set as reference as its hue is close to the target hue of the discussed invention and aids to judge the performance of the invention compared to state-of-the-art PV 19/PR 122 mixed crystals (Comparative Examples).
  • colorimetric evaluation is carried out according to the spectral method (ISO 18314-1 (2015)) with d/8° or 87d geometry with the specular component included and subsequent computed 4% specular component excluded.
  • the hue is determined according to ISO 11664-4 (2008) for light source D65 and 10° standard observer after matching the depths of shade.
  • the color strength CS is measured in accordance with ISO 18314-2 (2015) by iterative matching of the color depth to the 1/3 depth of shade.
  • the relative color strength is evaluated against Cinquasia Magenta D 4570 as its hue is close to the target hue of the discussed invention and aids to judge the performance of the invention compared to state-of-the-art PV 19/PR 122 mixed crystals (Comparative Examples).
  • PXRD was measured using a powder X-ray diffractometer (MiniFlex 600 by Rigaku or Bruker D8 Advance Series 2) which uses a Cu Ka ray as a source of an X-ray.
  • the scanning range (20) was set to 4° to 35° 20.
  • the intensity ratio was defined by the following formula:
  • Intensity ratio (Diffraction peak intensity at a diffraction angle 20 of around 5.9°) I (Diffraction peak intensity at a diffraction angle 20 of around 11 .9°)
  • 25g pigment is added into a 400ml glass jar containing 75g of a blend of de-ionized water (37.5g), isopropanol (4.5g), diethyleneglycol monobutylether (3.0g) and high molecular weight block copolymer dispersant solution (Disperbyk-190 from BYK-Chemie GmbH, 30.0g).
  • the dispersant on pigment ratio is 0.48 (on a dry basis).
  • the pigment is then pre-dispersed by mixing the obtained mixture during 5 minutes at 5000 rpm using a high-speed disperser (Dispermat LC-230), equipped with a 30mm sawtooth blade.
  • 200g Zirconia beads (0.7-0.9mm diameter) is then added into the glass jar and the pigment is dispersed for 4 hours using a Disperser DAS 200 device (Lau GmbH).
  • the obtained pigment dispersion is left for stand for 24 hours and then analyzed for particle size distribution by the dynamic light scattering method (Malvern Zetasizer from Malvern Instruments Ltd). Test Results
  • the inventive examples 1 through 8 fulfill (O) all requirements in terms of transparency, color strength and hue to exhibit excellent coloristic properties.
  • the comparative examples 1 and 2 fail to meet (X) the target properties in terms of transparency, color strength and hue each in at least one instance.
  • the inventive examples 1 through 8 exhibit the X-ray diffraction signals characteristic of a mixed crystal of PV 19 and PR 122. Furthermore, Table 2 shows that PR 264 and PR 272 are not incorporated into the mixed crystal but are present in a physical mixture as confirmed by the occurrence of X-ray diffraction signals characteristic of the crystal lattices of the individual PR 264 or PR 272 component.
  • Inventive Example 9 exhibits a particle size distribution with Dv(50) ⁇ 150 nm. This is in contrast to the reference sample Cinquasia Magenta D 4570 which exhibits Dv(50) > 150 nm.
  • the narrow particle size distribution of the inventive example 9 is demonstrated by the Dv(10), Dv(50) and Dv(90) values compared to values obtained for the reference sample Cinquasia Magenta D 4570.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

The present application describes a method of manufacturing a mixed crystal pigment composition in a one-step process by solvent-salt-kneading. The composition may be a magenta pigment consisting of a mixed crystal of two quinacridones (PV 19 and PR 122) in a physical mixture with at least one diketopyrrolopyrrole.

Description

Mixed crystal composition of quinacridones with diketopyrrolopyrroles and manufacturing process
The cited references do not refer to the composition of the products of the present application and do not refer to the targeted properties (hue, color strength, transparency). Furthermore, the references do not refer to the use of solvent-salt- kneading for the manufacturing of the mixed crystal as well as the overall composition.
All of the references that refer to a generation of a solid solution or mixed crystal by cosynthesis require additional finishing steps (e.g. milling, solvent finish, blending) to obtain pigmentary material. The multitude of handling steps require increased production time and energy output. Furthermore, each processing step exhibits an inherent liability regarding process stability. By reducing the number of processing steps to a single step, the process becomes more efficient, faster and less prone to instabilities regarding product quality.
None of the references refers to a chlorine-free alternative that matches the composition of the present application.
For the most part, the printing industry uses four process colors in inks: cyan, magenta, yellow and black (CMYK). In recent years, the demand for halogen-free alternatives to established standard pigments is increasing to prevent the release of halogens into the environment upon, e.g. incineration of printed materials after their life cycle ends. There is a particular issue with regards to yellowish magenta pigments, as the widely established pigments either contain halogen atoms (PR 48:2, PR 48:8, PR 146) or are weak in color strength (PV 19, mixed crystal of PV 19 and PR 122) and therefore exhibit low value-in-use or exhibit high opacity.
PV 19 is 5, 12-dihydroquinolino[2,3-b]acridine-7, 14-dione (C.l. PV 19, CAS 1047-16-1). PR 122 is 2, 9-dimethyl-5,12-dihydroquinolino[2,3-b]acridine-7, 14-dione (C.l. PR 122, CAS 980-26-7). It is known that PV 19 and PR 122 can form a mixed crystal in ratios of 85:15 to 60:40 by synthesis through co-cyclization reaction of a diarylaminoterephthalic acid and a dialkylarylaminoterephthalic acid in pholyphosphoric acid. The co-synthesis, however, only produces crude pigment and requires an additional finishing step to produce a useful pigment (e.g. EP3778784A1). This approach provides a magenta that is low in color strength and/or too bluish in hue.
Investigation showed that current commercial mixed crystal of PV 19 and PR 122 do not fulfil the requirements regarding color strength and hue. Surprisingly, we found that by forming a physical mixture of a DPP (d i keto pyrro Io pyrrole) (Color Index PR 264 or PR 272) and optionally a synergist, e.g. a quinacridone pigment derivative such as a monosulfonic acid metal salt derivative of PV 19, with a mixed crystal of PV 19 + PR 122 by solvent-salt kneading, we can achieve a chlorine-free, yellow-shade magenta with high transparency and color strength.
PR 264 is 3, 6-bis-biphenyl-4-yl-2,5-dihydropyrrolo[3,4-c]pyrrole-1 , 4-dione (C.l. PR 264, CAS 88949-33-1). PR 272 is 3,6-bis(4-methylphenyl)-2,5-dihydropyrrolo[3,4-c]pyrrole- 1 ,4-dione (C.l. PR 272, CAS 84632-66-6).
It is well known that quinacridones can form solid solutions or mixed crystals by cosynthesis in the polyphosphoric acid process or by wet milling. The co-synthesis, however, only produces crude pigment and an additional finishing step is necessary to produce a useful pigment. In this approach, particle size and morphology are difficult to control. Furthermore, if the co-synthesis approach is already implemented at the nucleophilic substitution of a dialkyl succinyl succinate with an aniline derivate as in US2005011403A1 , the unsymmetric QA (quinacridone) is formed prompting the necessity of cumbersome global registration of C.l. PR 282. Additionally, producing the solid solution or mixed crystal by co-synthesis makes the control of the specific ratio of the individual components difficult as the yields of the individual syntheses differ.
The process of the present invention is advantageous in that the mixed crystal can be formed from crude pigment of the individual components (PV 19 and PR 122) by solvent-salt-kneading. Solvent-salt-kneading aids as a comminution technology to reduce particle size and simultaneously enables re-growth of the crystals in a suitable solvent system. We found that the intense intermixing of the individual components facilitates the formation of solid solutions I mixed crystals. The parameters influencing the particle size during the solvent-salt-kneading-process are known to persons skilled in the art and can be readily adjusted to tune the particle size and, therefore, the properties of the resulting pigment.
In one embodiment, the crude pigment of the individual components (PV 19 and PR 122) comprises the pigment of the individual components (PV 19 and PR 122) as obtained from the synthesis of the individual components (PV 19 and PR 122), preferably as obtained from the synthesis without a finishing step, wherein the finishing step preferably comprises a modification selected from the group consisting of a particle size modification and a surface modification.
For the purposes of the present application, solid solutions may be defined as a crystalline material, which consists of a host compound and one or more guest compounds that are incorporated in the crystal lattice of the host. Therefore, the solid solution is characterized by the crystal lattice of the host. Furthermore, for the purpose of the present application, mixed crystals may be defined as a crystalline material, which consists of two or more compounds and exhibits a crystal lattice that is different from the crystal lattices of the individual components. (High Performance Pigments, ed. Hugh M. Smith, p. 296, Wiley-VCH Verlag-GmbH, 2002, ISBN 3-527-30204-2).
Both, a solid solution and a mixed crystal can be characterized, for example, by powder X-ray diffractometry. In the present application, a mixed crystal can be viewed as a type of solid solution.
The crude materials used in the solvent-salt-kneading process to form a mixed crystal can be synthesized separately; therefore, no co-synthesis is necessary. As solvent-salt- kneading simultaneously acts as comminution and re-growth process, no pre-milling of the material is necessary, and crude large-particle material can be utilized. Another advantage is the ease of adding further components into the product (PR 264, PR 272 or any QA (quinacridone) synergist, DPP (d i keto pyrro Io pyrrole) synergist, resin or additive) by introducing the material into the solvent-salt-kneading process either before and/or during and/or after the formation of the QA (quinacridone) mixed-crystal. The added material can be readily incorporated into the product and helps to adjust the coloristic properties and secondary properties (e.g. rheology, durability) of the product. Therefore, the invented approach acts as a one-step process compared to conventional methods that include several processes (milling, solvent finish, blending, etc.)
In one embodiment, the crude materials used in the solvent-salt-kneading process comprise the materials as obtained from the synthesis of the individual material, preferably as obtained from the synthesis without a finishing step, wherein the finishing step preferably comprises a modification selected from the group consisting of a particle size modification and a surface modification.
In a further embodiment, the crude large-particle materials comprise materials as obtained from the synthesis of the individual components, preferably as obtained from the synthesis without a finishing step, wherein the finishing step preferably comprises a modification selected from the group consisting of a particle size modification and a surface modification.
Solvent-salt-kneading is a highly versatile method to produce solid solutions or mixed crystals as it can be easily adapted to different chemistries without the necessity of cosynthesis.
Solvent-salt-kneading simultaneously facilitates the formation of a solid solution or mixed crystal and finishes the material by comminution and re-growth into optimized particle sizes and distributions. Therefore, solvent-salt-kneading is a one-step process (formation of mixed crystal + finishing) compared to state-of-the-art multi-step processes requiring formation of mixed crystal followed by milling, finishing, blending steps.
A pigment finished in such a one-step procedure exhibits more homogeneous particle size for both the mixed crystal and the physical mixture components, and therefore exhibits equal or very similar dispersion properties for each of its components. This is highly advantageous for color matching compared to paints I inks that are prepared with several components blended in a mill base (e.g. EP3480264B1). The present composition differentiates itself from industry standards, as it is a halogen- free, yellowish magenta with excellent color strength and transparency. No other commercially available pigment matches these properties.
Citation or identification of any document in this application is not an admission that such represents prior art to the present invention.
The present application describes a one-step solvent-salt-kneading process for making a magenta pigment consisting of a mixed crystal of two quinacridones (PV 19 and PR 122). In the resulting composition, the magenta pigment would further comprise in the ratio of 60:40 to 85:15 or 60:40 to 75:25 in a physical mixture with at least one diketopyrrolopyrrole (Pigment Red 264 and Pigment Red 272) contributing 1-15wt% or 4-10wt% the total composition. The composition can furthermore optionally include 0- 15% of a quinacridone synergist, for example a monosulfonic acid metal salt derivative of PV 19. The composition is advantageously manufactured in a one-step process by solvent-salt-kneading.
Yellow-shade magenta (“process red” colors) mostly constitute azo-pigments (e.g. PR 57:1 ; PR 48:2; PR 146, PR 269) that are known to not be able to match the excellent properties of high-performance pigments such as quinacridones or diketopyrrolopyrroles. Furthermore, among the mentioned azo-pigments, only PR 57:1 is chlorine-free.
Therefore, the composition of the present application, formed by a solvent-salt-kneading process, offers a unique chlorine-free, high-performance alternative to azo-pigments in the field of “process red” colors for printing applications. Quinacridone-based magentas such as PV 19 or a mixed crystal of PV 19 and PR 122 are chlorine-free and considered high-performance pigments, but cannot meet the requirements regarding hue, transparency and color strength.
In the present invention, the quinacridone mixed crystal indicates a quinacridone mixed crystal, which contains PV 19 and PR 122 as essential components; more specifically, a quinacridone solid solution in which a mixed crystal phase of PR 122 and PV 19 is formed. Accordingly, this mixed crystal has inherent peaks at 5.9° ± 0.2° 20 and 11 .9° ± 0.2° of the diffraction angle as measured by powder X-ray diffraction, which are not present in any of the single crystal of PV 19 and the single crystal of PR 122. Therefore, it is possible to easily check by crystal X-ray diffraction whether the quinacridone pigment is a mixed crystal or merely a mixture of the single crystals.
The composition of the present application further contains either PR 264 or PR 272 as well as possibly a quinacridone synergist, e.g. a monosulfonic acid metal salt derivative of PV 19 in a physical mixture with the mixed crystal described above. The presence of either can be found, for example, by mass spectrometry.
The composition of the present invention may advantageously be prepared by solvent- salt-kneading, which facilitates the formation of the quinacridone mixed crystal by intense intermixing in the continuous comminution and re-growth during the process.
Solvent-salt-kneading is carried out with an organic solvent, for example one or more of ethylene glycol, diethylene glycol, diacetone alcohol, dimethylformamide, glycerine, triethylene glycol, dipropylene glycol, ethylene glycol monobutyl ether, methyl ethyl ketone, cyclohexanone, dimethylacetamide, N-methylpyrrolidone, butyl acetate, glycerol triacetate, sulfolane, xylene, tetrahydrofuran, butanol, water and dimethyl sulfoxide. In one embodiment the at least one solvent comprises one or more of diethylene glycol, diacetone alcohol, and glycerine. In one embodiment the at least one solvent is diethylene glycol.
In one embodiment of the present invention would optionally include the addition of one or more quinacridone synergists, for example sulfonic acid derivatives and/or salts of quinacridone; formaldehyde reaction products with 5,12-dihydroquino[2,3-b]acridine- 7, 14-dione and 3,5-dimethyl-1 H-pyrazole; formaldehyde reaction products with 5,12- dihydroquino[2,3-b]acridine-7, 14-dione and 3, 5-dimethyl-1 H-pyrazole, sulfonated or 2- [(1 ,3-Dihydro-1 , 3-d ioxo-2H-isoindol-2-yl)methyl]-5,12-dihydroquino[2,3-b]acridine-7, 14- dione.
In one embodiment of the present invention would optionally include the addition of one or more synergists, for example a natural or synthetic resin comprising esters and salts of abietic acid; hydrated or partially hydrogenated or dimerized rosin; a polysorbate-type nonionic surfactant comprising an ester or a mixture of esters formed from fatty acids, such as lauric or sebacic acid; and polyols, such as like sorbitic monolaureate or dibutylsebacate. The synergist may be added either before and/or during and/or after kneading and/or grinding.
In powder X-ray diffractograms, the mixed crystal of PR 122 and PV 19 exhibits two signals at 5.9° ± 0.2° 20 and 11 .9° ± 0.2° 20 that are both not present in the diffractograms of the individual components, nor in the lattice of a typical commercial PR 122 solid solution, such as Hostaperm Pink E (Heubach). These signals are well separated from other signals in the diffractograms and are, therefore, ideal to characterize the mixed crystal.
The successful formation of the mixed crystal can be evaluated by the intensity ratio of the two signals.
Intensity ratio = (Diffraction peak intensity at a diffraction angle 20 of around 5.9°) I (Diffraction peak intensity at a diffraction angle 20 of around 11 .9°) > 3.
As described, upon adding a DPP (diketopyrrolopyrrole) component to the solvent-salt- kneading of the QA (quinacridone) mixed crystal, a physical mixture between the mixed crystal and the DPP (diketopyrrolopyrrole) is formed. This is evidenced by PXRD (powder X-ray diffraction) as the diffractogram resembles a superposition of the QA (quinacridone) mixed crystal diffractogram with the diffractogram of the individual DPP components. Exemplarily, this can be seen through an additional signal at 8.0°± 0.2° 20 and 17.9°± 0.2° 20 (PR 264) or at 7.7° ± 0.2° 20 and 15.7° ± 0.2° 20 (PR 272) upon the addition thereof.
Solvent-salt-kneading uses an inorganic salt as grinding medium, for example sodium chloride, sodium sulfate or anhydrous aluminium sulfate or a mixture thereof. In one embodiment, the pigment to salt ratio is between 1 :3 and 1 :18. In another embodiment, between 1 :4 and 1 :12. In another embodiment between 1 :6 and 1 :8. Solvent-salt- kneading is advantageously performed at temperatures between 25°C and 120°C, such as between 40°C and 100°C, or between 60°C and 80°C. Solvent-salt-kneading is typically carried out for 4 hours to 48 hours, such as 6 hours to 24 hours, or 8 hours to 18 hours.
During the solvent-salt-kneading process, the pigment is formed as crystalline particles with particle sizes Dv(50) < 150 nm. Preferably, the pigment has a particle size distribution Dv(50) in the rage of from 10 to 145 nm, more preferably 20 to 140 nm, more preferably from 25 to 130 nm, more preferably from 30 to 120 nm. The individual crude components can be of significantly larger particle size and still result in product with excellent coloristic properties.
According to the method of the present invention, the mixed crystal quinacridone pigment composition has a particle size distribution of Dv(50) < 150 nm, preferably the mixed crystal quinacridone pigment composition has a particle size distribution of Dv(50) in the range of from 10 to 145 nm, more preferably from 20 to 140 nm, more preferably from 25 to 130 nm, more preferably from 30 to 120 nm, determined according to reference example 5.
Further, according to the method of the present invention, the method further comprises grinding the crude quinacridone pigment in the presence of a diketopyrrolopyrrole selected from the group consisting of PR 264, PR 272 and a mixture thereof.
According to the method of the present invention, PV 19 is 5,12-dihydroquinolino[2,3- b]acridine-7, 14-dione and/or PR 122 is 2,9-dimethyl-5,12-dihydroquinolino[2,3- b]acridine-7, 14-dione and/or PR 264 is 3,6-bis-biphenyl-4-yl-2,5-dihydropyrrolo[3,4- c]pyrrole-1 , 4-dione and/or PR 272 is 3,6-bis(4-methylphenyl)-2,5-dihydropyrrolo[3,4- c]pyrrole-1 , 4-dione.
According to the method of the present invention, the 1-step solvent-salt-kneading process is a solvent-salt-kneading process.
According to the method of the present invention, in (a), the crude quinacridone pigment comprises the pigment as obtained from the synthesis of the quinacridone pigment, preferably as obtained from the synthesis without a finishing step, wherein the finishing step preferably comprises a modification selected from the group consisting of a particle size modification and a surface modification. According to the method of the present invention, in (a), the temperature is ranging from 60 to 90°C, preferably from 40 to 90°C, more preferably from 80 to 90 °C or the temperature is ranging from 45 to 100 °C, preferably from 50 to 90 °C.
According to the method of the present invention, in (a)(i), the inorganic salt is selected from the group consisting of alkali metal halide, alkali metal sulfate, alkaline earth metal halide, alkaline earth metal sulfate, and a mixture of two or more thereof, preferably wherein the inorganic salt is selected from the group consisting of sodium chloride, sodium sulfate, anhydrous aluminium sulfate, and a mixture of two or more thereof, more preferably wherein the inorganic salt is sodium chloride.
According to the method of the present invention, in (a)(ii), the solubility of the crude quinacridone pigment and the salt in the organic liquid is in the range of from 0 to 10 g/L, preferably from 0.0001 to 9.5 g/L, more preferably from 0.0005 to 9 g/L, at a temperature in the range of from 20 to 25 °C.
The method of any of any preceding paragraph, wherein in (a)(ii), the salt comprises an inorganic salt.
According to the method of the present invention, the mixed crystal quinacridone pigment composition comprises a quinacridone synergist, wherein from 0 to 10 wt% of the mixed crystal quinacridone pigment composition consist of the quinacridone synergist.
According to the method of the present invention, the particle size distribution Dv(50) is determined according to reference example 5.
According to the method of the present invention, in (c), the quinacridone pigment has a particle size distribution of Dv(50) in the range of from 10 to 145 nm, preferably from 20 to 140 nm, more preferably from 25 to 130 nm, more preferably from 30 to 120 nm, determined according to reference example 5.
According to the method of the present invention in (a)(ii), the organic liquid comprises a solvent.
In one embodiment, the crude components comprise the components as obtained in the synthesis of the individual component, preferably as obtained from the synthesis without a finishing step, wherein the finishing step preferably comprises a modification selected from the group consisting of a particle size modification and a surface modification. The present invention is further illustrated by the following numbered paragraphs, which represent a set of embodiments and combinations of embodiments resulting from the dependencies and back-references as indicated. In particular, it is noted that in each instance where a range of embodiments is mentioned, for example in the context of a term such as "The method of any one of embodiments 1 to 5", every embodiment in this range is meant to be explicitly disclosed for the skilled person, i.e. the wording of this term is to be understood by the skilled person as being synonymous to" The method of any one of embodiments 1 , 2, 3, 4 and 5". Further, it is explicitly noted that the following set of embodiments is not the set of claims determining the extent of protection but represents a suitably structured part of the description directed to general and preferred aspects of the present invention.
1 . A method of making a mixed crystal quinacridone pigment composition comprising a 1-step solvent-salt-kneading process, comprising the steps of:
(a) grinding crude quinacridone pigment at a temperature ranging from about 40- 120°C or 60-90°C or 40-90°C or 80-90°C in the presence of:
(i) an inorganic salt ranging from about 3 to about 12 parts by weight, relative to the crude quinacridone pigment;
(ii) an organic liquid in which the crude quinacridone pigment and salt are substantially insoluble; and
(iii) optionally a quinacridone synergist;
(b) discharging the crude quinacridone pigment from step (a) into water; thereby attaining a water pigment mixture; and
(c) isolating from the mixture a quinacridone pigment having a particle size distribution of Dv(50) < 150 nm.
2. The method of paragraph 1 , wherein the composition comprises a combination of PV 19 and PR 122, preferably wherein the composition is a combination of PV 19 and PR 122.
3. The method of paragraph 2, further comprising a diketopyrrolopyrrole selected from the group consisting of PR 264, PR 272 or both in the range of 0.1-15wt% or 1- 15wt% or 5-10wt% of the total composition.
4. The method of paragraph 2, wherein the PV 19 and PR 122 are present in the ratio of 60:40 to 85:15 or 60:40 to 75:25. 5. The method of any preceding paragraph, wherein the mixed crystal quinacridone pigment composition has a particle size distribution of Dv(50) < 150 nm, preferably the mixed crystal quinacridone pigment composition has a particle size distribution of Dv(50) in the range of from 10 to 145 nm, more preferably from 20 to 140 nm, more preferably from 25 to 130 nm, more preferably from 30 to 120 nm, determined according to reference example 5.
6. The method of any preceding paragraph, wherein (a) further comprises grinding the crude quinacridone pigment in the presence of a diketopyrrolopyrrole selected from the group consisting of PR 264, PR 272 and a mixture thereof.
7. The method of any preceding paragraph, wherein PV 19 is 5,12- dihydroquinolino[2,3-b]acridine-7, 14-dione and/or PR 122 is 2,9-dimethyl-5,12- dihydroquinolino[2,3-b]acridine-7, 14-dione and/or PR 264 is 3,6-bis-biphenyl-4-yl-
2.5-dihydropyrrolo[3,4-c]pyrrole-1 , 4-dione and/or PR 272 is 3,6-bis(4-methylphenyl)-
2.5-dihydropyrrolo[3,4-c]pyrrole-1 , 4-dione.
8. The method of any preceding paragraph, wherein the 1-step solvent-salt-kneading process is a solvent-salt-kneading process.
9. The method of any preceding paragraph, wherein in (a), the crude quinacridone pigment comprises the pigment as obtained from the synthesis of the quinacridone pigment, preferably as obtained from the synthesis without a finishing step, wherein the finishing step preferably comprises a modification selected from the group consisting of a particle size modification and a surface modification.
10. The method of any of any preceding paragraph, wherein in (a), the temperature is ranging from 60 to 90°C, preferably from 40 to 90°C, more preferably from 80 to 90 °C or the temperature is ranging from 45 to 100 °C, preferably from 50 to 90 °C.
11 . The method of any of any preceding paragraph, wherein in (a)(i), the inorganic salt is selected from the group consisting of alkali metal halide, alkali metal sulfate, alkaline earth metal halide, alkaline earth metal sulfate, and a mixture of two or more thereof, preferably wherein the inorganic salt is selected from the group consisting of sodium chloride, sodium sulfate, anhydrous aluminium sulfate, and a mixture of two or more thereof, more preferably wherein the inorganic salt is sodium chloride.
12. The method of any preceding paragraph, wherein in (a)(ii), the solubility of the crude quinacridone pigment and the salt in the organic liquid is in the range of from 0 to 10 g/L, preferably from 0.0001 to 9.5 g/L, more preferably from 0.0005 to 9 g/L, at a temperature in the range of from 20 to 25 °C.
13. The method of any of any preceding paragraph, wherein in (a)(ii), the salt comprises an inorganic salt.
14. The method of any of any preceding paragraph, wherein the mixed crystal quinacridone pigment composition comprises a quinacridone synergist, wherein from 0 to 10 wt% of the mixed crystal quinacridone pigment composition consist of the quinacridone synergist.
15. The method of any of any preceding paragraph, wherein the particle size distribution Dv(50) is determined according to reference example 5.
16. The method of any of any preceding paragraph, wherein in (c), the quinacridone pigment has a particle size distribution of Dv(50) in the range of from 10 to 145 nm, preferably from 20 to 140 nm, more preferably from 25 to 130 nm, more preferably from 30 to 120 nm, determined according to reference example 5.
17. The method of any preceding paragraph, wherein in (a)(ii), the organic liquid comprises a solvent.
18. The method of any preceding paragraph, comprising a solvent selected from the group consisting of ethylene glycol, diethylene glycol, diacetone alcohol, dimethylformamide, glycerine, triethylene glycol, dipropylene glycol, ethylene glycol monobutyl ether, methyl ethyl ketone, cyclohexanone, dimethylacetamide, N- methylpyrrolidone, butyl acetate, glycerol triacetate, sulfolane, xylene, tetrahydrofuran, butanol, water, dimethyl sulfoxide and blends thereof, preferably the solvent is selected from the group consisting of ethylene glycol, diethylene glycol, diacetone alcohol, dimethylformamide, glycerine, triethylene glycol, dipropylene glycol, ethylene glycol monobutyl ether, methyl ethyl ketone, cyclohexanone, dimethylacetamide, N-methylpyrrolidone, butyl acetate, glycerol triacetate, sulfolane, xylene, tetrahydrofuran, dimethyl sulfoxide and a mixture of two or more thereof.
19. The method of paragraph 18, wherein at least one solvent comprises one or more of diethylene glycol, diacetone alcohol, and glycerine, preferably the solvent is diethylene glycol.
20. The method of any preceding paragraph, wherein the synergist is a quinacridone derivative selected from the group consisting of quinacridone sulfonic acids and salts thereof, phthalimidoalkyl-quinacridones, imidazolylalkyl-quinacridones, pyrazolylalkyl-quinacridones, sulfonic acids and salts of pyrazolylalkyl-quinacridones, and dialkylaminoalkylsulfonamide derivatives of quinacridones.
21 . The method of any preceding paragraph, wherein the synergist is selected from the group consisting of sulfonic acid derivatives and/or salts of quinacridone; quino[2,3- b]acridine-2-sulfonic acid, 5,7,12,14-tetrahydro-7,14-dioxo-, and its metal salt; formaldehyde reaction products with 5, 12-dihydroquino[2,3-b]acridine-7, 14-dione and 3,5-dimethyl-1 H-pyrazole; formaldehyde reaction products with 5,12- dihydroquino[2,3-b]acridine-7, 14-dione and 3,5-dimethyl-1 H-pyrazole, sulfonated or 2-[(1 ,3-dihydro-1 ,3-dioxo-2H-isoindol-2-yl)methyl]-5,12-dihydroquino[2,3-b]acridine- 7, 14-dione; a natural or synthetic resin comprising esters and salts of abietic acid; hydrated or partially hydrogenated or dimerized rosin; a polysorbate-type nonionic surfactant comprising an ester or a mixture of esters formed from fatty acids, such as lauric or sebacic acid; polyols, such as sorbitan monolaureate or dibutylsebacate; and blends thereof.
22. The method of any preceding paragraph, wherein the synergist is present in the amount of 1-10 wt% relative to the crude quinacridone pigment, preferably the synergist in (a)(iii) is present in the amount of 1-10 wt% relative to the crude quinacridone pigment in (a).
23. The method of any preceding paragraph, wherein the synergist is present in the amount of 1-5 wt% relative to the crude quinacridone pigment, preferably the synergist in (a)(iii) is present in the amount of 1-5 wt% relative to the crude quinacridone pigment in (a).
24. The method of any preceding paragraph, wherein the synergist is present in a range of about 0.001 to about 0.1 parts by weight, relative to the crude quinacridone pigment, preferably the synergist in (a)(iii) is present in a range of about 0.001 to about 0.1 parts by weight, relative to the crude quinacridone pigment in (a).
25. The method of any preceding paragraph, wherein a narrow particle size distribution obtained with Dv(50) is < 150 nm, preferably the narrow particle size distribution obtained with Dv(50) is in the rage of from 10 to 145 nm, more preferably from 20 to 140 nm, more preferably from 25 to 130 nm, more preferably from 30 to 120 nm, determined according to reference example 5. 26. The method of any preceding paragraph, wherein the composition is characterised by powder X-ray diffractometry signals at the diffraction angles 20 at about 5.9°±0.2° and 11.9°±0.2°.
27. The method of paragraph 26, wherein the composition is further characterised by powder X-ray diffractometry signals at the diffraction angles of 8.0°± 0.2° 20 and 17.9°± 0.2° 20 after adding PR 264.
28. The method of paragraph 26, wherein the composition is further characterised by powder X-ray diffractometry signals at the diffraction angles of 7.7° ± 0.2° 20 and 15.7° ± 0.2° 20 after adding PR 272.
29. A mixed crystal quinacridone pigment composition, resulting from the method of any one or more of paragraphs 1-28.
30. The pigment composition of paragraph 29, wherein the ratio of a diffraction peak intensity at a diffraction angle 20 of 5.9 ± 0.2° to a diffraction peak intensity at a diffraction angle of 20 of 11 .9 ± 0.2°C is 3 or higher, preferably the ratio of a diffraction peak intensity at a diffraction angle 20 of 5.9 ± 0.2° to a diffraction peak intensity at a diffraction angle of 20 of 11 .9 ± 0.2°C is in the range of from 3 to 20, more preferably from 6 to 10, as measured by powder X-ray diffractometry, preferably the ratio of the diffraction peak intensity is measured according to reference example 4.
31 . The pigment composition of paragraphs 29 or 30, wherein the amount of quinacridone pigment derivative contained is from 0.1 to 10 parts by mass, relative to 100 parts by mass of pigment, preferably the amount of quinacridone pigment derivative contained in (a)(iii) is from 0.1 to 10 parts by mass, relative to 100 parts by mass of the mixed crystal quinacridone pigment composition.
32. The pigment composition of paragraphs 29 or 30, wherein the amount of quinacridone pigment derivative contained is from 1 to 5 parts by mass, relative to 100 parts by mass of pigment, preferably the amount of quinacridone pigment derivative contained in (a)(iii) is from 1 to 5 parts by mass, relative to 100 parts by mass of the mixed crystal quinacridone pigment composition.
33. The pigment composition of paragraphs 29 or 30, wherein the amount of quinacridone pigment derivative contained is from 0.5 to 3 parts by mass, preferably from 1 to 3 parts by mass, relative to 100 parts by mass of pigment, preferably the amount of quinacridone pigment derivative contained in (a)(iii) is from 0.5 to 3 parts by mass, preferably from 1 to 3 parts by mass, relative to 100 parts by mass of the mixed crystal quinacridone pigment composition.
34. The pigment composition of any one or more of paragraphs 29-33, wherein a narrow particle size distribution obtained with Dv(50) is <150 nm, preferably the narrow particle size distribution obtained with Dv(50) is in the rage of from 10 to 145 nm, more preferably 20 to 140 nm, more preferably from 25 to 130 nm, more preferably from 30 to 120 nm, determined according to reference example 5.
35. The pigment composition of any one or more of paragraphs 29-34, wherein the composition is chlorine-free.
36. A printing ink or coating or plastic composition comprising the pigment composition of any one or more of paragraphs 29-35.
37. The printing ink or coating composition of paragraph 36, wherein the composition is suitable for use as printing ink, automotive coating, architectural coating or industrial coating.
38. The printing ink composition of paragraph 37, wherein the composition is suitable for use as a digital printing ink, inkjet ink, electrophotographic toner, aqueous ink, UV- curable ink, solvent-based ink or oil-based ink.
39. A printed or coated article comprising the printing ink or coating composition of any one or more of paragraphs 35-38.
40. The printed article of paragraph 39, wherein the article is a plastic article.
41 . A plastic article comprising the pigment composition of any one or more of paragraphs 29-35.
Further, the present invention relates to a method for making a mixed crystal quinacridone pigment composition, the method comprising
(a) grinding at least two quinacridone pigments at a temperature in the range of from 40 to 120 °C in the presence of:
(i) an inorganic salt in an amount in the range of from 3 to 12 parts by weight, based on the at least two quinacridone pigments;
(ii) an organic liquid selected from the group consisting of ethylene glycol, diethylene glycol, diacetone alcohol, dimethylformamide, glycerine, triethylene glycol, dipropylene glycol, ethylene glycol monobutyl ether, methyl ethyl ketone, cyclohexanone, dimethylacetamide, N-methylpyrrolidone, butyl acetate, glycerol triacetate, sulfolane, xylene, tetra hydrofuran, dimethyl sulfoxide and a mixture of two or more thereof; and (iii) 0 to 10 wt% of a synergist, based on the mixed crystal quinacridone pigment composition;
(b) discharging the ground at least two quinacridone pigments from step (a) into water; and
(c) isolating the ground at least two quinacridone pigments from step (b); wherein the ground at least two quinacridone pigments have a particle size distribution of Dv(50) is in the range of from 10 to 145 nm.
It is preferred that the mixed crystal quinacridone pigment composition comprises PV 19 and PR 122.
It is preferred that the at least two quinacridone pigments comprise PV 19 and PR 122.
It is preferred that PV 19 and PR 122 are present in the ratio of 60:40 to 85:15 or 60:40 to 75:25.
It is preferred that PV 19 is 5, 12-dihydroquinolino[2,3-b]acridine-7, 14-dione and/or PR 122 is 2,9-dimethyl-5,12-dihydroquinolino[2,3-b]acridine-7, 14-dione.
It is preferred that the method further comprises a diketopyrrolopyrrole selected from the group consisting of PR 264, PR 272 and a mixture thereof, wherein preferably PR 264 is 3, 6-bis-biphenyl-4-yl-2,5-dihydropyrrolo[3,4-c]pyrrole-1 ,4-dione and PR 272 is 3,6-bis(4- methylphenyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1 , 4-dione.
In case where the method further comprises a diketopyrrolopyrrole, the amount of the diketopyrrolopyrrole is in the range of from 0.1 to 15 wt%, preferably from 1 to 15 wt%, more preferably from 5 to 10 wt% based on the mixed crystal quinacridone pigment composition.
It is preferred that in (a), the at least two quinacridone pigments comprise at least two crude quinacridone pigments, wherein the at least two crude pigments comprise at least two quinacridone pigments as obtained from the synthesis of the at least two quinacridone pigments, preferably as obtained from the synthesis without a finishing step, wherein the finishing step preferably comprises a modification selected from the group consisting of a particle size modification and a surface modification.
It is preferred that in (a), the temperature is in the range of from 60 to 90°C, preferably from 40 to 90°C, more preferably from 80 to 90 °C or the temperature is in the range of from 45 to 100 °C, preferably from 50 to 90 °C.
It is preferred that in (a)(i), the inorganic salt is selected from the group consisting of alkali metal halide, alkali metal sulfate, alkaline earth metal halide, alkaline earth metal sulfate, and a mixture of two or more thereof, preferably wherein the inorganic salt is selected from the group consisting of sodium chloride, sodium sulfate, anhydrous aluminium sulfate, and a mixture of two or more thereof, more preferably wherein the inorganic salt is sodium chloride.
It is preferred that in (a), the at least two quinacridone pigments and the inorganic salt are substantially insoluble in the organic liquid, preferably wherein the solubility of the at least two quinacridone pigments and the inorganic salt in the organic liquid is in the range of from 0 to 10 g/L, preferably from 0.0001 to 9.5 g/L, more preferably from 0.0005 to 9 g/L, at a temperature in the range of from 20 to 25 °C.
The solubility of the at least two quinacridone pigments is determined by methods known to a skilled person.
It is preferred that the particle size distribution of Dv(50) is determined according to reference example 5.
It is preferred that the ground at least two quinacridone pigments have a particle size distribution of Dv(50) in the range of from, 20 to 140 nm, preferably from 25 to 130 nm, more preferably from 30 to 120 nm, determined according to reference example 5.
It is preferred that the mixed crystal quinacridone pigment composition has a particle size distribution of Dv(50) < 150 nm, preferably the mixed crystal quinacridone pigment composition has a particle size distribution of Dv(50) in the range of from 10 to 145 nm, more preferably from 20 to 140 nm, more preferably from 25 to 130 nm, more preferably from 30 to 120 nm, determined according to reference example 5.
It is preferred that (a) further comprises grinding the crude quinacridone pigment in the presence of a diketopyrrolopyrrole selected from the group consisting of PR 264, PR 272 and a mixture thereof.
It is preferred that the organic liquid is selected from the group consisting of diethylene glycol, glycerine, diacetone alcohol, and a mixture of two or more thereof, preferably the organic liquid is diethylene glycol.
It is preferred that the synergist in (a)(iii) is a quinacridone derivative selected from the group consisting of quinacridone sulfonic acids and salts thereof, phthalimidoalkyl- quinacridones, imidazolylalkyl-quinacridones, pyrazolylalkyl-quinacridones, sulfonic acids and salts of pyrazolylalkyl-quinacridones, dialkylaminoalkylsulfonamide derivatives of quinacridones, and a mixture of two or more thereof.
In case where the synergist in (a)(iii) is a quinacridone derivative, the quinacridone derivative is selected from the group consisting of sulfonic acid derivatives and/or salts of quinacridone; quino[2,3-b]acridine-2-sulfonic acid, 5,7,12,14-tetrahydro-7,14-dioxo-, and its metal salt; formaldehyde reaction products with 5,12-dihydroquino[2,3-b]acridine- 7, 14-dione and 3,5-dimethyl-1 H-pyrazole; formaldehyde reaction products with 5,12- dihydroquino[2,3-b]acridine-7, 14-dione and 3, 5-dimethyl-1 H-pyrazole, sulfonated or 2- [(1 ,3-dihydro-1 ,3-dioxo-2H-isoindol-2-yl)methyl]-5,12-dihydroquino[2,3-b]acridine-7, 14- dione, and a mixture of two or more thereof, preferably the quinacridone derivative is a monosulfonic acid metal salt derivative of PV 19.
It is further preferred that the synergist in (a)(iii) is selected from the group consisting of a natural or synthetic resin comprising esters and salts of abietic acid; a hydrated or partially hydrogenated or dimerized rosin; a polysorbate-type nonionic surfactant comprising an ester or a mixture of esters formed from fatty acids, preferably from lauric or sebacic acid; polyols, preferably sorbitan monolaureate and dibutylsebacate; and a mixture of two or more thereof.
It is preferred that the synergist in (a)(iii) is present in an amount of 1-10 wt% based on the at least two quinacridone pigments in (a), preferably in an amount of 1-5 wt% based on the at least two quinacridone pigments in (a).
It is preferred that the synergist in (a)(iii) is present in a range of 0.001 to 0.1 parts by weight, based on the at least two quinacridone pigments in (a).
It is preferred that the mixed crystal quinacridone pigment composition comprising the at least two quinacridone pigments has a particle size distribution of Dv(50) in the rage of from 10 to 145 nm, preferably from 20 to 140 nm, more preferably from 25 to 130 nm, more preferably from 30 to 120 nm, determined according to reference example 5.
It is preferred that the mixed crystal quinacridone pigment composition is characterised by powder X-ray diffractometry signals at the diffraction angles 20 at 5.9°±0.2° and 11.9°±0.2°.
It is preferred that the mixed crystal quinacridone pigment composition is further characterised by powder X-ray diffractometry signals at the diffraction angles 20 at 8.0°± 0.2° and 17.9°± 0.2° after adding PR 264.
It is preferred that the mixed crystal quinacridone pigment composition is further characterised by powder X-ray diffractometry signals at the diffraction angles 20 at 7.7° ± 0.2° and 15.7° ± 0.2° after adding PR 272.
It is preferred that the method comprises a 1-step solvent-salt-kneading process.
The present invention also relates to a mixed crystal quinacridone pigment composition, obtainable or obtained according to the method of any one of the particular and preferred embodiments of the present invention for the production of a mixed crystal quinacridone pigment composition. It is preferred that the mixed crystal quinacridone pigment composition has a ratio of a diffraction peak intensity at a diffraction angle 20 of 5.9 ± 0.2° to a diffraction peak intensity at a diffraction angle of 20 of 11 .9 ± 0.2°C is 3 or higher, preferably the ratio of a diffraction peak intensity at a diffraction angle 20 of 5.9 ± 0.2° to a diffraction peak intensity at a diffraction angle of 20 of 11 .9 ± 0.2°C is in the range of from 3 to 20, more preferably from 6 to 10, as measured by powder X-ray diffractometry, preferably the ratio of the diffraction peak intensity is measured according to reference example 4, described therein.
It is preferred that the amount of the synergist of the mixed crystal quinacridone pigment composition is in the range of from 0.1 to 10 parts by mass, preferably from 0.5 to 3 parts by mass or from 1 to 5 parts by mass, relative to 100 parts by mass of the mixed crystal quinacridone pigment composition.
It is preferred that the particle size distribution of Dv(50) the mixed crystal quinacridone pigment composition is in the rage of from 10 to 145 nm, preferably from 20 to 140 nm, more preferably from 25 to 130 nm, more preferably from 30 to 120 nm, determined according to reference example 5 described therein.
It is preferred that the mixed crystal quinacridone pigment composition is chlorine-free.
The present invention also relates to a printing ink or coating or plastic composition comprising the mixed crystal quinacridone pigment composition of any one of the particular and preferred embodiments of the present invention. It is preferred that the printing ink or coating composition of the present invention is suitable for use as printing ink, automotive coating, architectural coating or industrial coating. It is preferred that the printing ink composition of of the present invention is suitable for use as a digital printing ink, inkjet ink, electrophotographic toner, aqueous ink, UV-curable ink, solvent-based ink or oil-based ink. The present invention also relates to a printed or coated article comprising the printing ink or coating composition of any one of the particular and preferred embodiments of the present invention.lt is preferred that the printed article is a plastic article.
The present invention also relates to a plastic article comprising the mixed crystal quinacridone pigment composition of any one of the particular and preferred embodiments of the present invention.
The present invention is further illustrated by the following set of embodiments and combinations of embodiments resulting from the dependencies and back-references as indicated. In particular, it is noted that in each instance where a range of embodiments is mentioned, for example in the context of a term such as "The method of any one of embodiments 1 to 4", every embodiment in this range is meant to be explicitly disclosed for the skilled person, i.e. the wording of this term is to be understood by the skilled person as being synonymous to "The method of any one of embodiments 1 , 2, 3 and 4". Further, it is explicitly noted that the following set of embodiments represents a suitably structured part of the general description directed to preferred aspects of the present invention, and, thus, suitably supports, but does not represent the claims of the present invention.
1 . A method for making a mixed crystal quinacridone pigment composition, the method comprising
(a) grinding at least two quinacridone pigments at a temperature in the range of from 40 to 120 °C in the presence of:
(i) an inorganic salt in an amount in the range of from 3 to 12 parts by weight, based on the at least two quinacridone pigments;
(ii) an organic liquid selected from the group consisting of ethylene glycol, diethylene glycol, diacetone alcohol, dimethylformamide, glycerine, triethylene glycol, dipropylene glycol, ethylene glycol monobutyl ether, methyl ethyl ketone, cyclohexanone, dimethylacetamide, N-methylpyrrolidone, butyl acetate, glycerol triacetate, sulfolane, xylene, tetrahydrofuran, dimethyl sulfoxide and a mixture of two or more thereof; and (iii) 0 to 10 wt% of a synergist, based on the mixed crystal quinacridone pigment composition;
(b) discharging the ground at least two quinacridone pigments from step (a) into water; and
(c) isolating the ground at least two quinacridone pigments from step (b); wherein the ground at least two quinacridone pigments have a particle size distribution of Dv(50) is in the range of from 10 to 145 nm.
2. The method of embodiment 1 , wherein the mixed crystal quinacridone pigment composition comprises PV 19 and PR 122.
3. The method of embodiment 1 or 2, wherein the at least two quinacridone pigments comprise PV 19 and PR 122.
4. The method of embodiment 2 or 3, wherein PV 19 and PR 122 are present in the ratio of 60:40 to 85: 15 or 60:40 to 75:25.
5. The method of any one of embodiments 2 to 4, wherein PV 19 is 5,12- dihydroquinolino[2,3-b]acridine-7, 14-dione and/or PR 122 is 2,9-dimethyl-5,12- dihydroquinolino[2,3-b]acridine-7, 14-dione.
6. The method of any one of embodiments 1 to 5, further comprising a diketopyrrolopyrrole selected from the group consisting of PR 264, PR 272 and a mixture thereof, wherein preferably PR 264 is 3,6-bis-biphenyl-4-yl-2, 5- dihydropyrrolo[3,4-c]pyrrole-1 , 4-dione and PR 272 is 3,6-bis(4-methylphenyl)-2,5- dihydropyrrolo[3,4-c]pyrrole-1 , 4-dione.
7. The method of embodiment 6, wherein the amount of the diketopyrrolopyrrole is in the range of from 0.1 to 15 wt%, preferably from 1 to 15 wt%, more preferably from 5 to 10 wt% based on the mixed crystal quinacridone pigment composition.
8. The method of any one of embodiments 1 to 7, wherein in (a), the at least two quinacridone pigments comprise at least two crude quinacridone pigments, wherein the at least two crude pigments comprise at least two quinacridone pigments as obtained from the synthesis of the at least two quinacridone pigments, preferably as obtained from the synthesis without a finishing step, wherein the finishing step preferably comprises a modification selected from the group consisting of a particle size modification and a surface modification. The method of any one of embodiments 1 to 8, wherein in (a), the temperature is in the range of from 60 to 90°C, preferably from 40 to 90°C, more preferably from 80 to 90 °C or the temperature is in the range of from 45 to 100 °C, preferably from 50 to 90 °C. The method of any of any one of embodiments 1 to 9, wherein in (a)(i), the inorganic salt is selected from the group consisting of alkali metal halide, alkali metal sulfate, alkaline earth metal halide, alkaline earth metal sulfate, and a mixture of two or more thereof, preferably wherein the inorganic salt is selected from the group consisting of sodium chloride, sodium sulfate, anhydrous aluminium sulfate, and a mixture of two or more thereof, more preferably wherein the inorganic salt is sodium chloride. The method of any one of embodiments 1 to 10, wherein in (a), the at least two quinacridone pigments and the inorganic salt are substantially insoluble in the organic liquid, preferably wherein the solubility of the at least two quinacridone pigments and the inorganic salt in the organic liquid is in the range of from 0 to 10 g/L, preferably from 0.0001 to 9.5 g/L, more preferably from 0.0005 to 9 g/L, at a temperature in the range of from 20 to 25 °C. The method of any one of embodiments 1 to 11 , wherein the particle size distribution Dv(50) is determined according to reference example 5. The method of any of any one of embodiments 1 to 12, wherein the ground at least two quinacridone pigments have a particle size distribution of Dv(50) in the range of from 20 to 140 nm, preferably from 25 to 130 nm, more preferably from 30 to 120 nm, determined according to reference example 5. The method of any one of embodiments 1 to 13, wherein the mixed crystal quinacridone pigment composition has a particle size distribution of Dv(50) < 150 nm, preferably the mixed crystal quinacridone pigment composition has a particle size distribution of Dv(50) in the range of from 10 to 145 nm, more preferably from 20 to 140 nm, more preferably from 25 to 130 nm, more preferably from 30 to 120 nm, determined according to reference example 5. The method of any one of embodiments 1 to 14, wherein (a) further comprises grinding the crude quinacridone pigment in the presence of a diketopyrrolopyrrole selected from the group consisting of PR 264, PR 272 and a mixture thereof. The method of any one of embodiments 1 to 15, wherein the organic liquid is selected from the group consisting of diethylene glycol, glycerine, diacetone alcohol, and a mixture of two or more thereof, preferably the organic liquid is diethylene glycol. The method of any one of embodiments 1 to 16, wherein the synergist in (a)(iii) is a quinacridone derivative selected from the group consisting of quinacridone sulfonic acids and salts thereof, phthalimidoalkyl-quinacridones, imidazolylalkyl- quinacridones, pyrazolylalkyl-quinacridones, sulfonic acids and salts of pyrazolylalkyl-quinacridones, dialkylaminoalkylsulfonamide derivatives of quinacridones, and a mixture of two or more thereof. The method of embodiment 17, wherein the quinacridone derivative is selected from the group consisting of sulfonic acid derivatives and/or salts of quinacridone; quino[2,3-b]acridine-2-sulfonic acid, 5,7,12,14-tetrahydro-7,14-dioxo-, and its metal salt; formaldehyde reaction products with 5, 12-dihydroquino[2,3-b]acridine-7, 14- dione and 3,5-dimethyl-1 H-pyrazole; formaldehyde reaction products with 5,12- dihydroquino[2,3-b]acridine-7, 14-dione and 3, 5-dimethyl-1 H-pyrazole, sulfonated or 2-[(1 ,3-dihydro-1 ,3-dioxo-2H-isoindol-2-yl)methyl]-5,12-dihydroquino[2,3-b]acridine- 7,14-dione, and a mixture of two or more thereof, preferably the quinacridone derivative is a monosulfonic acid metal salt derivative of PV 19. The method of any one of embodiments 1 to 16, wherein the synergist in (a)(iii) is selected from the group consisting of a natural or synthetic resin comprising esters and salts of abietic acid; a hydrated or partially hydrogenated or dimerized rosin; a polysorbate-type nonionic surfactant comprising an ester or a mixture of esters formed from fatty acids, preferably from lauric or sebacic acid; polyols, preferably sorbitan monolaureate and dibutylsebacate; and a mixture of two or more thereof. The method of any one of embodiments 1 to 19, wherein the synergist in (a)(iii) is present in an amount of 1-10 wt% based on the at least two quinacridone pigments in (a), preferably in an amount of 1-5 wt% based on the at least two quinacridone pigments in (a). The method of any one of embodiments 1 to 20, wherein the synergist in (a)(iii) is present in a range of 0.001 to 0.1 parts by weight, based on the at least two quinacridone pigments in (a). The method of any one of embodiments 1 to 21 , wherein the mixed crystal quinacridone pigment composition comprising the at least two quinacridone pigments has a particle size distribution of Dv(50) in the rage of from 10 to 145 nm, preferably from 20 to 140 nm, more preferably from 25 to 130 nm, more preferably from 30 to 120 nm, determined according to reference example 5. The method of any one of embodiments 1 to 22, wherein the mixed crystal quinacridone pigment composition is characterised by powder X-ray diffractometry signals at the diffraction angles 20 at 5.9°±0.2° and 11 .9°±0.2°. The method of embodiment 23, wherein the mixed crystal quinacridone pigment composition is further characterised by powder X-ray diffractometry signals at the diffraction angles 20 at 8.0°± 0.2° and 17.9°± 0.2° after adding PR 264. The method of embodiment 23, wherein the mixed crystal quinacridone pigment composition is further characterised by powder X-ray diffractometry signals at the diffraction angles 20 at 7.7° ± 0.2° and 15.7° ± 0.2° after adding PR 272. 26. The method of any one of embodiments 1 to 25, wherein the method comprising a 1 - step solvent-salt-kneading process.
27. A mixed crystal quinacridone pigment composition, obtainable or obtained by the method of any one of embodiments 1 to 26.
28. The mixed crystal quinacridone pigment composition of embodiment 27, wherein the ratio of a diffraction peak intensity at a diffraction angle 20 of 5.9 ± 0.2° to a diffraction peak intensity at a diffraction angle of 20 of 11 .9 ± 0.2°C is 3 or higher, preferably the ratio of a diffraction peak intensity at a diffraction angle 20 of 5.9 ± 0.2° to a diffraction peak intensity at a diffraction angle of 20 of 11 .9 ± 0.2°C is in the range of from 3 to 20, more preferably from 6 to 10, as measured by powder X-ray diffractometry, preferably the ratio of the diffraction peak intensity is measured according to reference example 4.
29. The mixed crystal quinacridone pigment composition of embodiment 27 or 28, wherein the amount of the synergist is in the range of from 0.1 to 10 parts by mass, preferably from 0.5 to 3 parts by mass or from 1 to 5 parts by mass, relative to 100 parts by mass of the mixed crystal quinacridone pigment composition.
30. The mixed crystal quinacridone pigment composition of any one of embodiments 27 to 29, wherein the particle size distribution of Dv(50) is in the rage of from 10 to 145 nm, preferably from 20 to 140 nm, more preferably from 25 to 130 nm, more preferably from 30 to 120 nm, determined according to reference example 5.
31 . The mixed crystal quinacridone pigment composition of any one of embodiments 27 to 30, wherein the composition is chlorine-free.
32. A printing ink or coating or plastic composition comprising the mixed crystal quinacridone pigment composition of any one of embodiments 27 to 31 . 33. The printing ink or coating composition of embodiment 32, wherein the composition is suitable for use as printing ink, automotive coating, architectural coating or industrial coating.
34. The printing ink composition of embodiment 32, wherein the composition is suitable for use as a digital printing ink, inkjet ink, electrophotographic toner, aqueous ink, UV-curable ink, solvent-based ink or oil-based ink.
35. A printed or coated article comprising the printing ink or coating composition of any one of embodiments 32 to 34.
36. The printed article of embodiment 35, wherein the article is a plastic article.
37. A plastic article comprising the mixed crystal quinacridone pigment composition of any one of embodiments 27 to 31 .
The present invention has been described in detail, including the preferred embodiments thereof. However, it will be appreciated that those skilled in the art, upon consideration of the present disclosure, may make modifications and/or improvements on this invention that fall within the scope and spirit of the invention.
EXAMPLES
The invention is further described by the following non-limiting examples which further illustrate the invention, and are not intended, nor should they be interpreted to, limit the scope of the invention.
Example 1
A kneading apparatus (duplex-blade kneader) with a capacity of 0.6 litre was charged with 20.0 g of crude y-PV 19 and 11.1 g of PR 122. 214.3 g of sodium chloride and 45.0 g of diethylene glycol (DEG) were added to the kneader. The walls of the apparatus were thermostated at 80°C. After 12 h of kneading, 3.6 g of PR 264 and 1.1 g of a monosulfonic acid metal salt derivative of PV 19 was added and kneading was continued for 12 h with the walls thermostated at 80 °C. Then, the kneading was stopped and 1 .6 L water was added to the kneading mass and stirred for 3 h. The mixture was filtered and the pigment was washed with water until the conductivity of the filtrate was below 100 pS/cm. The wet presscake was dried in an oven at 80°C for 24 h. The yield of the obtained pigment was 34.1 g and comprised 56% PV 19 and 31 % PR 122 in a mixed crystal as a physical mixture with 10% PR 264 and 3% of a monosulfonic acid metal salt derivative of PV 19. The pigment was pulverized in a mill to obtain a magenta powder.
Example 2
A kneading apparatus (duplex-blade kneader) with a capacity of 0.6 litre was charged with 21.7 g of crude y-PV 19 and 9.3 g of PR 122. 214.3 g of sodium chloride and 45.0 g of diethylene glycol (DEG) were added to the kneader. The walls of the apparatus were thermostated at 80°C. After 12 h of kneading, 3.6 g of PR 272 and 1.1 g of a monosulfonic acid metal salt derivative of PV 19 was added and kneading was continued for 12 h with the walls thermostated at 80°C. Then, the kneading was stopped and 1 .6 L water was added to the kneading mass and stirred for 3 h. The mixture was filtered and the pigment was washed with water until the conductivity of the filtrate was below 100 pS/cm. The wet presscake was dried in an oven at 80°C for 24 h. The yield of the obtained pigment was 34.5 g and comprised 61 % PV 19 and 26% PR 122 in a mixed crystal as a physical mixture with 10% PR 272 and 3% of a monosulfonic acid metal salt derivative of PV 19. The pigment was pulverized in a mill to obtain a magenta powder.
Example 3
A kneading apparatus (duplex-blade kneader) with a capacity of 0.6 litre was charged with 24.5 g of crude y-PV 19 and 8.2 g of PR 122. 214.3 g of sodium chloride and 45.0 g of diethylene glycol (DEG) were added to the kneader. The walls of the apparatus were thermostated at 80°C. After 6 h of kneading, 1.8 g of PR 272 and 1.1 g of a monosulfonic acid metal salt derivative of PV 19 was added and kneading was continued for 6 h with the walls thermostated at 80°C. Then, the kneading was stopped and 1 .6 L water was added to the kneading mass and stirred for 3 h. The mixture was filtered and the pigment was washed with water until the conductivity of the filtrate was below 100 pS/cm. The wet presscake was dried in an oven at 80°C for 24 h. The yield of the obtained pigment was 34.5 g and comprised 69% PV 19 and 23% PR 122 in a mixed crystal as a physical mixture with 5% PR 272 and 3% of a monosulfonic acid metal salt derivative of PV 19. The pigment was pulverized in a mill to obtain a magenta powder.
Example 4
A kneading apparatus (duplex-blade kneader) with a capacity of 0.6 litre was charged with 20.7 g of crude y-PV 19 and 11.4 g of PR 122. 214.3 g of sodium chloride and 45.0 g of diethylene glycol (DEG) were added to the kneader. The walls of the apparatus were thermostated at 80°C. After 12 h of kneading, 3.6 g of PR 272 was added and kneading was continued for 12 h with the walls thermostated at 75-80°C. Then, the kneading was stopped and 1 .6 L water was added to the kneading mass and stirred for 3 h. The mixture was filtered and the pigment was washed with water until the conductivity of the filtrate was below 100 pS/cm. The wet presscake was dried in an oven at 80°C for 24 h. The yield of the obtained pigment was 34.5 g and comprised 58% PV 19 and 32% PR 122 in a mixed crystal as a physical mixture with 10% PR 272. The pigment was pulverized in a mill to obtain a magenta powder.
Example 5
A kneading apparatus (duplex-blade kneader) with a capacity of 0.6 litre was charged with 20.7 g of crude y-PV 19 and 11.4 g of PR 122. 214.3 g of sodium chloride and 45.0 g of diethylene glycol (DEG) were added to the kneader. The walls of the apparatus were thermostated at 76-80°C. After 12 h of kneading, 3.6 g of PR 264 was added and kneading was continued for 12 h with the walls thermostated at 76 °C. Then, the kneading was stopped and 1 .6 L water was added to the kneading mass and stirred for 3 h. The mixture was filtered and the pigment was washed with water until the conductivity of the filtrate was below 100 pS/cm. The wet presscake was dried in an oven at 80 °C for 24 h. The yield of the obtained pigment was 34.9 g and comprised 58% PV 19 and 32% PR 122 in a mixed crystal as a physical mixture with 10% PR 264. The pigment was pulverized in a mill to obtain a magenta powder.
Example 6
A kneading apparatus (duplex-blade kneader) with a capacity of 0.6 litre was charged with 25.1 g of crude y-PV 19 and 8.4 g of PR 122. 214.3 g of sodium chloride and 45.0 g of diethylene glycol (DEG) were added to the kneader. The walls of the apparatus were thermostated at 80°C. After 6 h of kneading, 1.8 g of PR 264 and 0.4 g of a monosulfonic acid metal salt derivative of PV 19 was added and kneading was continued for 6 h with the walls thermostated at 80°C. Then, the kneading was stopped and 1 .6 L water was added to the kneading mass and stirred for 3 h. The mixture was filtered and the pigment was washed with water until the conductivity of the filtrate was below 100 pS/cm. The wet presscake was dried in an oven at 80 °C for 24 h. The yield of the obtained pigment was 34.9 g and comprised 70% PV 19 and 24% PR 122 in a mixed crystal as a physical mixture with 5% PR 272 and 1 % of a monosulfonic acid metal salt derivative of PV 19. The pigment was pulverized in a mill to obtain a magenta powder.
Example 7
A kneading apparatus (duplex-blade kneader) with a capacity of 0.6 litre was charged with 18.8g of crude y-PV 19 and 12.9g of PR 122. 214.3 g of sodium chloride and 45.0 g of diethylene glycol (DEG) were added to the kneader. The walls of the apparatus were thermostated at 75°C. After 12 h of kneading, 3.6 g of PR 272 and 0.4 g of a monosulfonic acid metal salt derivative of PV 19 was added and kneading was continued for 12 h with the walls thermostated at 75°C. Then, the kneading was stopped and 1 .6 L water and 45 mL of 20% hydrochloric acid (aq) was added to the kneading mass and stirred for 2 h at 70 °C. The mixture was filtered and the pigment was washed with water until the conductivity of the filtrate was below 100 pS/cm and the pH above 6. The wet presscake was dried in an oven at 80 °C for 24 h. The yield of the obtained pigment was 34.6 g and comprised 53% PV 19 and 36% PR 122 in a mixed crystal as a physical mixture with 10% PR 272 and 1% of a monosulfonic acid metal salt derivative of PV 19. The pigment was pulverized in a mill to obtain a magenta powder.
Example 8
A kneading apparatus (duplex-blade kneader) with a capacity of 0.6 litre was charged with 20.2g of crude y-PV 19 and 10.9g of PR 122. 214.3 g of sodium chloride and 45.0 g of diethylene glycol (DEG) were added to the kneader. The walls of the apparatus were thermostated at 80°C. After 12 h of kneading, 3.6 g of PR 272 and 1.1 g of a monosulfonic acid metal salt derivative of PV 19 was added and kneading was continued for 12 h with the walls thermostated at 78 °C. Then, the kneading was stopped and 1 .6 L water was added to the kneading mass and stirred for 3 h. The mixture was filtered and the pigment was washed with water until the conductivity of the filtrate was below 100 pS/cm. The wet presscake was dried in an oven at 80°C for 24 h. The yield of the obtained pigment was 34.5 g and comprised 57% PV 19 and 30% PR 122 in a mixed crystal as a physical mixture with 10% PR 272 and 3% of a monosulfonic acid metal salt derivative of PV 19. The pigment was pulverized in a mill to obtain a magenta powder.
Example 9
A kneading apparatus (sigma-blade kneader) with a capacity of 10 litres was charged with 367.5 g of crude y-PV 19 and 157.5 g of PR 122. 3300 g of sodium chloride and 650 g of diethylene glycol (DEG) were added to the kneader. The walls of the apparatus were thermostated at 50 °C. After 6 h of kneading, 22.1 g of PR 264 and 5.5 g of a monosulfonic acid metal salt derivative of PV 19 was added and kneading was continued for 4 h with the walls thermostated at 50°C to ensure an internal temperature of 70°C. Then, the kneading was stopped and 5 L water was added to the kneading mass. The mixture was stirred for 3 h at room temperature. Then, 7 L of water and 140 g of 20% HOI (aq) were added and stirring was continued at 80 °C for 2 h. The mixture was filtered and the pigment was washed with water until the conductivity of the filtrate was below 100 pS/cm. The wet presscake was dried in an oven at 80 °C for 20 h. The yield of the obtained pigment was 500 g and comprised 67% PV 19 and 28% PR 122 in a mixed crystal as a physical mixture with 4% PR 264 and 1 % of a monosulfonic acid metal salt derivative of PV 19. The pigment was pulverized in a mill to obtain a magenta powder.
Comparative Example 1
A kneading apparatus (duplex-blade kneader) with a capacity of 0.6 litre was charged with 26.8 g of crude y-PV 19 and 8.9 g of PR 122. 214.3 g of sodium chloride and 45.0 g of diethylene glycol (DEG) were added to the kneader. The walls of the apparatus were thermostated at 80°C and the mixture was kneaded for 12h. Afterwards, 1.6L of water were added, the mixture was stirred for 3 h and then filtered. The pigment was washed with water until the conductivity of the filtrate was below 100 pS/cm. The wet presscake was dried in an oven at 80°C for 24 h. The yield of the obtained pigment was 35.0 g and comprised 75% PV 19 and 25% PR 122 in a mixed crystal. The pigment was pulverized in a mill to obtain a magenta powder.
Comparative Example 2
A kneading apparatus (duplex-blade kneader) with a capacity of 0.6 litre was charged with 25.9 g of crude y-PV 19 and 8.7 g of PR 122. 214.3 g of sodium chloride and 45.0 g of diethylene glycol (DEG) were added to the kneader. The walls of the apparatus were thermostated at 80-83°C and the mixture was kneaded for 6h. Then, 1.1 g of a monosulfonic acid metal salt derivative of PV 19 was added and kneading was continued for 6 h with the walls thermostated at 83 °C. Afterwards, 1 ,6L of water were added, the mixture was stirred for 3 h and then filtered. The pigment was washed with water until the conductivity of the filtrate was below 100 pS/cm. The wet presscake was dried in an oven at 80°C for 24 h. The yield of the obtained pigment was 33.2 g and comprised of 73% PV 19 and 24% PR 122 in a mixed crystal as a physical mixture with 3% of a monosulfonic acid metal salt derivative of PV 19. The pigment was pulverized in a mill to obtain a magenta powder.
Test methods
Coloristic properties:
Preparation of the 5 wt% pigment millbase (Preparation 1)
A 5 wt% pigment millbase was prepared by combining 5 wt% of the pigment with 95 wt% of a stoving-alkyd based solvent borne binder test system in a sealable container. Dispersion media (e.g. glass beads 0 3mm) were added to the container in the weight ratio 1 :1.5 millbase components:beads and the container loaded into a Skandex disperser and the millbase components dispersed for 4 hrs.
Preparation of the 45 wt% pigment titanium dioxide millbase (Preparation 2)
A 45 wt% white millbase was prepared by combining 45 wt% of Titanium Dioxide pigment (e.g. Kronos 2310 supplied by Kronos International Inc.) with 55 wt% of a stoving-alkyd based solvent borne binder test system in a sealable container. Dispersion media (e.g. glass beads 0 3mm) were added to the container in the weight ratio 1 :1.5 millbase components:beads and the container loaded into a Skandex disperser and the millbase components dispersed for 1 hr.
Preparation of the white reduction (Preparation 3)
50 wt% of the 5 wt% pigment millbase (Preparation 1) and 50 wt% of the 45 wt% pigment titanium dioxide millbase (Preparation 2) are mixed for 60s with a speed mixer (e.g. Hauschild series DAC 800 FVZ) at 2000 min-1 to provide a 10:90 pigment:Titanium Dioxide white reduction.
Preparation mass tone panels (Preparation 4)
The 5 wt% pigment millbase (Preparation 1) is drawn-down manually on a black and white contrast board (e.g. Leneta 2A-3) using a 150 pm spiral applicator. The coating is left to dry for 20 minutes at room temperature and then baked for 30 min at 130°C.
Preparation of white reduction panels (Preparation 5)
The white reduction (Preparation 3) is drawn-down manually on a black and white contrast board (e.g. Leneta 2A-3) using a 150 pm spiral applicator. The coating is left to dry for 20 minutes at room temperature and then baked for 30 min at 130°C.
Evaluation of transparency (ddE) (Reference Example 1)
Colorimetric evaluation is carried out according to the spectral method (ISO 18314-1 (2015)) with d/8° or 87d geometry with the specular component excluded. Using the mass tone panels (prepared according to Preparation 4), the transparency is determined on the basis of DIN 55988 using the colorimetric parameter scattering-dE. The difference between the transparency of any of the Examples 1 through 8 or Comparative Examples 1 and 2 and the reference material Cinquasia Magenta D 4570 is given as ddE.
Cinquasia Magenta D 4570 was set as reference as its hue is close to the target hue of the discussed invention and aids to judge the performance of the invention compared to state-of-the-art PV 19/PR 122 mixed crystals (Comparative Examples)
Evaluation of the hue (dH) (Reference Example 2)
The term H (hue) used herein means the hue in the L*C*H color space (also referred to as CIELAB) specified by the Commission Internationale de I’Eclairage. dH expresses the difference in hue between two samples. Cinquasia Magenta D 4570 was set as reference as its hue is close to the target hue of the discussed invention and aids to judge the performance of the invention compared to state-of-the-art PV 19/PR 122 mixed crystals (Comparative Examples).
Using the white reduction panels (prepared according to Preparation 5), colorimetric evaluation is carried out according to the spectral method (ISO 18314-1 (2015)) with d/8° or 87d geometry with the specular component included and subsequent computed 4% specular component excluded. The hue is determined according to ISO 11664-4 (2008) for light source D65 and 10° standard observer after matching the depths of shade.
Evaluation of the relative color strength (CS) (Reference Example 3)
Using the white reduction panels (Preparation 5), the color strength CS is measured in accordance with ISO 18314-2 (2015) by iterative matching of the color depth to the 1/3 depth of shade. The relative color strength is evaluated against Cinquasia Magenta D 4570 as its hue is close to the target hue of the discussed invention and aids to judge the performance of the invention compared to state-of-the-art PV 19/PR 122 mixed crystals (Comparative Examples).
The criteria used for the evaluation are as shown below.
O = criteria successfully met
X = criteria not met
Transparency:
The more negative the value, the more transparent:
O: ddE < -3.0
X: ddE > -3.0
Color strength:
The higher the value, the higher the relative color strength.
O: CS > 75
X: CS < 75 Hue:
The more positive the dH value, the more yellowish or excellent the shade. O: dH > -3
X: dH < -3
Method for measuring PXRD (powder X-ray diffraction) and evaluating the peak intensity ratio (Reference Example 4)
PXRD was measured using a powder X-ray diffractometer (MiniFlex 600 by Rigaku or Bruker D8 Advance Series 2) which uses a Cu Ka ray as a source of an X-ray. The scanning range (20) was set to 4° to 35° 20.
The intensity ratio was defined by the following formula:
Intensity ratio = (Diffraction peak intensity at a diffraction angle 20 of around 5.9°) I (Diffraction peak intensity at a diffraction angle 20 of around 11 .9°)
Criteria for formation of mixed crystal of PR 19 with PR 122:
O: Intensity ratio > 3
X: Intensity ratio < 3
Method for determining the particle size distribution (Dv) (Reference Example 5)
To prepare the dispersion, 25g pigment is added into a 400ml glass jar containing 75g of a blend of de-ionized water (37.5g), isopropanol (4.5g), diethyleneglycol monobutylether (3.0g) and high molecular weight block copolymer dispersant solution (Disperbyk-190 from BYK-Chemie GmbH, 30.0g). The dispersant on pigment ratio is 0.48 (on a dry basis). The pigment is then pre-dispersed by mixing the obtained mixture during 5 minutes at 5000 rpm using a high-speed disperser (Dispermat LC-230), equipped with a 30mm sawtooth blade. 200g Zirconia beads (0.7-0.9mm diameter) is then added into the glass jar and the pigment is dispersed for 4 hours using a Disperser DAS 200 device (Lau GmbH).
The obtained pigment dispersion is left for stand for 24 hours and then analyzed for particle size distribution by the dynamic light scattering method (Malvern Zetasizer from Malvern Instruments Ltd). Test Results
Table 1
Figure imgf000037_0001
As shown in Table 1 , the inventive examples 1 through 8 fulfill (O) all requirements in terms of transparency, color strength and hue to exhibit excellent coloristic properties. In contrast, the comparative examples 1 and 2 fail to meet (X) the target properties in terms of transparency, color strength and hue each in at least one instance.
Table 2
Figure imgf000037_0002
W = weak, M = medium, S = strong As shown in Table 2, the inventive examples 1 through 8 exhibit the X-ray diffraction signals characteristic of a mixed crystal of PV 19 and PR 122. Furthermore, Table 2 shows that PR 264 and PR 272 are not incorporated into the mixed crystal but are present in a physical mixture as confirmed by the occurrence of X-ray diffraction signals characteristic of the crystal lattices of the individual PR 264 or PR 272 component.
Table 3
Figure imgf000038_0001
As shown in Table 3, Inventive Example 9 exhibits a particle size distribution with Dv(50) < 150 nm. This is in contrast to the reference sample Cinquasia Magenta D 4570 which exhibits Dv(50) > 150 nm. The narrow particle size distribution of the inventive example 9 is demonstrated by the Dv(10), Dv(50) and Dv(90) values compared to values obtained for the reference sample Cinquasia Magenta D 4570.
Cited literature:
- JP2019112534
- EP3786236A1
- EP3778784
- EP3533842
- US 7166158
- EP 3480264B1
High Performance Pigments, ed. Hugh M. Smith, p. 296, Wiley-VCH Verlag-
GmbH, 2002, ISBN 3-527-30204-2

Claims

Claims
1 . A method of making a mixed crystal quinacridone pigment composition comprising a 1-step solvent-salt-kneading process, comprising the steps of:
(a) grinding crude quinacridone pigment at a temperature ranging from about 40- 120°C or 60-90°C or 40-90°C or 80-90°C in the presence of:
(i) an inorganic salt ranging from about 3 to about 12 parts by weight, relative to the crude quinacridone pigment;
(ii) an organic liquid in which the crude quinacridone pigment and salt are substantially insoluble; and
(iii) optionally a quinacridone synergist;
(b) discharging the crude quinacridone pigment from step (a) into water; thereby attaining a water pigment mixture; and
(c) isolating from the mixture a quinacridone pigment having a particle size distribution of Dv(50) < 150 nm.
2. The method of claim 1 , wherein the composition comprises a combination of PV 19 and PR 122, preferably wherein the composition is a combination of PV 19 and PR 122.
3. The method of claim 2, further comprising a diketopyrrolopyrrole selected from the group consisting of PR 264, PR 272 or both in the range of 0.1 -15wt% or 1 -15wt% or 5-10wt% of the total composition.
4. The method of claim 2, wherein the PV 19 and PR 122 are present in the ratio of 60:40 to 85: 15 or 60:40 to 75:25.
5. The method of any preceding claim, wherein the mixed crystal quinacridone pigment composition has a particle size distribution of Dv(50) < 150 nm, preferably the mixed crystal quinacridone pigment composition has a particle size distribution of Dv(50) in the range of from 10 to 145 nm, more preferably from 20 to 140 nm, more preferably from 25 to 130 nm, more preferably from 30 to 120 nm, determined according to reference example 5.
6. The method of any preceding claim, wherein (a) further comprises grinding the crude quinacridone pigment in the presence of a diketopyrrolopyrrole selected from the group consisting of PR 264, PR 272 and a mixture thereof. The method of any preceding claim, wherein PV 19 is 5,12-dihydroquinolino[2,3- b]acridine-7, 14-dione and/or PR 122 is 2,9-dimethyl-5,12-dihydroquinolino[2,3- b]acridine-7, 14-dione and/or PR 264 is 3,6-bis-biphenyl-4-yl-2,5-dihydropyrrolo[3,4- c]pyrrole-1 , 4-dione and/or PR 272 is 3,6-bis(4-methylphenyl)-2,5-dihydropyrrolo[3,4- c]pyrrole-1 , 4-dione. The method of any preceding claim, wherein the 1-step solvent-salt-kneading process is a solvent-salt-kneading process. The method of any preceding claim, wherein in (a), the crude quinacridone pigment comprises the pigment as obtained from the synthesis of the quinacridone pigment, preferably as obtained from the synthesis without a finishing step, wherein the finishing step preferably comprises a modification selected from the group consisting of a particle size modification and a surface modification. The method of any of any preceding claim, wherein in (a), the temperature is ranging from 60 to 90°C, preferably from 40 to 90°C, more preferably from 80 to 90 °C or the temperature is ranging from 45 to 100 °C, preferably from 50 to 90 °C. The method of any of any preceding claim, wherein in (a)(i), the inorganic salt is selected from the group consisting of alkali metal halide, alkali metal sulfate, alkaline earth metal halide, alkaline earth metal sulfate, and a mixture of two or more thereof, preferably wherein the inorganic salt is selected from the group consisting of sodium chloride, sodium sulfate, anhydrous aluminium sulfate, and a mixture of two or more thereof, more preferably wherein the inorganic salt is sodium chloride. The method of any preceding claim, wherein in (a)(ii), the solubility of the crude quinacridone pigment and the salt in the organic liquid is in the range of from 0 to 10 g/L, preferably from 0.0001 to 9.5 g/L, more preferably from 0.0005 to 9 g/L, at a temperature in the range of from 20 to 25 °C. The method of any of any preceding claim, wherein in (a)(ii), the salt comprises an inorganic salt. The method of any of any preceding claim, wherein the mixed crystal quinacridone pigment composition comprises a quinacridone synergist, wherein from 0 to 10 wt% of the mixed crystal quinacridone pigment composition consist of the quinacridone synergist. The method of any of any preceding claim, wherein the particle size distribution Dv(50) is determined according to reference example 5.
16. The method of any of any preceding claim, wherein in (c), the quinacridone pigment has a particle size distribution of Dv(50) in the range of from 10 to 145 nm, preferably from 20 to 140 nm, more preferably from 25 to 130 nm, more preferably from 30 to 120 nm, determined according to reference example 5.
17. The method of any preceding claim, wherein in (a)(ii), the organic liquid comprises a solvent.
18. The method of any preceding claim, comprising a solvent selected from the group consisting of ethylene glycol, diethylene glycol, diacetone alcohol, dimethylformamide, glycerine, triethylene glycol, dipropylene glycol, ethylene glycol monobutyl ether, methyl ethyl ketone, cyclohexanone, dimethylacetamide, N- methylpyrrolidone, butyl acetate, glycerol triacetate, sulfolane, xylene, tetrahydrofuran, butanol, water, dimethyl sulfoxide and blends thereof, preferably the solvent is selected from the group consisting of ethylene glycol, diethylene glycol, diacetone alcohol, dimethylformamide, glycerine, triethylene glycol, dipropylene glycol, ethylene glycol monobutyl ether, methyl ethyl ketone, cyclohexanone, dimethylacetamide, N-methylpyrrolidone, butyl acetate, glycerol triacetate, sulfolane, xylene, tetrahydrofuran, dimethyl sulfoxide and a mixture of two or more thereof.
19. The method of claim 18, wherein at least one solvent comprises one or more of diethylene glycol, diacetone alcohol, and glycerine, preferably the solvent is diethylene glycol.
20. The method of any preceding claim, wherein the synergist is a quinacridone derivative selected from the group consisting of quinacridone sulfonic acids and salts thereof, phthalimidoalkyl-quinacridones, imidazolylalkyl-quinacridones, pyrazolylalkyl-quinacridones, sulfonic acids and salts of pyrazolylalkyl-quinacridones, and dialkylaminoalkylsulfonamide derivatives of quinacridones.
21 . The method of any preceding claim, wherein the synergist is selected from the group consisting of sulfonic acid derivatives and/or salts of quinacridone; quino[2,3- b]acridine-2-sulfonic acid, 5,7,12,14-tetrahydro-7,14-dioxo-, and its metal salt; formaldehyde reaction products with 5, 12-dihydroquino[2,3-b]acridine-7, 14-dione and 3,5-dimethyl-1 H-pyrazole; formaldehyde reaction products with 5,12- dihydroquino[2,3-b]acridine-7, 14-dione and 3,5-dimethyl-1 H-pyrazole, sulfonated or 2-[(1 ,3-dihydro-1 ,3-dioxo-2H-isoindol-2-yl)methyl]-5,12-dihydroquino[2,3-b]acridine- 7, 14-dione; a natural or synthetic resin comprising esters and salts of abietic acid; hydrated or partially hydrogenated or dimerized rosin; a polysorbate-type nonionic surfactant comprising an ester or a mixture of esters formed from fatty acids, such as lauric or sebacic acid; polyols, such as sorbitan monolaureate or dibutylsebacate; and blends thereof.
22. The method of any preceding claim, wherein the synergist is present in the amount of 1-10 wt% relative to the crude quinacridone pigment, preferably the synergist in (a)(iii) is present in the amount of 1-10 wt% relative to the crude quinacridone pigment in (a).
23. The method of any preceding claim, wherein the synergist is present in the amount of 1-5 wt% relative to the crude quinacridone pigment, preferably the synergist in (a)(iii) is present in the amount of 1-5 wt% relative to the crude quinacridone pigment in (a).
24. The method of any preceding claim, wherein the synergist is present in a range of about 0.001 to about 0.1 parts by weight, relative to the crude quinacridone pigment, preferably the synergist in (a)(iii) is present in a range of about 0.001 to about 0.1 parts by weight, relative to the crude quinacridone pigment in (a).
25. The method of any preceding claim, wherein a narrow particle size distribution obtained with Dv(50) is < 150 nm, preferably the narrow particle size distribution obtained with Dv(50) is in the rage of from 10 to 145 nm, more preferably from 20 to 140 nm, more preferably from 25 to 130 nm, more preferably from 30 to 120 nm, determined according to reference example 5.
26. The method of any preceding claim, wherein the composition is characterised by powder X-ray diffractometry signals at the diffraction angles 20 at about 5.9°±0.2° and 11.9°±0.2°.
27. The method of claim 26, wherein the composition is further characterised by powder X-ray diffractometry signals at the diffraction angles of 8.0°± 0.2° 20 and 17.9°± 0.2° 20 after adding PR 264.
28. The method of claim 26, wherein the composition is further characterised by powder X-ray diffractometry signals at the diffraction angles of 7.7° ± 0.2° 20 and 15.7° ± 0.2° 20 after adding PR 272.
29. A mixed crystal quinacridone pigment composition, resulting from the method of any one or more of claims 1-28. The pigment composition of claim 29, wherein the ratio of a diffraction peak intensity at a diffraction angle 20 of 5.9 ± 0.2° to a diffraction peak intensity at a diffraction angle of 20 of 11 .9 ± 0.2°C is 3 or higher, preferably the ratio of a diffraction peak intensity at a diffraction angle 20 of 5.9 ± 0.2° to a diffraction peak intensity at a diffraction angle of 20 of 11 .9 ± 0.2°C is in the range of from 3 to 20, more preferably from 6 to 10, as measured by powder X-ray diffractometry, preferably the ratio of the diffraction peak intensity is measured according to reference example 4. The pigment composition of claim 29 or 30, wherein the amount of quinacridone pigment derivative contained is from 0.1 to 10 parts by mass, relative to 100 parts by mass of pigment, preferably the amount of quinacridone pigment derivative contained in (a)(iii) is from 0.1 to 10 parts by mass, relative to 100 parts by mass of the mixed crystal quinacridone pigment composition. The pigment composition of claim 29 or 30, wherein the amount of quinacridone pigment derivative contained is from 1 to 5 parts by mass, relative to 100 parts by mass of pigment, preferably the amount of quinacridone pigment derivative contained in (a)(iii) is from 1 to 5 parts by mass, relative to 100 parts by mass of the mixed crystal quinacridone pigment composition. The pigment composition of claim 29 or 30, wherein the amount of quinacridone pigment derivative contained is from 0.5 to 3 parts by mass, preferably from 1 to 3 parts by mass, relative to 100 parts by mass of pigment, preferably the amount of quinacridone pigment derivative contained in (a)(iii) is from 0.5 to 3 parts by mass, preferably from 1 to 3 parts by mass, relative to 100 parts by mass of the mixed crystal quinacridone pigment composition. The pigment composition of any one or more of claims 29-33, wherein a narrow particle size distribution obtained with Dv(50) is <150 nm, preferably the narrow particle size distribution obtained with Dv(50) is in the rage of from 10 to 145 nm, more preferably 20 to 140 nm, more preferably from 25 to 130 nm, more preferably from 30 to 120 nm, determined according to reference example 5. The pigment composition of any one or more of claims 29-34, wherein the composition is chlorine-free. A printing ink or coating or plastic composition comprising the pigment composition of any one or more of claims 29-35.
37. The printing ink or coating composition of claim 36, wherein the composition is suitable for use as printing ink, automotive coating, architectural coating or industrial coating.
38. The printing ink composition of claim 37, wherein the composition is suitable for use as a digital printing ink, inkjet ink, electrophotographic toner, aqueous ink, UV- curable ink, solvent-based ink or oil-based ink.
39. A printed or coated article comprising the printing ink or coating composition of any one or more of claims 35-38.
40. The printed article of claim 39, wherein the article is a plastic article. 41 . A plastic article comprising the pigment composition of any one or more of claims 29-
PCT/EP2023/060793 2022-04-26 2023-04-25 Mixed crystal composition of quinacridones with diketopyrrolopyrroles and manufacturing process WO2023208924A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP22170119 2022-04-26
EP22170119.6 2022-04-26

Publications (1)

Publication Number Publication Date
WO2023208924A1 true WO2023208924A1 (en) 2023-11-02

Family

ID=81387167

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2023/060793 WO2023208924A1 (en) 2022-04-26 2023-04-25 Mixed crystal composition of quinacridones with diketopyrrolopyrroles and manufacturing process

Country Status (1)

Country Link
WO (1) WO2023208924A1 (en)

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3148191A (en) * 1962-11-02 1964-09-08 Du Pont Process for preparing quinacridone pigments
US5847143A (en) * 1995-09-22 1998-12-08 Ciba Specialty Chemicals Corporation Process for preparing quinacridones
US6468341B2 (en) * 2000-02-04 2002-10-22 Dainichiseika Color & Chemicals Pigment compositions, production process thereof, colorants, and colored articles
US20050011403A1 (en) 2003-07-18 2005-01-20 Mitina Valentina K. Quinacridone pigment compositions comprising unsymmetrically substituted components
US7211139B2 (en) * 2005-05-03 2007-05-01 Sun Chemical Corporation Process for preparing nanoscale quinacridone
JP4336118B2 (en) * 2003-02-24 2009-09-30 東洋インキ製造株式会社 Color filter pigment, coloring composition for color filter using the same, and color filter
JP2019112534A (en) 2017-12-25 2019-07-11 東洋インキＳｃホールディングス株式会社 Diketopyrrolopyrrole pigment solid solution composition, and coloring composition using diketopyrrolopyrrole pigment solid solution composition
EP3533842A1 (en) 2016-10-28 2019-09-04 Dainichiseika Color & Chemicals Mfg. Co., Ltd. Method for producing quinacridone solid solution pigment, pigment dispersion, and inkjet ink
EP3778784A1 (en) 2018-03-30 2021-02-17 Dainichiseika Color & Chemicals Mfg. Co., Ltd. Method for producing quinacridone solid-solution pigment, pigment dispersion, and ink-jet ink
EP3786236A1 (en) 2018-04-17 2021-03-03 DIC Corporation Solid solution of quinacridone and ink composition containing same
EP3480264B1 (en) 2016-06-29 2021-11-03 Sakata INX Corporation Nonaqueous ink-jet magenta ink composition

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3148191A (en) * 1962-11-02 1964-09-08 Du Pont Process for preparing quinacridone pigments
US5847143A (en) * 1995-09-22 1998-12-08 Ciba Specialty Chemicals Corporation Process for preparing quinacridones
US6468341B2 (en) * 2000-02-04 2002-10-22 Dainichiseika Color & Chemicals Pigment compositions, production process thereof, colorants, and colored articles
JP4336118B2 (en) * 2003-02-24 2009-09-30 東洋インキ製造株式会社 Color filter pigment, coloring composition for color filter using the same, and color filter
US20050011403A1 (en) 2003-07-18 2005-01-20 Mitina Valentina K. Quinacridone pigment compositions comprising unsymmetrically substituted components
US7166158B2 (en) 2003-07-18 2007-01-23 Ciba Specialty Chemicals Corporation Quinacridone pigment compositions comprising unsymmetrically substituted components
US7211139B2 (en) * 2005-05-03 2007-05-01 Sun Chemical Corporation Process for preparing nanoscale quinacridone
EP3480264B1 (en) 2016-06-29 2021-11-03 Sakata INX Corporation Nonaqueous ink-jet magenta ink composition
EP3533842A1 (en) 2016-10-28 2019-09-04 Dainichiseika Color & Chemicals Mfg. Co., Ltd. Method for producing quinacridone solid solution pigment, pigment dispersion, and inkjet ink
JP2019112534A (en) 2017-12-25 2019-07-11 東洋インキＳｃホールディングス株式会社 Diketopyrrolopyrrole pigment solid solution composition, and coloring composition using diketopyrrolopyrrole pigment solid solution composition
EP3778784A1 (en) 2018-03-30 2021-02-17 Dainichiseika Color & Chemicals Mfg. Co., Ltd. Method for producing quinacridone solid-solution pigment, pigment dispersion, and ink-jet ink
EP3786236A1 (en) 2018-04-17 2021-03-03 DIC Corporation Solid solution of quinacridone and ink composition containing same

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"High Performance Pigments", 2002, WILEY-VCH VERLAG-GMBH, pages: 296
CAS , no. 88949-33-1
CAS, no. 84632-66-6

Similar Documents

Publication Publication Date Title
KR101009900B1 (en) Method for the production of phthalocyanine pigment preparations
EP1646691B1 (en) Quinacridone pigment compositions comprising unsymmetrically substituted components
KR100588884B1 (en) Perylene compounds and pigment preparations
JP3518300B2 (en) Pigment dispersant and pigment composition containing the same
JP3337234B2 (en) New pigment preparations based on dioxazine compounds
EP0643109B1 (en) Preparation of pigmentary 2,9-dichloroquinacridone
EP1689746A2 (en) A process for aqueous milling of quinacridone pigments
EP0704496B1 (en) Pigmentary solid solutions of pyrrolo 3,4-C pyrroles and quinacridones
KR100484685B1 (en) Preparation of Phthalocyanine-Containing Waterborne Coating Systems
WO2023208924A1 (en) Mixed crystal composition of quinacridones with diketopyrrolopyrroles and manufacturing process
JP5481873B2 (en) β-type phthalocyanine pigment and coloring composition using the same
WO2016207113A1 (en) Naphthol as-pigment-mixtures
JP4126725B2 (en) δ-type indanthrone blue pigment and method for producing the same
JP2024501369A (en) Near-infrared (NIR) transparent neutral black solid solution pigment
EP1387870A2 (en) New crystal modification of diketopyrrolpyrrole solid solution pigment
EP4038145A1 (en) Isoindoline derivatives
JPH1053714A (en) Introduction of pigment derivative in the quinacridone process
JP5481872B2 (en) ε-type phthalocyanine pigment and coloring composition using the same
EP0905199A2 (en) Microwave syntheses of quinacridones, 6, 13-dihydroquinacridones and 6, 13-quinacridonequinones
JP4696937B2 (en) Method for producing dichloroquinacridone pigment
US10711137B2 (en) Pigment compositions containing chlorinated copper phthalocyanine pigments in the gamma crystal form
JP2024502260A (en) Near-infrared (NIR) transparent neutral black perylene solid solution
WO2000026303A1 (en) Solid solutions of monoazo pigments
EP3197954A1 (en) Pigment composition

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23722316

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)