BIO-sourced phthalocyanine complex, preparation and use thereof

Abstract

The invention is directed to a phthalocyanine complex, a method for preparing the phthalocyanine complex, a colour composition comprising the phthalocyanine complex, a method for preparing a colour composition comprising the phthalocyanine complex, an article, and uses of the phthalocyanine complex. The phthalocyanine complex of the invention has general formula (I): wherein R1 - R16 are the same or different and each R1 to R16 is individually selected from the group consisting of hydrogen, C1-C22 alkyl, C3-C22 alkenyl, C3-C22 alkynyl, chlorine, bromine, fluorine, iodine, sulphonate, and −[(CH2)n−O−(CH2)m]o−CH3, wherein n = 0-16, m = 1-16, o = 1-20, wherein M is selected from the group consisting of Cu, Ni, Zn, Co, Fe, Mn, and Al, and wherein the phthalocyanine complex has a biobased carbon content of at least 10 % relative to the total mass of carbon in the phthalocyanine complex, as determined according to ASTM D 6866-22.

Description

[0001] Title: BIO-SOURCED PHTHALOCYANINE COMPLEX,

[0002] PREPARATION AND USE THEREOF

[0003] The invention is directed to a phthalocyanine complex, a method for preparing the phthalocyanine complex, a colour composition comprising the phthalocyanine complex, a method for preparing a colour composition comprising the phthalocyanine complex, an article, and uses of the phthalocyanine complex.

[0004] Phthalocyanines are an important class of synthetic colourants, used for instance as automotive paints, printing inks and as pigments for polymers, textiles, and paper. Most relevant manufacturing processes for the production of phthalocyanines are a phthalonitrile process, and a phthalic anhydride / urea process, as discussed in Industrial Organic Pigments (2004), Chapter 3.1 by W. Herbst, K. Hunger.

[0005] US-A-5 393 339 relates to a process for preparing metal-containing phthalocyanines and chlorinated phthalocyanines for the use as colourants.

[0006] US-A-2007 / 0 179 285 discloses a process for preparing alkoxy-substituted, metal-containing phthalocyanines for the use as light-absorbent compounds in the light-writable information layer of optical data stores.

[0007] WO-A-01 / 42368 describes a process for preparation of alkyl-, alkenyl-, alkynyL, aryl-, heteroaryL, amine-, halogen-, ether-, ester-, and / or amide-substituted metal-containing phthalocyanines. These phthalocyanines seem to particularly useful for photosensitisation in pharmaceutical compositions due to their photodynamic properties.

[0008] WO-A-2022 / 255135 discloses a process for preparation of a biomass-derived Phthalocyanine Blue 15 (CAS number 147-14-8) from biomass-derived phthalic anhydride, obtained from biomass-derived furan and biomass-derived maleic anhydride, urea, and copper chloride in the presence of ammonium molybdate tetrahydrate. WO-A-2022 / 255135 teaches numerous biobased phthalocyanines with various substituents, as disclosed, e.g., in claim 1 of WO-A-2022 / 255135. However, the disclosure of WO-A-2022 / 255135 does not teach the skilled person in an enabling manner how to obtain all the biobased phthalocyanines falling within the scope of claim 1 of WO-A-2022 / 255135. WO-A-2022 / 255135 provides limited teaching regarding how to obtain said phthalocyanines starting from available biobased precursors starting from furan and its derivatives, maleic anhydride, urea, and a metal salt. In particular, WO-A-2022 / 255135 teaches an extensive list of possible furan compounds with multiple substituents, while providing no guidance on how to derive such molecules from biomass. For example, WO-A-2022 / 255135 is silent on how to obtain methylated phthalocyanines denoted as 1-2-1, 1-3-1, 1-4-1, 1-5-1, and I- 10-1 in Chemical structure 26 of WO-A-2022 / 255135.

[0009] The conventional, industrial-scale phthalocyanines synthesis routes, i.e. the phthalonitrile process, and the phthalic anhydride / urea process, typically utilise fossil-fuel based starting materials, i.e. chemicals, such phthalic anhydride or phthalonitrile derived through petrochemical processes. Due to the environmental and social concerns related to depleting fossil fuels reserves, there is a need to replace petroleum -based products, including dyes and pigments, with the corresponding products derived from natural, e.g. bio-sourced resources, as starting materials, i.e. chemicals.

[0010] Furthermore, certain phthalocyanine pigments, such as Phthalocyanine Blue 15 and Pigment Green 7, suffer from limited thermal stability which limits their application in colouring certain polymers, e.g. poly(vinyl chloride), polyolefins, such as polystyrene, polyethylene, polypropylene acrylonitrile butadiene styrene, polyphenylene oxide, polyether ketones, such as polyether ether ketone, and polyamides.

[0011] Additionally, phthalocyanine complexes in general exhibit limited solubility in organic solvents, polymeric matrices, and other suitable colourant compositions carriers. There is a need to improve the thermal stability of phthalocyanine dyes and pigments and / or their solubility in organic solvent, polymeric matrices, and / or other suitable colourant compositions carriers.

[0012] An objective of the invention is to overcome one or more of the disadvantages faced in the prior art.

[0013] A further objective of the invention is to provide a non petroleum-sourced phthalocyanine complex.

[0014] Yet a further objective of the invention is to provide a phthalocyanine complex with low carbon footprint.

[0015] Yet a further objective of the invention is to provide a phthalocyanine complex with low embodied energy.

[0016] Yet a further objective of the invention is to provide a phthalocyanine complex with improved thermal stability.

[0017] Yet a further objective of the invention is to provide a phthalocyanine complex with improved solubility in organic solvent, polymeric matrices, in particular in suitable colourant compositions carriers.

[0018] A further objective of the invention is to provide a colour composition, in particular a colour concentrate, comprising a non petroleum-sourced phthalocyanine complex.

[0019] Yet a further objective of the invention is to provide a phthalocyanine complex wherein all carbon sources of the phthalocyanine complex are from natural sources, such as plant, instead of from petroleum.

[0020] The inventors found that one or more of these objectives can, at least in part, be met by providing a phthalocyanine complex with a biobased carbon content of at least 10 %.

[0021] The term “pigment” as used herein is meant to refer to an organic or inorganic material, which is substantially insoluble, e.g. at least 95 wt.% of the material is insoluble, e.g. in organic solvent, polymeric matrix, and other suitable colourant compositions carrier.

[0022] The term “dye” as used herein is meant to refer to an organic or inorganic material, which is substantially or completely soluble, e.g. at least 95 wt.% of the material is soluble, e.g. in organic solvent, polymeric matrix, and other suitable colourant compositions carrier.

[0023] Thereby, the same material, e.g. a chemical compound such as a phthalocyanine complex, can be both a pigment and a dye, depending on the medium in which it is dispersed or dissolved, respectively.

[0024] The terms “biobased” and “bio-sourced” as used herein is meant to express that the compound was synthesised from a biological precursor, and specifically a renewable biological carbon source, such as biomass (as opposed to a non-renewable petroleum -based carbon source). The biomass can suitably be in the form of a plant. In particular, the terms “biobased” and “bio-sourced” as used herein are meant to refer to a material or a chemical compound that is “isotopically rich” in carbon 14 (14C) as compared to a fossil-based material or a fossil-based chemical compound, as determined by ASTM D 6866-22, i.e. as a biobased carbon content of a material of a product referred to as a percent of a total organic carbon in the material or the product. The term “isotopically rich” as used herein is meant to refer to a higher carbon 14 (14C) to carbon 12 (12C) ratio (14C / 12C) in a material or a chemical compound as compared to the carbon 14 (14C) to carbon 12 (12C) ratio (14C / 12C) in a fossil-based material or a fossil-based chemical compound. Suitably, the biobased content, as determined by ASTM D 6866-22, is calculated by dividing a percent modern carbon (pMC) by an atmospheric correction factor (REF). The pMC is determined as an isotopic ratio of14C / 12C relative to a modern reference standard. The modern reference standard is NIST SRM 4990C (oxalic acid)14C standard. The REF value depends on14C activity in the atmosphere at the time of testing, the REF for given year is given in Table 1 of ASTM D 6866-22, which is herewith completely incorporated by reference. The skilled person understands that for future REF values, corresponding new editions of ASTM D 6866 will have to be consulted. Optionally, the term “biobased carbon content” refers to the pMC, as described herein.

[0025] The term “C1-C22 alkyl” as used herein is meant to refer to any alkyl substituent, linear or branched, consisting of from 1 to 22 carbon atoms, e.g. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl, sec-isopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosanyl, heneicosanyl, docosanyl.

[0026] The term “C3-C22 alkenyl” as used herein is meant to refer a substituent, linear or branched, consisting of from 3 to 22 carbon atoms and comprising at least one double bond, e.g. propenyl, butenyl, isobutenyl, sec-butenyl, tert-butenyl, pentenyl, isopentenyl, sec-pentenyl, tert-pentenyl, neopentenyl, sec-isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, docosenyl.

[0027] The term “C3-C22 alkynyl” as used herein is meant to refer to a substituent, linear or branched, consisting of from 3 to 22 carbon atoms and comprising at least one triple bond, e.g. propynyl, butynyl, isobutynyl, sec-butynyl, tert-butynyl, pentynyl, isopentynyl, sec-pentynyl, tert-pentynyl, neopentynyl, sec-isopentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonadecynyl, eicosynyl, heneicosynyl, docosynyl.

[0028] The term “Ce-C is fatty acid” as used herein is meant to refer to a substituent, linear or branched, saturated or unsaturated, consisting of from 6 to 18 carbon atoms, e.g. hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, decenoic acid, undecenoic acid, dodecenoic acid, tridecenoic acid, tetradecenoic acid, pentadecenoic acid, hexadecenoic acid, heptadecenoic acid, octadecenoic acid.

[0029] The term “colour composition” as used herein is meant to refer to a composition that can suitably be used in a polymer composition, e.g. fibres, films, and coatings, inks, paints, e.g. water-based paints or solvent-based paints, textiles, or cosmetics. Preferably, the polymer composition comprises a thermoplastic polymer or a thermoset polymer such as polyurethane and copolymers thereof; epoxy and copolymers thereof; poly(vinyl chloride); polyolefin and copolymers thereof, such as polystyrene, polyethylene, polypropylene acrylonitrile butadiene styrene, poly(ethylene-vinyl acetate); polyamide and co-polymers thereof; polycarbonate and copolymers thereof.

[0030] The composition may be prepared by concentrating one or more chemical compounds. If used as a colour concentrate, the colour composition typically comprises a component which is present in the colour composition at a higher level than intended for the final polymer composition. Hence, the colour composition of the invention that is intended for use as a dye or a pigment preferably in cosmetics, colour compositions, textiles, paints, and inks, comprises the phthalocyanine complex of the invention. The colour composition may be easy to dose, and has the advantage that it is possible to add the required amounts of the phthalocyanine complex of the invention to a polymer composition without unduly adding separate chemical compounds and / or unwanted other components in large amounts to the polymer composition. The colour composition can be incorporated in a polymer composition, e.g. in a (final) article. Typically, the colour composition may be an intermediate product, primarily destined for further processing to acquire finished polymer products. Such colour compositions are well-known in the technical field to influence one or more chemical and / or physical properties (such as light transmittance and colour) of a polymer composition. At production temperatures, the colour composition may be solid or liquid. Preferably, the colour composition is solid at room temperature, and liquid at production temperature.

[0031] The colour composition may be liquid, e.g. the phthalocyanine complex can be dispersed in a liquid carrier, e.g. hydrocarbon oil, edible oil, ester, alcohol, trimethylolpropane ester, silicone oil, or a mixture of two or more thereof, preferably fatty acid ester of trimethylolpropane, more preferably wherein the fatty acid is a Ce to Cis fatty acid having a linear or branched chain, oleate or isostearate.

[0032] The colour composition may be solid, e.g. the phthalocyanine complex can be dispersed in a solid carrier, e.g. a polymer, such as polyurethane and copolymers thereof; epoxy and copolymers thereof; poly(vinyl chloride); polyolefin and copolymers thereof, such as polystyrene, polyethylene, polypropylene acrylonitrile butadiene styrene, poly(ethylene-vinyl acetate); polyamide and copolymers thereof; polycarbonate and copolymers thereof.

[0033] Furthermore, the colour composition may be mixed with one or more commercially available colour compositions. In the art, the terms “colour composition” “concentrate” and “masterbatch” are used interch ange ably .

[0034] The term “D90” as used herein is meant to refer to a particles (preferably a phthalocyanine complex particles) having at least 90 % of the particles having a particle size, i.e. a largest dimension, up to the D90 value based on number weighted particle size distribution.

[0035] In a first aspect, the invention is directed to a phthalocyanine complex of general formula (I): wherein each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16, are the same or different and each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16is individually selected from hydrogen, C1-C22 alkyl, C3-C22 alkenyl, C3-C22 alkynyl, chlorine, bromine, fluorine, iodine, sulphonate, and -[(CH2)n-O-(CH2)m]o_CH3, wherein n = 0-16, m = 1-16, 0 = 1-20, wherein M is a metal atom selected from Cu, Ni, Zn, Co, Fe, Mn, and Al, and wherein the phthalocyanine complex has a biobased carbon content of at least 10 % relative to the total mass of carbon in the phthalocyanine complex, as determined according to ASTM D 6866-22.

[0036] Preferably, the phthalocyanine complex has a biobased carbon content of 15 % relative to the total mass of carbon in the phthalocyanine complex or more, such as 20 % or more, 25 % or more, 30 % or more, 35 % or more, 40 % or more, 45 % or more, 50 % or more, 55 % or more, 60 % or more, 65 % or more, 70 % or more, 75 % or more, 80 % or more, 85 % or more, 90 % or more, or 95 % or more, and / or 100 % or less, as determined according to ASTM D 6866-22.

[0037] Suitably, the phthalocyanine complex has a biobased carbon content between 40 and 80 % relative to the total mass of carbon in the phthalocyanine complex, such as between 45 and 75 %, or between 50 and 70 %, as determined according to ASTM D 6866-22.

[0038] Suitably, the phthalocyanine complex has a biobased carbon content between 95 % and 100 % relative to the total mass of carbon in the phthalocyanine complex, as determined according to ASTM D 6866-22. The phthalocyanine complex of the invention wherein the phthalocyanine complex has a biobased carbon content of at least 10 % relative to the total mass of carbon in the phthalocyanine complex, is particularly suitable to be used as, at least partially, preferably fully, biobased colourant. The phthalocyanine complex is a desired alternative to the currently used phthalocyanine colourants obtained from the petroleum resources. Furthermore, the production of the phthalocyanine complex of the invention, wherein the phthalocyanine complex has a biobased carbon content of at least 10 % relative to the total mass of carbon in the phthalocyanine complex, has advantageously lower impact on the environment, for instance the biobased phthalocyanine has lower carbon footprint compared with the petroleum-based phthalocyanine.

[0039] Preferably, in the phthalocyanine complex each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16is hydrogen.

[0040] The phthalocyanine complex, wherein M is Cu, is advantageously the biobased form of well-known phthalocyanine colourant, Phthalocyanine Blue 15 (CAS number 147-14-8). Advantageously, biobased Phthalocyanine Blue 15 can be used without any major technology or equipment investments by the end-user while exhibiting desired performance of the petroleum-based Phthalocyanine Blue 15 (PB 15), such as PB15:0, PB15:1, PB15:3, PB15:4 or PB15:6.

[0041] Preferably, in the phthalocyanine complex at least one of Rx-R16is not hydrogen. Preferably, at least one of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16is C1-C22 alkyl, C3-C22 alkenyl, and / or C3-C22 alkynyl, more preferably Ci-Ce alkyl, C3-C6 alkenyl, and / or C3-C6 alkynyl. Preferably, at least four of R1, R2, R3, R4, R5, R6, R7, R8, R9, Rio, Rn, Ri2, R13, R14, R15, and R16are C1-C22 alkyl, C3-C22 alkenyl, and / or C3-C22 alkynyl, more preferably Ci-Ce alkyl, C3-C6 alkenyl, and / or C3-C6 alkynyl. Preferably, at least eight of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16are C1-C22 alkyl, C3-C22 alkenyl, and / or C3-C22 alkynyl, more preferably Ci-Ce alkyl, C3-C6 alkenyl, and / or C3-C6 alkynyl.

[0042] The inventors unexpectedly found that when at least one of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16is C1-C22 alkyl, C3-C22 alkenyl, and / or C3-C22 alkynyl, the phthalocyanine complex advantageously exhibits higher thermal stability as compared to Phthalocyanine Blue 15. Advantageously, the phthalocyanine complexes of the invention are particularly suitable for the use, e.g. as a colourant for polymers, e.g. polyolefins, polyurethanes, polyamides, polycarbonates, requiring processing at high temperatures, e.g. 250 °C or more, and / or which are exposed to high temperatures in their use.

[0043] Preferably, one of R1and R4is methyl and one of R1and R4is hydrogen, one of R5and R8is methyl and one of R5and R8is hydrogen, one of R9and R12is methyl and one of R9and R12is hydrogen, one of R13and R16is methyl and one of R13and R16is hydrogen, and each of R2, R3, R6, R7, R10, R11, R14, and R15is hydrogen.

[0044] Preferably, each of R1, R4, R5, R8, R9, R12, R13, and R16is methyl, and each of R2, R3, R6, R7, R10, R11, R14, and R15is hydrogen. The inventors unexpectedly found that when at least one of R1and R4is C1-C22 alkyl, more preferably Ci-Ce alkyl, and one of R1and R4is hydrogen, one of R5and R8is C1-C22 alkyl, more preferably Ci-Ce alkyl, and one of R5and R8is hydrogen, one of R9and R12is C1-C22 alkyl, more preferably Ci-Ce alkyl, and one of R9and R12is hydrogen, one of R13and R16is C1-C22 alkyl, more preferably Ci-Ce alkyl, and one of R13and R16is hydrogen, and each of R2, R3, R6, R7, R10, R11, R14, and R15is hydrogen, the phthalocyanine complex advantageously exhibits improved resistance to weathering, in particular when present in a colour composition comprising a polymer, such as poly(vinyl chloride) (PVC), as compared to Phthalocyanine Blue 15, as shown in Example 11.

[0045] Preferably, one of R1and R4is C1-C22 alkyl, more preferably Ci-Ce alkyl, and one of R1and R4is selected from chlorine, bromine, fluorine, and iodine, one of R5and R8is C1-C22 alkyl, more preferably Ci-Ce alkyl, and one of R5and R8is selected from chlorine, bromine, fluorine, and iodine, one of R9and R12is C1-C22 alkyl, more preferably Ci-Ce alkyl, and one of R9and R12is selected from chlorine, bromine, fluorine, and iodine, one of R13and R16is C1-C22 alkyl, more preferably Ci-Ce alkyl, and one of R13and R16is selected from chlorine, bromine, fluorine, and iodine, and each of R2, R3, R6, R7, R10, R11, R14, and R15is selected from chlorine, bromine, fluorine, and iodine. Preferably, each Rx-R16selected from chlorine, bromine, fluorine, and iodine is the same.

[0046] Even more preferably, one of R1and R4is methyl and one of R1and R4is selected from chlorine, bromine, fluorine, and iodine, one of R5and R8is methyl and one of R5and R8is selected chlorine, bromine, fluorine, and iodine, one of R9and R12is methyl and one of R9and R12is selected from chlorine, bromine, fluorine, and iodine, one of R13and R16is methyl and one of R13and R16is selected from chlorine, bromine, fluorine, and iodine, and each of R2, R3, R6, R7, R10, R11, R14, and R15is selected from chlorine, bromine, fluorine, and iodine. Preferably, each Rx-R16selected from chlorine, bromine, fluorine, and iodine is the same. Even more preferably, one of R1and R4is methyl and one of R1and R4is chlorine, one of R5and R8is methyl and one of R5and R8chlorine, one of R9and R12is methyl and one of R9and R12is chlorine, one of R13and R16is methyl and one of R13and R16is chlorine, and each of R2, R3, R6, R7, R10, R11, R14, and R15is chlorine.

[0047] Even more preferably, one of R1and R4is methyl and one of R1and R4is bromine, one of R5and R8is methyl and one of R5and R8bromine, one of R9and R12is methyl and one of R9and R12is bromine, one of R13and R16is methyl and one of R13and R16is bromine, and each of R2, R3, R6, R7, R10, R11, R14, and R15is bromine.

[0048] Preferably, each of R1, R4, R5, R8, R9, R12, R13, and R16is C1-C22 alkyl, more preferably Ci-Ce alkyl, and each of R2, R3, R6, R7, R10, R11, R14, and R15is selected from chlorine, bromine, fluorine, and iodine. Preferably, each R2, R3, R6, R7, R10, R11, R14, and R15selected from chlorine, bromine, fluorine, and iodine is the same. Preferably, each R1, R4, R5, R8, R9, R12, R13, and R16is the same.

[0049] More preferably, each of R1, R4, R5, R8, R9, R12, R13, and R16is methyl, and each of R2, R3, R6, R7, R10, R11, R14, and R15is selected chlorine, bromine, fluorine, and iodine. Preferably, each R2, R3, R6, R7, R10, R11, R14, and R15selected from chlorine, bromine, fluorine, and iodine is the same.

[0050] Even more preferably, each of R1, R4, R5, R8, R9, R12, R13, and R16is methyl, and each of R2, R3, R6, R7, R10, R11, R14, and R15is chlorine.

[0051] Even more preferably, each of R1, R4, R5, R8, R9, R12, R13, and R16is methyl, and each of R2, R3, R6, R7, R10, R11, R14, and R15is bromine.

[0052] Preferably, at least one of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16is an ether with a structure [(CH2)n- O- (CH2)m]o, wherein n = 0-16, m = 1-16, 0 = 1-20. Preferably, the ether either has a structure [O-(CH2)]o, [O-(CH2)2]o, i.e. the ether is a polyethylene glycol oligomer or a polypropylene glycol oligomer, or the ether has a structure O-(CH2)m. The skilled person will understand that the ether comprises the general structure [(CH2)n-O-(CH2)m]o, [O-(CH2)]o, [O- (CH2)2]O, and / or O-(CH2)mand an end group, e.g. a methyl group. Preferably, at least one of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16is an ether having a structure - [(CH2)n- O- (CH2)m]o_CH3, wherein n = 0-16, m = 1-16, o = 1-20. Preferably, the ether either has a structure -[O-(CH2)]o_CH3, -[O-(CH2)2]o_CH3, i.e. the ether is a polyethylene glycol oligomer or a polypropylene glycol oligomer, or the ether has a structure -O-(CH2)m-CH3.

[0053] Without wishing to be bound by any theory, the inventors believe that ether-substituted phthalocyanines of general formula (I) exhibit improved solubility in organic solvents, such as acetone, acetonitrile, anisole, benzene, butanol, chlorobenzene, chloroform, decanol, dichloromethane, diethyl ether, 1,4-dioxane, dimethylacetamide, dimethylformamide, dimethyl sulphoxide, ethanol, ethyl acetate, hexane, hexanol, heptane, heptanol, pentanol, propanol, isopropanol, methanol, iV-methyl-2 -pyrrolidone, tetrahydrofuran, 2-methyltetrahydrofuran, toluene, xylene, polymeric matrices, such as polyurethane, epoxy resins, poly(vinyl chloride), polycarbonates, polyolefins, and polyamides, aromatic polymers other than polyesters, and carriers, such as silicon oils, hydrocarbon oils, vegetable oils, hydrogenated vegetable oils, esters, e.g., trimethylolpropane esters, fatty acids, fatty acid methyl esters, fatty acid sorbitol esters, fatty acid sorbitan esters, fatty acid pentaerythritol esters, monoglycerides, diglycerides, triglycerides, salts of fatty acids, amide waxes, polyethoxylated glycols and derivatives, polyethylene waxes and ethylene vinyl acetate waxes, and mixtures thereof. Improved solubility advantageously enables to use the phthalocyanine of general formula (I) as a dye, for example in textiles and printing inks.

[0054] Preferably, at least one of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16is chlorine, bromine, fluorine, and / or iodine, preferably at least one of R2, R3, R6, R7, R10, R11, R14, and R15is chlorine, bromine, fluorine, and / or iodine. More preferably, at least one of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16is chlorine and / or bromine. More preferably, at least one of R2, R3, R6, R7, R10, R11, R14, and R15is chlorine or at least one of R2, R3, R6, R7, R10, R11, R14, and R15is bromine. Even more preferably, at least four of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16are chlorine, bromine, fluorine, and / or iodine.

[0055] Even more preferably, at least four of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16are chlorine and / or bromine.

[0056] More preferably, one of R2and R3is chlorine or bromine and one of R2and R3is hydrogen, one of R6and R7is chlorine or bromine and one of R6and R7is hydrogen, one of R10and R11is chlorine or bromine and one of R10and R11is hydrogen, one of R14and R15is chlorine or bromine and one of R14and R15is hydrogen, and each of R1, R4, R5, R8, R9, R12, R13, and R16is hydrogen or at least one of R1, R4, R5, R8, R9, R12, R13, and R16is C3-C22 alkyl, C3-C22 alkenyl, C3-C22 alkynyl, and / or -[(CH2)n-O-(CH2)m]o_CH3, wherein n = 0-16, m = 1-16, 0 = 1-20.

[0057] Preferably, one of R2and R3is chlorine and one of R2and R3is hydrogen, one of R6and R7is chlorine and one of R6and R7is hydrogen, one of R10and R11is chlorine and one of R10and R11is hydrogen, one of R14and R15is chlorine and one of R14and R15is hydrogen, and each of R1, R4, R5, R8, R9, R12, R13, and R16is hydrogen or at least one of R1, R4, R5, R8, R9, R12, R13, and R16is C3-C22 alkyl, C3-C22 alkenyl, C3-C22 alkynyl, and / or - [(CH2)n- O- (CH2)m]o_CH3, wherein n = 0-16, m = 1-16, o = 1-20.

[0058] Preferably, at least eight of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16are chlorine, bromine, fluorine, and / or iodine. More preferably, each of R2and R3is chlorine or bromine, each of R6and R7is chlorine or bromine, each of R10and R11is chlorine or bromine, and each of R14and R15is chlorine or bromine. Most preferably, each of R2, R3, R6, R7, R10, R11, R14and R15is chlorine or each of R2, R3, R6, R7, R10, R11, R14and R15is bromine. Preferably, each of R1, R4, R5, R8, R9, R12, R13, and R16is hydrogen or at least one of R1, R4, R5, R8, R9, R12, R13, and R16is C3-C22 alkyl, C3-C22 alkenyl, C3-C22 alkynyl, and / or -[(CH2)n-O-(CH2)m]o_CH3, wherein n = 0-16, m = 1-16, 0 = 1-20.

[0059] Preferably, at least fourteen, more preferably fifteen or sixteen, of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16are chlorine, bromine, fluorine, and / or iodine, more preferably chlorine and / or bromine.

[0060] The phthalocyanine complex of the invention, in particular wherein M is Cu and at least fourteen of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16are chlorine, can advantageously replace a well-known phthalocyanine colourant, Pigment Green 7 (PG7, CAS number 1328-53-6). Advantageously, biobased Pigment Green 7 can be used without any major technology or equipment investments by the end-user while exhibiting desired performance of the petroleum-based Pigment Green 7. Without wishing to be bound by theory, the inventors believe that at least partially halogenated phthalocyanines advantageously exhibit improved lightfastness and thermal stability compared to Phthalocyanine Blue 15.

[0061] Preferably, 50 % or more of the number of the phthalocyanine complex particles, preferably 55 % or more, 60 % or more, 65 % or more, 70 % or more, 75 % or more, 80 % or more, 85 % or more, 90 % or more, 95 % or more, or 97 % or more, and / or 100 % or less is in a crystal form, as determined by X-ray diffraction (XRD). At least 50 % of the number of the phthalocyanine complexes, such as at least 60 %, at least 70 %, at least 80 %, at least 90 %, or at least 95 %, may be in an a crystal form, as determined by X-ray diffraction. At least 50 % of the number of the phthalocyanine complexes, such as at least 60 %, at least 70 %, at least 80 %, at least 90 %, or at least 95 %, may be in an 0 crystal form, as determined by X-ray diffraction.

[0062] The phthalocyanine complex may be a Phthalocyanine Blue 15:1, that predominantly exists in the a crystal form crystal form.

[0063] The phthalocyanine complex may be a Phthalocyanine Blue 15:3, that predominantly exists in the 0 crystal form crystal form.

[0064] The crystal form of the phthalocyanine can be determined, e.g., by X-ray diffraction, by Raman spectroscopy, or a combination thereof.

[0065] Without wishing to be bound by any theory, the inventors believe that the phthalocyanine complex of the invention at least partially present in its crystalline form exhibits stable, desired colour. Preferably, the phthalocyanine complex of the invention is in particulate form having a D90 of 50 pm or less, more from 5 to 30 pm, even more from 5 to 25 pm, as determined by an optical microscopy.

[0066] The inventors observed that the phthalocyanine complex of the invention having such D90 exhibits excellent colour strength and good overall performance.

[0067] In a further aspect, the invention pertains to a method for preparing a phthalocyanine complex according to the invention comprising a step A) of reacting a urea or derivative thereof, a phthalic anhydride or derivative thereof, and a metal salt, optionally in a solvent, optionally in the presence of a catalyst to obtain the phthalocyanine complex particles, wherein the phthalic anhydride or derivative thereof has a biobased carbon content of at least 10 % relative to the total mass of carbon in phthalic anhydride or derivative thereof, or at least 15 %, at least 20 %, at least 25 %, at least 30 %, at least 35 %, at least 40 %, at least 45 %, at least 50 %, at least 55 %, at least 60 %, at least 65 %, at least 70 %, at least 75 %, at least 80 %, at least 85 %, at least 90 %, at least 95 %, or at least 97 %, and / or 100 % or less, as determined according to ASTM D 6866-22.

[0068] Advantageously, the phthalic anhydride or derivative thereof having a biobased carbon content of at least 10 % relative to the total mass of carbon in phthalic anhydride or derivative thereof exhibits lower carbon footprint and lower embodied energy compared to their petrochemical counterparts.

[0069] Suitably, urea or derivative thereof, e.g. ammonia, biuret, guanidine, dicyandiamide, can be used in the method of the invention. Preferably, urea is used in the method of the invention.

[0070] The phthalic anhydride or derivative thereof has a structure according to general formula (II), wherein each of R1, R2, R3, and R4are the same or different and each of R1, R2, R3, and R4is individually selected from hydrogen, C1-C22 alkyl, C3-C22 alkenyl, C3-C22 alkynyl, chlorine, bromine, fluorine, iodine, sulphonate, and - [(CH2)n- O- (CH2)m]o_CH3, wherein n = 0-16, m = 1-16, o = 1-20. Preferably, each of R1, R2, R3, and R4is hydrogen. Suitably, at least one of Rx-R4is not hydrogen.

[0071] Preferably, at least one of R1, R2, R3, and R4is C1-C22 alkyl, C3-C22 alkenyl, C3-C22 alkynyl, preferably at least one of Ci-Ce alkyl, C3-C6 alkenyl, C3-C6 alkynyl. More preferably, R1is methyl and each of R2, R3, and R4is hydrogen. More preferably, each of R1and R4is methyl, and each of R2and R3is hydrogen.

[0072] Preferably, R2is chlorine or bromine, and each of R1, R3, and R4is hydrogen. Suitably, each of R2and R3is chlorine or bromine, and each of R1and R4is hydrogen. Suitably, each of R1, R2, R3, and R4is chlorine or bromine.

[0073] Preferably, each of R2and R3is selected from chlorine, bromine, fluorine, and iodine, and each of R1and R4is selected from C1-C22 alkyl, C3-C22 alkenyl, and C3-C22 alkynyl, preferably from Ci-Ce alkyl, C3-C6 alkenyl, and C3-C6 alkynyl. More preferably, each of R2and R3is chlorine, and each of R1and R4is methyl. More preferably, each of R2and R3is bromine, and each of R1and R4is methyl. Preferably, each of R1, R2and R3is selected from chlorine, bromine, fluorine, and iodine, and R4is selected from C1-C22 alkyl, C3-C22 alkenyl, and C3-C22 alkynyl, preferably from Ci-Ce alkyl, C3-C6 alkenyl, and C3-C6 alkynyl. More preferably, each of R1, R2and R3is chlorine and R4is methyl. More preferably, each of R1, R2and R3is bromine and R4is methyl. Preferably, R1is -[(CH2)n-O-(CH2)m]o_CH3, wherein n = 0-16, m = 1-16, o = 1-20, and each of R2, R3, and R4is hydrogen. Suitably, each of R1and R4is -[(CH2)n-O-(CH2)m]o_CH3, wherein n = 0-16, m = 1-16, o = 1-20, and each of R2and R3is hydrogen.

[0074] Certain phthalic anhydride derivatives, e.g. phthalic anhydride derivative of general formula with a biobased carbon content of at least 10 % relative to the total mass of carbon in the phthalic anhydride derivative, or at least 15 %, at least 20 %, at least 25 %, at least 30 %, at least 35 %, at least 40 %, at least 45 %, at least 50 %, at least 55 %, at least 60 %, at least 65 %, at least 70 %, at least 75 %, at least 80 %, at least 85 %, at least 90 %, at least 95 %, or at least 97 %, and / or 100 % or less, as determined according to ASTM D 6866-22, are available from Relement BV.

[0075] Biobased phthalic anhydride and derivatives thereof can be obtained by Diels-Alder reaction between biobased furan or derivative thereof and, preferably biobased, maleic anhydride.

[0076] A method for obtaining biobased phthalic anhydride and derivatives thereof is, for instance, disclosed in US-A-2017 / 0 355 710, the complete content of which is herewith incorporated by reference.

[0077] Maleic anhydride can be obtained from biobased levulinic acid derivatives, e.g. methyl levulinate, via its oxidation to form maleic anhydride, as disclosed in US-B-10 556 852, the complete content of which is herewith incorporated by reference.

[0078] Alternatively or in addition, biobased phthalic anhydride or derivatives thereof can be obtained via oxidation of biobased o-xylene. Biobased o-xylene is available from BioBTX BV, as a part to a mixture comprising biobased benzene, toluene, and xylene isomers. Oxidation of o-xylene is disclosed by Dubey et al. in Asian Journal of Chemistry 1996, 8(3), 341-345, the complete content of which is herewith incorporated by reference, in particular pages 341-342.

[0079] The metal salt is any organic or inorganic salt of the metal M selected from Cu, Ni, Zn, Co, Fe, Mn, and Al. Preferably, the salt is selected from chloride, bromide, iodide, fluoride, carbonate, sulphate, phosphate, and nitrate, most preferably from chloride, carbonate, and sulphate.

[0080] Preferably, the method comprises reacting urea or derivative thereof, phthalic anhydride or phthalic derivative thereof and the metal salt in the solvent, in the presence of a catalyst to obtain the phthalocyanine complex particles.

[0081] The solvent can be any suitable solvent with a boiling point above 180 °C, e.g. 1,2,4-trichlorobenzene, nitrobenzene, naphthalene, kerosene, ethylene glycol, camphor, dimethyl sulphoxide, and mixtures thereof. More preferably, the solvent is selected form 1,2,4-trichlorobenzene, nitrobenzene, naphthalene, kerosene, ethylene glycol, and any mixture thereof.

[0082] The catalyst can be any suitable catalyst for catalysing phthalocyanine synthesis known in the art, more preferably the catalyst is selected from boric acid, molybdenum oxide, zirconium tetrachloride, titanium tetrachloride, ammonium molybdate, most preferably the catalyst is ammonium molybdate or molybdenum oxide.

[0083] Preferably, step A) is performed at a temperature of 160-300 °C, more preferably 180-250 °C, most preferably 200-220 °C.

[0084] The method may be performed in bulk, i.e. without substantial amount of solvent, using a so-called baking process. Preferably all reactants, i.e. urea or derivative thereof, phthalic anhydride or derivative thereof, the metal salt and optionally the catalyst are grinded, optionally in the presence of a small amount of the solvent, e.g. with less than 70 % of solvent based on total weight of the starting materials, to form a slurry. The slurry is preferably subsequently subjected to a thermal treatment at a temperature of 160-300 °C.

[0085] Advantageously, the method of the invention allows for obtaining the phthalocyanine complex with a biobased carbon content of at least 10 % relative to the total mass of carbon in the phthalocyanine complex, or at least 15 %, at least 20 %, at least 25 %, at least 30 %, at least 35 %, at least 40 %, at least 45 %, at least 50 %, at least 55 %, at least 60 %, at least 65 %, at least 70 %, at least 75 %, at least 80 %, at least 85 %, at least 90 %, at least 95 %, or at least 97 %, and / or 100 % or less, as determined according to ASTM D 6866-22. Such phthalocyanine complex production method advantageously has decreased carbon footprint and is long desired by the colourants industry and consumers of end-products comprising phthalocyanine complex.

[0086] Preferably, the method further comprises a step B) of recrystalising the phthalocyanine complex particles to obtain crystalline phthalocyanine complex particles, and / or a step C) of reducing the size of the phthalocyanine complex particles or the crystalline phthalocyanine complex particles to obtain size reduced phthalocyanine complex particles or size reduced crystalline phthalocyanine complex particles.

[0087] Step B) can be carried out by dissolving the crude phthalocyanine in concentrated acid, preferably sulphuric acid or oleum, and precipitation of the crude phthalocyanine in water. Suitably, step B) may be carried out at elevated temperature, e.g. at a temperature of 30-80 °C, preferably 40-60 °C. Suitably, step B) may be carried out using sulphuric acid, preferably having a concentration of 40-100 wt.%, more preferably 50-100 wt.%.

[0088] Step C) can carried out by grinding. Suitably, grinding may be performed at ambient or at elevated temperatures, in dry or in humid conditions, with or without the presence of a grinding agent, e.g. sodium chloride, and optionally in the presence of a solvent, preferably selected from xylene, nitrobenzene, chlorobenzene, alcohols, ketones, esters, and any mixture thereof.

[0089] The steps of recrystalising and / or reducing the size of the phthalocyanine complex particles advantageously allow for obtaining phthalocyanine complex particles in the desired size, e.g. the particles having a D90 of 50 pm or less, such as from 5 to 25 pm, and in the desired crystalline form to obtain the phthalocyanine complex with the excellent colour performance, such as colour strength, tone, and purity among others.

[0090] The method may further comprise a post- synthesis modification of the crude phthalocyanine or the crystalline phthalocyanine complex particles, such as by halogenation, e.g. chlorination or bromination, sulphonation, chlorosulphonation, or chloromethylation. Post-synthesis modification methods are e.g. disclosed in Lobbert, G. (2012), Phthalocyanines, in Ullmann’s Encyclopedia of Industrial Chemistry, the disclosure of which is herewith completely incorporated by reference.

[0091] Preferably, the method further comprises halogenation, e.g. chlorination or bromination, of the phthalocyanine complex. Preferably, at least one of Rx-R16of the phthalocyanine complex is hydrogen, more preferably at least 8 of Rx-R16are hydrogen, e.g. one of R1and R4is C1-C22 alkyl, more preferably Ci-Ce alkyl, and one of R1and R4is hydrogen, one of R5and R8is C1-C22 alkyl, more preferably Ci-Ce alkyl, and one of R5and R8hydrogen, one of R9and R12is C1-C22 alkyl, more preferably Ci-Ce alkyl, and one of R9and R12is hydrogen, one of R13and R16is C1-C22 alkyl, more preferably Ci-Ce alkyl, and one of R13and R16is hydrogen, and each of R2, R3, R6, R7, R10, R11, R14, and R15is hydrogen; or each of R1, R4, R5, R8, R9, R12, R13, and R16is C1-C22 alkyl, more preferably Ci-Ce alkyl, and each of R2, R3, R6, R7, R10, R11, R14, and R15is hydrogen. Even more preferably one of R1and R4is methyl and one of R1and R4is hydrogen, one of R5and R8is methyl and one of R5and R8hydrogen, one of R9and R12is methyl and one of R9and R12is hydrogen, one of R13and R16is methyl and one of R13and R16is hydrogen, and each of R2, R3, R6, R7, R10, R11, R14, and R15is hydrogen; or each of R1, R4, R5, R8, R9, R12, R13, and R16is methyl, and each of R2, R3, R6, R7, R10, R11, R14, and R15is hydrogen.

[0092] Suitably, halogenation is performed using a halogenating agent, e.g. chlorine, bromine, or one or more halogen salts, such as aluminium, sodium, potassium, iron halogen salt, e.g. chloride or bromide. Optionally, halogenation can be performed in the presence of a solvent, such as 1,2,4-trichlorobenzene, nitrobenzene, naphthalene, kerosene, ethylene glycol, or mixtures thereof. Suitably, halogenation may be performed at an elevated temperature, e.g. at a temperature of 110-260 °C, preferably 180-230 °C.

[0093] Suitably, the method further comprises a step of oxidising biobased o-xylene to obtain phthalic anhydride, wherein the biobased o-xylene has a biobased carbon content of at least 10 % relative to the total mass of carbon in the o-xylene, or at least 15 %, at least 20 %, at least 25 %, at least 30 %, at least 35 %, at least 40 %, at least 45 %, at least 50 %, at least 55 %, at least 60 %, at least 65 %, at least 70 %, at least 75 %, at least 80 %, at least 85 %, at least 90 %, at least 95 %, or at least 97 %, and / or 100 % or less, as determined according to ASTM D 6866-22.

[0094] Suitably, the oxidation may performed in the presence of an oxidising agent, such as oxygen, ozone, hydrogen peroxide, osmium tetroxide, or a permanganate compound. Suitably, the permanganate compound can be potassium permanganate, sodium permanganate, or ammonium permanganate. Preferably, the oxidising agent is potassium permanganate.

[0095] Suitably, the oxidation step may be caried out in the presence of a solvent, e.g. an alcohol, such as methanol, ethanol, 1 -prop anol, 2 -prop anol,

[0096] 1-butanol, 2-butanol, 2 -methyl- 1 -prop anol, 2-methyl-2-propanol, 1-pentanol,

[0097] 2 -methyl- 1 -butanol, 3-methyl- 1-butanol, 2,2-dimethyl-l-propanol, 2-pentanol, 3-methyl-2-butanol, 3-pentanol, 2 -methyl-2 -butanol, or mixtures thereof. Preferably, the solvent is 2-methyl-2-propanol. Optionally, the oxidation step is performed in bulk, i.e. substantially without the presence of a solvent, e.g. 10 wt.% or less of a solvent.

[0098] Preferably, the oxidation reaction is carried out at a temperature of 60-120 °C, more preferably 70-100 °C. Suitably, the oxidation step yields phthalic acid.

[0099] The phthalic acid can subsequently be subjected to dehydration to yield phthalic anhydride. Suitably, dehydration may be carried out in bulk or substantially in bulk, i.e. wherein the compound having a structure according to general formula (IV) comprises 10 % or less by total weight of solvent, e.g. water and / or alcohol, at an elevated temperature, e.g., at a temperature of 150-280 °C, preferably 180-220 °C.

[0100] Optionally, dehydration is carried out in the presence of a dehydrating agent. The dehydrating agent may, e.g., be acetic anhydride, sulphuric acid, polyphosphoric acid, benzene sulphonic acid, jo-toluene sulphonic acid, methane sulphonic acid, trifluoromethane sulphonic acid or phosphorus pentoxide. Suitably, dehydration is performed in the presence of a dehydrating agent at a temperature of 180 °C or less, such as 50-150 °C.

[0101] Alternatively, the conversion of o-xylene to phthalic anhydride may be carried out in a single step in the gas phase. Suitably, in such conversion, molecular oxygen may be used as an oxidant. Suitably, the conversion may be carried out at a temperature of 220 °C or more, preferably 250-450 °C, more preferably 290-310 °C. Preferably, said conversion is carried out in the presence of a catalyst, more preferably V2O5, NH4VO3, V2O5, and / or NH4VO3, supported on, e.g., TiO2, SiO2, MgO, SnO2, porcelain, SiC, AI2O3, aluminium silicate, zirconium silicate, cerium silicate, and mixtures thereof. Most preferably, the catalyst is V2O5 supported on TiO2 or SiO2.

[0102] Suitably, the method may further comprise chlorination or bromination of phthalic anhydride to 3,4,5,6-tetrachlorophthalic anhydride or 3,4,5,6-tetrabromophthalic anhydride, preferably in the gas phase. Elemental chlorine or bromine may be used as a chlorinating or brominating agent, respectively. Suitably, chlorination or bromination may be carried out in the presence of a catalyst, e.g. molybdenum salts, such as CI10M02, iron salts, e.g., FeCE, aluminium salts, e.g., AICI3, or antimony salts, e.g., SbCp. Suitably, chlorination or bromination may be carried out at a temperature of 100 °C or more, preferably 150-280 °C.

[0103] Suitably, the method further comprises reacting biobased furan or substituted biobased furan with, preferably biobased, maleic anhydride to obtain phthalic anhydride or derivative thereof, wherein the biobased furan or substituted biobased furan has a biobased carbon content of at least 10 % relative to the total mass of carbon in furan or substituted furan, or at least 15 %, at least 20 %, at least 25 %, at least 30 %, at least 35 %, at least 40 %, at least 45 %, at least 50 %, at least 55 %, at least 60 %, at least 65 %, at least 70 %, at least 75 %, at least 80 %, at least 85 %, at least 90 %, at least 95 %, or at least 97 %, and / or 100 % or less, as determined according to ASTM D 6866-22. Preferably, the biobased maleic anhydride has a biobased carbon content of at least 10 % relative to the total mass of carbon in maleic anhydride, or at least 15 %, at least 20 %, at least 25 %, at least 30 %, at least 35 %, at least 40 %, at least 45 %, at least 50 %, at least 55 %, at least 60 %, at least 65 %, at least 70 %, at least 75 %, at least 80 %, at least 85 %, at least 90 %, at least 95 %, or at least 97 %, and / or 100 % or less, as determined according to ASTM D 6866-22.

[0104] Preferably, the method further comprises oxidising biobased levulinic acid to obtain biobased maleic anhydride, wherein the biobased levulinic acid has a biobased carbon content of at least 10 %, relative to the total mass of carbon in levulinic acid, or at least 15 %, at least 20 %, at least 25 %, at least 30 %, at least 35 %, at least 40 %, at least 45 %, at least 50 %, at least 55 %, at least 60 %, at least 65 %, at least 70 %, at least 75 %, at least 80 %, at least 85 %, at least 90 %, at least 95 %, or at least 97 %, and / or 100 % or less, as determined according to ASTM D 6866-22.

[0105] The method as presented herein advantageously allows for the synthesis of phthalocyanine complex with a high biobased carbon content, such as 50-70 %, or up to 100 %.

[0106] In another aspect the invention pertains to a colour composition comprising the phthalocyanine complex of the invention and preferably a carrier, more preferably a biobased carrier.

[0107] Preferably, the colour composition has a biobased content of at least 1 % relative to the total mass of carbon in the colour composition, preferably at least 2 %, or at least 5 %, at least 10 %, at least 15 %, at least 20 %, at least 25 %, at least 30 %, at least 35 %, at least 40 %, at least 45 %, at least 50 %, at least 55 %, at least 60 %, at least 65 %, at least 70 %, at least 75 %, at least 80 %, at least 85 %, at least 90 %, at least 95 %, or at least 97 %, and / or 100 % or less, as determined according to ASTM D 6866-22.

[0108] Suitably, the colour composition can have a biobased content of from 40 % to 80 % relative to the total mass of carbon in the colour composition, such as from 45 % to 75 %, or from 50 % to 70 %, as determined according to ASTM 6866-22. The colour composition may have a biobased content of from 95 % to 100 % relative to the total mass of carbon in the colour composition, as determined according to ASTM 6866-22.

[0109] Preferably, the carrier and / or biobased carrier has a biobased carbon content of at least 10 % relative to the total mass of carbon in the carrier, or at least 15 %, at least 20 %, at least 25 %, at least 30 %, at least 35 %, at least 40 %, at least 45 %, at least 50 %, at least 55 %, at least 60 %, at least 65 %, at least 70 %, at least 75 %, at least 80 %, at least 85 %, at least 90 %, at least 95 %, or at least 97 %, and / or 100 % or less, as determined according to ASTM D 6866-22.

[0110] Suitably, the carrier and / or biobased carrier has a biobased content of from 40 % to 80 % relative to the total mass of carbon in the carrier, such as from 45 % and 75 %, or from 50 % and 70 %, as determined according to ASTM 6866-22.

[0111] Suitably, the carrier or the biobased carrier is a liquid carrier.

[0112] Preferably, the colour composition comprises 1 % or more by total weight of the phthalocyanine complex of the invention, preferably 2 % or more, 5 % or more, 7 % or more, 10 % or more, 15 % or more, 20 % or more, such as 25 % or more, and / or typically 30 % or less.

[0113] Preferably, the colour composition comprises the phthalocyanine complex of the invention in particulate form having a D90 of 50 pm or less, more preferably 5-30 pm, and even more preferably 5-25 pm, as determined by an optical microscopy.

[0114] Preferably, the colour composition comprises a carrier, more preferably a biobased carrier. Suitably, the composition comprises one or more carriers, preferably one or more biobased carriers. Preferably, the colour composition comprises 10 % or more by total weight of the carrier, preferably the biobased carrier, preferably 15 % or more, 20 % or more, 25 % or more, 30 % or more, 35 % or more, 40 % or more, 45 % or more, 50 % or more, 55 % or more, 60 % or more, 65 % or more, 70 % or more, 75 % or more, 80 % or more, 85 % or more, 90 % or more, 95 % or more, such as 97 % or more, and / or 99 % or less.

[0115] Preferably, the carrier is selected from waxes, polyolefins, polyamides, aromatic polymers other than polyesters, silicone oils, and mixtures thereof.

[0116] Preferably, waxes are selected from hydrogenated vegetable oils, fatty acids, fatty acids methyl esters, trimethylolpropane esters, fatty acids sorbitol esters, fatty acids sorbitan esters, fatty acids pentaerythritol esters, monoglycerides, diglycerides, triglycerides, fatty acid isosorbide esters, salts of fatty acids, amide waxes, polyethoxylated glycols and derivatives, and polyethylene waxes and ethylene vinyl acetate waxes. Preferably, the waxes as are biobased waxes.

[0117] Suitably hydrogenated vegetable oils include hydrogenated canola oil, hydrogenated castor oil, hydrogenated coconut oil, hydrogenated colza oil, hydrogenated corn oil, hydrogenated cottonseed oil, hydrogenated dammar oil, hydrogenated false flax oil, hydrogenated hemp oil, hydrogenated jatropha oil, hydrogenated jojoba oil, hydrogenated linseed oil, hydrogenated mustard oil, hydrogenated nahor oil, hydrogenated palm oil, hydrogenated paradise oil, hydrogenated peanut oil, hydrogenated petroleum nut oil, hydrogenated pongamia oil, hydrogenated poppyseed oil, hydrogenated radish oil, hydrogenated ramtil oil, hydrogenated rapeseed oil, hydrogenated rice bran oil, hydrogenated safflower oil, hydrogenated salicornia oil, hydrogenated soybean oil, hydrogenated stillingia oil, hydrogenated sunflower oil, hydrogenated tigernut oil, hydrogenated tung oil, and hydrogenated vernonia oil.

[0118] Suitably fatty acids include saturated or unsaturated fatty acids. Preferably, saturated fatty acids are selected from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, and mixtures thereof. Preferably, unsaturated fatty acids are selected from myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, a-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, and docosahexaenoic acid.

[0119] Suitable salts of fatty acids include zinc, magnesium, calcium, sodium, lithium, or aluminium salts of saturated or unsaturated fatty acids, selected from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, a-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, and docosahexaenoic acid.

[0120] Suitable amide waxes include amides of saturated or unsaturated fatty acids, selected from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, a-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, and docosahexaenoic acid.

[0121] Suitable fatty acids methyl esters include methyl esters of saturated or unsaturated fatty acids, selected from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, a-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, and docosahexaenoic acid.

[0122] Suitable trimethylolpropane esters include trimethylolpropane esters of saturated or unsaturated fatty acids, selected from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, a-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, and docosahexaenoic acid. Suitable fatty acid sorbitol esters include sorbitol mono-, di-, tri-, tetra-, penta-, or hexaesters of saturated or unsaturated fatty acids, selected from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, a-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, and docosahexaenoic acid.

[0123] Suitable fatty acid sorbitan esters include sorbitan mono-, di-, tri-, tetraesters of saturated or unsaturated fatty acids, selected from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, lin oleic acid, linoelaidic acid, a-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, and docosahexaenoic acid.

[0124] Suitable fatty acid pentaerythritol esters include pentaerythritol mono-, di-, tri-, or tetraesters of saturated or unsaturated fatty acids, selected from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, a-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, and docosahexaenoic acid.

[0125] Suitably, monoglycerides, diglycerides, and triglycerides are esters of glycerol and one, two, or three fatty acids, respectively. Preferably, the fatty acid is selected from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, a-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, and docosahexaenoic acid.

[0126] Suitable fatty acid isosorbide esters include isosorbide mono- or diesters of saturated or unsaturated fatty acids, selected from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, a-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, and docosahexaenoic acid.

[0127] Waxes preferably comprise one or more selected from natural oil based waxes, such as glycerol monostearate, magnesium stearate, zinc stearate, hydrogenated castor oil, amide waxes, such as stearamide, ethylene bis(stearamide), and / or synthetic waxes, such as monoesters of stearic acid, polyethoxylated glycols and derivatives, and esters of pentaerythritol, polyethylene waxes and ethylenevinylacetate waxes. Preferably, the natural oil waxes and the synthetic waxes are biobased.

[0128] Suitable polyolefins include aliphatic homopolymers, aliphatic copolymers, and / or cyclic olefin polymers. Examples of such aliphatic polymers may be polyethylene (PE) and polypropylene (PP).

[0129] Suitable polyamide include one or more selected from the group consisting of aliphatic homopolymer polyamides, aliphatic copolymer polyamides, semi-aromatic copolymer polyamides, semi-aromatic homopolymer polyamides, aromatic copolymer polyamides, and aromatic homopolymer polyamides. The polyamide preferably comprises polyamide 4.6, (PA 4.6), polyamide 4.10 (PA 4.10), polyamide 4.12 (PA 4.12), polyamide 5.6 (PA 5.6), polyamide 6 (PA 6), polyamide 6.6 (PA 6.6), polyamide 6.10 (PA 6.10), polyamide 6.12 (PA 6.12), polyamide 10 (PA 10), polyamide 10.10 (PA 10.10), polyamide 10.12 (PA 10.12), polyamide 11 (PA 11), polyamide 12 (PA 12), polyphthalamide (PPA), aramid, e.g. poly-paraphenylene terephthalamide.

[0130] Suitable aromatic polymers include aromatic homopolymers and / or aromatic copolymers other than polyesters. Examples of such aromatic polymers include polystyrene, polysulphone, polyphenylsulphone, and acrylonitrile-butadiene-styrene.

[0131] Suitable silicon oils include polymerised siloxanes comprising one or more substituents, such as C1-C16 alkyl, halogen, e.g., fluorine or chlorine, phenyl, or substituted phenyl, an example of such silicon oil is polydimethylsiloxane. Preferably, silicone oils may have a viscosity at 20 °C of 100 - 12 500 cSt, more preferably 500 - 12 000 cSt.

[0132] Preferably, the biobased carrier is selected from biobased waxes, aliphatic polymers, aromatic polymers other than polyesters, and mixtures thereof. Suitable biobased waxes, aliphatic polymers, and aromatic polymers other than polyesters include biobased version of the biobased waxes, aliphatic polymers, aromatic polymers other than polyesters as described herein.

[0133] Preferably, biobased waxes are selected from hydrogenated vegetable oils, fatty acids, fatty acids methyl esters, fatty acids sorbitol esters, fatty acids sorbitan esters, fatty acids pentaerythritol esters, monoglycerides, diglycerides, triglycerides, salts of fatty acids, amide waxes, polyethoxylated glycols and derivatives, and mixtures thereof. Suitable biobased hydrogenated vegetable oils, fatty acids, fatty acids methyl esters, fatty acid sorbitol esters, fatty acid sorbitan esters, fatty acid pentaerythritol esters, monoglycerides, diglycerides, triglycerides, salts of fatty acids, amide waxes, polyethoxylated glycols and derivatives include biobased versions of the hydrogenated vegetable oils, fatty acids, fatty acid methyl esters, fatty acid sorbitol esters, fatty acid sorbitan esters, fatty acid pentaerythritol esters, monoglycerides, diglycerides, triglycerides, salts of fatty acids, amide waxes, polyethoxylated glycols and derivatives as described herein.

[0134] Suitable biobased aliphatic polymers are selected from biobased PE, PP, PA 4.6, PA 4.10, PA 4.12, PA 5.6, PA 6, PA 6.6, PA 6.10, PA 6.12, PA 10, PA 10.10, PA 10.12, PA 11, and PA 12.

[0135] Suitably, the biobased aromatic polymer is biobased PS or ABS. The colour composition according to the invention may further comprise one or more optional additive that do not adversely affect the desired properties of the final product, e.g. a preform or a textile. Suitably, the one or more optional additive include, i.e. is selected from the group consisting of, dyes and pigments, scavengers, such as acetaldehyde scavengers and oxygen scavengers, stabilisers, antioxidants, visible light screening agents, UV light screening agents, extrusion aids, drying agents, fillers, anti-clogging agents, crystallisation aids, impact modifiers, and additives designed to make the polymer more (bio-)degradable or combustible. Preferably, the one or more optional additive is used in an amount to provide a specific colour and / or to enhance the light protection of the preforms and / or textiles. The one or more optional additive may be present in the colour composition in an amount neither adversely influencing the light transmittance property nor the specific colour nor other desired properties.

[0136] Preferably, the dyes and pigments are selected from Solvent Yellow 43 (CAS number 19125-99-6 / 1226-96-9), Solvent Yellow 72 (CAS number 61813-98-7), Solvent Yellow 93 (CAS number 4702-90-3 / 61969-52-6), Solvent Yellow 114 (CAS number 75216-45-4), Disperse Yellow 64 (CAS number 10319-14-9), Disperse Yellow 201 (CAS number 80748-21-6), Disperse Yellow 241 (CAS number 83249-52-9), Solvent Violet 36 (CAS number 61951-89-1), Solvent Red 23 (CAS number 85-86-9), Solvent Red 26 (CAS number 477-79-6), Solvent Red 111 (CAS number 82-38-2), Solvent Red 135 (CAS number 71902-17-5), Solvent Red 149 (CAS number 71902-18-6 / 21295-57-8), Solvent Red 179 (CAS number 89106-94-5), Solvent Red 195 (CAS number 164251-88-1), Solvent Red 207 (CAS number 15958-68-6), Solvent Green 3 (CAS number 128-80-3), Solvent Green 28 (CAS number 71839-01-5), Disperse Blue 60 (CAS number 12217-80-0), Solvent Blue 36 (CAS number 14233-37-5), Solvent Blue 97 (CAS number 61969-44-6), Solvent Blue 101 (CAS number 6737-68-4), Solvent Blue 104 (CAS number 116-75-6), Solvent Orange 60 (CAS number 61969-47-9 / 6925-69-5), Disperse Orange 47 (CAS number 12236-03-2), Solvent Black 7 (CI number 50415:1, CAS number 8005-02-5), Pigment Blue 15:1 (CI number 74160, CAS number 147-14-8), Pigment Blue 15:3 (CI number 74160, CAS number 147-14-8), Pigment Green 7 (CI number 74260, CAS number 1328-53-6), Pigment Orange 43 (CI number 71105, CAS number 4424-06-0), Pigment Orange 64 (CI number 12760, CAS number 72102-84-2), Pigment Orange 72 (CI number 211095, CAS number 78245-94-0), Pigment Red 122 (CI number 73915, CAS number 980-26-7), Pigment Red 144 (CI number 20735, CAS number 5280-78-4), Pigment Red 149 (CI number 71137, CAS number 4948-15-6), Pigment Red 177 (CI number 65300, CAS number 4051-63-2), Pigment Red 178 (CI number 71155, CAS number 3049-71-6), Pigment Red 179 (CI number 71130, CAS number 5521-31-3), Pigment Red 187 (CI number 12486, CAS number 59487-23-9), Pigment Red 202 (CI number 73907, CAS number 3089-17-6), Pigment Red 214 (CI number 200660, CAS number 40618-31-3), Pigment Red 220 (CI number 20055, CAS number 68259-05-2), Pigment Red 242 (CI number 20067, CAS number 52238-92-3), Pigment Red 247 (CI number 15915, CAS number 43035-18-3), Pigment Red 254 (CI number 56110, CAS number 84632-65-5), Pigment Red 264 (CI number 561300, CAS number 88949-33-1), Pigment Violet 19 (CI number 73900, CAS number 1047-16-1), Pigment Violet 23 (CI number 51319, CAS number 6358-30-1), Pigment Violet 29 (CI number 71129, CAS number 81-33-3), Pigment Yellow 109 (CI number 56284, CAS number 5045-40-9), Pigment Yellow 110 (CI number 56280, CAS number 5590-18-1), Pigment Yellow 119 (CI number 77496, CAS number 68187-51-9), Pigment Yellow 128 (CI number 20037, CAS number 79953-85-8), Pigment Yellow 138 (CI number 56300, CAS number 30125-47-4), Pigment Yellow 147 (CI number 60645, CAS number 4118-16-5), Pigment Yellow 151 (CI number 13980, CAS number 31837-42-0), Pigment Yellow 180 (CI number 21290, CAS number 77804-81-0), Pigment Yellow 181 (CI number 11777, CAS number 74441-05-7), Pigment Yellow 183 (CI number 18792, CAS number 65212-77-3) Pigment Yellow 191 (CI number 18795, CAS number 129423-54-7), Pigment Yellow 53 (CI number 77788, CAS number 8007-18-9), Pigment Yellow 62 (CI number 13940, CAS number 12286-66-7), Pigment Yellow 95 (CI number 20034, CAS number 5280-80-8), Pigment Blue 60 (CI number 69800, CAS number 81-77-6); and / or inorganic compounds selected from the group consisting of Pigment Black 26 (CI number 77494, CAS number 68186-94-7), Pigment Brown 24 (CI number 77310, CAS number 68186-90-3), Pigment Brown 29 (CI number 77500, CAS number 12737-27-8), Pigment Green 36 (CI number 74265, CAS number 14302-13-7), Pigment Green 50 (CI number 77377, CAS number 68186-85-6), Pigment Red 101 (CI number 77491, CAS number 1332-37-2), Pigment Black 28 (CI number 77428, CAS number 68186-91-4), Pigment Black 29 (CI number 77498, CAS number 68187-50-8), Pigment Black 30 (CI number 77504, CAS number 71631-15-7), Pigment Black 33 (CI number 77537, CAS number 68186-94-7 or 75864-23-2), Pigment Brown 29 (CI number 77500, CAS number 12737-27-8), Pigment Brown 33 (CI number 77503, CAS number 68186-88-9), Pigment Blue 29 (CI number 77007, CAS number 057455-37-5), Pigment Blue 28 (CI number 77346, CAS number 1345-16-0), Pigment Blue 36 (CI number 77343, CAS number 68187-11-1), Pigment Green 17 (CI number 77288, CAS number 1308-38-9), Pigment Yellow 164 (CI number 77899, CAS number 68412-38-4), Pigment Yellow 184 (CI number 771740, CAS number 14059-33-7), Pigment Yellow 42 (CI number 77492, CAS number 51274-00-1), and oxides comprising metals or elements selected from the group consisting of Na, Al, Si, S, Zn, Ni, Fe, Mn, Ti, V, Bi, Co, Cr, Cu, Sn, and Sb. The colour composition may comprise one or more dyes and pigments.

[0137] The (optional) additives may be present in the colour composition in an amount of up to 25 %, such as 20 % or less, 15 % or less, or 10 % or less, or 7.5 % or less, or 5 % or less, or 2.5 % or less.

[0138] The invention also pertains to a method of producing a colour composition comprising mixing a phthalocyanine complex of the invention and a carrier, optionally two or more carriers, more preferably a biobased carrier.

[0139] The mixing may be carried out by stirring, agitation, tumbling, kneading, milling, shear mixing, extrusion, blending, ultrasonic mixing, and / or homogenisation. Suitably, the mixing is carried out at a temperature of 10-300 °C, preferably 15-250 °C. Optionally, if the method comprises extrusion, the method may further comprise strand cutting or granulation, e.g. underwater granulation. Optionally, if the method comprises using the wax as the carrier, the method may further comprise spray drying. Suitably, the method comprises mixing 1 % or more and preferably 30 % or less, e.g. 5 % or more, or 10 % or more, 15 % or more, 20 % or more, 25 % or more, or 2-25 %, 5-20 %, 5-15 %, 10-20 %, 10-25 %, or 15-25 % by total weight of the colour composition of the phthalocyanine complex of the invention, and 60 % or more and preferably 99 % or less, e.g. 70 % or more, or 75 % or more, 80 % or more, 85 % or more, 90 % or more, 95 % or more, or 70-85 %, 70-90 %, 70-95 %, 70-99 %, 80-85 %, 80-90 %, 80-95 %, 80-99 %, 85-90 %, 85-95 %, 85-99 %, 90-95 %, or 90-99 % by total weight of the colour composition of the carrier.

[0140] Optionally, the method involves mixing the (optional) additives, dyes and / or pigments. Suitably, the (optional) additives may be present in an amount of up to 25 %, based on total weight of the colour composition.

[0141] The invention also pertains to a method of producing a final article comprising the colour composition according to the invention and a base material. Suitably, the base material is selected from polyolefins, polyamides, aromatic polymers other than polyesters, and mixtures thereof. The preferences directed to the carrier apply equally to the corresponding base material. The invention has been described by reference to various embodiments, and methods. The skilled person understands that features of various embodiments and methods can be combined with each other. In particular, the preferences directed to a product apply equally to a preparation method of said product.

[0142] All references cited herein are hereby completely incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.

[0143] The use of the terms “a” and “an” and “the” and similar referents in the context of describing the invention (especially in the context of the claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms “comprising”, “having”, “including” and “containing” are to be construed as open-ended terms (i.e., meaning “including, but not limited to”) unless otherwise noted. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falhng within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention. For the purpose of the description and of the appended claims, except where otherwise indicated, all numbers expressing amounts, quantities, percentages, and so forth, are to be understood as being modified in all instances by the term “about”. Also, all ranges include any combination of the maximum and minimum points disclosed and include any intermediate ranges therein, which may or may not be specifically enumerated herein.

[0144] Preferred embodiments of this invention are described herein. Variation of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject-matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context. The claims are to be construed to include alternative embodiments to the extent permitted by the prior art.

[0145] For the purpose of clarity and a concise description features are described herein as part of the same or separate embodiments, however, it will be appreciated that the scope of the invention may include embodiments having combinations of all or some of the features described. Hereinafter, the invention will be illustrated in more detail, according to specific examples. However, the invention may be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein. Rather, these example embodiments are provided so that this description will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.

[0146] Examples

[0147] Example 1

[0148] A mixture of the following three copper phthalocyanines was prepared as follows using bio-sourced starting materials.

[0149] Methylated phthalic anhydride (10 g), urea (13 g) and trichlorobenzene (30 ml) were mixed in a vessel, equipped with an oil bath and stirrer. Then copper(H)chloride (2.4 g) and ammonium molybdate (0.05 g) were added. The mixture was heated up slowly within 1 h to 140 °C and then ramped up to 180 °C for remaining 0.5 h. Methylated copper phthalocyanine was formed within 1.5 h, filtered and washed with trichlorobenzene, then methanol, and then water. The blue solid was then dried within a vacuum oven. The yield of methylated copper phthalocyanine was 80-96 %.

[0150] The chemical formula of this copper phthalocyanines is CUC36NSH24. The theoretical molecular weight of the copper phthalocyanines is 631.14 g / mol. The molecular weight as determined by gel permeation chromatography was 632.19 g / mol. Quantitative elemental analysis yielded C, 68.40; H, 3.83; Cu, 10.05; and N, 17.73. Analysis by mass spectrometry of this Example is show in Figure 1. Example 2

[0151] The following copper phthalocyanines was prepared as follows using bio-sourced starting materials.

[0152] Dimethylated phthalic anhydride (10 g), urea (13 g) and trichlorobenzene (30 ml) were mixed in a vessel, equipped with an oil bath and stirrer. Then copper(II)chloride (2.4 g) and ammonium molybdate (0.05 g) were added. The mixture was heated up slowly within 1 h to 140 °C and then ramped up to 180 °C for remaining 0.5 h. Dimethylated copper phthalocyanine was formed within 1.5 h, filtered and washed with trichlorobenzene, then methanol, and then water. The blue solid was then dried within a vacuum oven. The yield of dimethylated copper phthalocyanine was 80-96 %.

[0153] The chemical formula of this copper phthalocyanines is CUC40N8H32. The theoretical molecular weight of the copper phthalocyanines is 687.20 g / mol. The molecular weight as determined by gel permeation chromatography was 688.30 g / mol. Quantitative elemental analysis yielded C, 69.80; H, 4.69; Cu, 9.23; and N, 16.28. Analysis by mass spectrometry of this Example is show in Figure 2.

[0154] Example 3

[0155] In a further example, the thermogravimetric analysis of the unsubstituted copper phthalocyanine shown below was compared with the thermogravimetric analysis of the substituted copper phthalocyanine mixture of Example 1.

[0156] The thermogravimetric analysis of the unsubstituted copper phthalocyanine is shown in Figure 3. This figure shows that at temperatures higher than about 500 °C, the phthalocyanine thermally degrades. The thermogravimetric analysis of the substituted copper phthalocyanine of Example 1 is shown in Figure 4. As compared to the unsubstituted phthalocyanine, this sample is surprisingly more thermally stable and degradation of the phthalocyanine at temperatures higher than about 500 °C is significantly less.

[0157] Example 4

[0158] A mixture of the following three copper phthalocyanines was prepared as follows. Methylated phthalic anhydride was synthesized according to the procedure described in Examples 4-5 of US-B-11 932 616, incorporated herein by reference, using maleic anhydride and biobased 2-methylfuran as starting materials.

[0159] Methylated phthalic anhydride (10 g), urea (19 g), copper(I)chloride (1.6 g), ammonium molybdate (2.0 g), and trichlorobenzene (18 ml) were mixed in a vessel, equipped with an oil bath and stirrer. The mixture was heated up at 140 °C for 1 h, and then at 180 °C for 0.5 h. Afterwards, the reaction mixture was allowed to cool down. The formed methylated copper phthalocyanine was filtered and washed with methanol, then with water, and then with acetone. The crude product was added to an Erlenmeyer flask containing approximately 50 g of ice. Then, concentrated sulfuric acid was added (80 ml, 65 %), and the mixture was stirred at room temperature for 20 h. Then, the resulting suspension was poured into 350 ml of cold water. Ammonium hydroxide was added until the solution had a pH of 8 and the mixture was refluxed for 10 min. Then, the methylated copper phthalocyanine was filtered and dried in a vacuum oven. 8 g of methylated copper phthalocyanine in the alpha form was obtained.

[0160] Methyl copper phthalocyanine was analysed using powder XRD and exhibited the alpha crystal form (Figure 5). The biobased carbon percentage of copper phthalocyanine was determined following ASTM D6866-22 and was 58 %.

[0161] Example 5

[0162] The methyl copper phthalocyanine of Example 4 was converted into an beta form as follows.

[0163] Methyl copper phthalocyanine of Example 4 (10 g) was mixed with 5 % sulfuric acid (80 ml, 5 %), and stirred at 90 °C overnight. Then, the obtained methyl copper phthalocyanine in beta form was filtered and washed with water. The blue solid was then dried within a vacuum oven. 8.7 g of methylated copper phthalocyanine was obtained with 87 % yield. Beta form of methyl copper phthalocyanine was confirmed using powder XRD (Figure 6).

[0164] Example 6

[0165] The following dimethyl copper phthalocyanine was prepared as follows using bio-sourced starting materials. Dimethylated phthalic anhydride was synthesised according to the procedure described by Mahmoud et al. (Green Chem. 2014, 16, 167) using 2,5-dimethylfuran and maleic anhydride as starting materials. The experimental section of Mahmoud et al. is incorporated herein by reference.

[0166] Dimethylated phthalic anhydride (20 g), urea (34 g), trifluoromethanesulphonate (11 g) and ammonium molybdate (3.6 g), trichlorobenzene (150 ml), and water (5 ml) were mixed in a vessel, equipped with an oil bath and stirrer. The reaction mixture was heated at 115 °C for 18 h, then ramped to 185 °C and heated at 185 °C for 4.5 h. Afterwards, the reaction mixture was allowed to cool down.

[0167] The formed dimethylated copper phthalocyanine was filtered and washed with methanol, then water, then isopropanol, and then acetone. The crude product was mixed with ice (approx. 100 g) and concentrated sulphuric acid (160 g, 98 %) at room temperature for 20 h. Then, ammonium hydroxide was added until the solution had a pH of 8 and the mixture was refluxed for 10 min. Afterwards, the mixture was allowed to cool down, and was filtered and washed with water, and then acetone. 11 g of dimethyl copper phthalocyanine in the alpha form was obtained with 55 % yield. Alpha form of dimethyl copper phthalocyanine was confirmed using powder XRD and was 100 % (Figure 7).

[0168] The biobased carbon content of dimethyl copper phthalocyanine was determined according to ASTM D6866-22 and was 46 %.

[0169] Example 7

[0170] The following copper phthalocyanine was prepared as follows using bio-sourced starting materials. A sample of a biobased fraction of biobased benzene-toluene-xylene (bio-BTX), was obtained from the company Bio-BTX in the Netherlands. The bio-BTX sample was purified by fractional distillation. Fractions having a boiling point between 130-135 °C were collected and used herein.

[0171] 500 g of the fractionated bio-BTX sample was mixed with t-butyl alcohol, and a potassium permanganate solution (3050 g dissolved in water). The reaction mixture was refluxed for 5 hours. Phthalic acid was isolated from the reaction mixture, after isolation of terephthalic acid and isophthalic acid, by precipitation from an acidified, concentrated reaction mixture. 364 g of phthalic acid and potassium chloride mixture was isolated. Said mixture comprised 67 g phthalic acid (8 % yield). Subsequently, 364 g of the phthalic acid and potassium chloride mixture was refluxed in 780 ml of acetic anhydride. Afterwards, the reaction mixture was cooled down, and the solids were filtered, the mother liquor was concentrated and the precipitated solids were isolated. All solid fractions were combined and extracted with dichloromethane, and the dichloromethane solution was subsequently evaporated. 42 g of phthalic anhydride was obtained.

[0172] Phthalic anhydride (35 g), urea (46 g) and trichlorobenzene (72 ml) were mixed in a vessel, equipped with an oil bath and stirrer. Then, copper(I)chloride (6.3 g) and ammonium molybdate (0.2 g) were added. The mixture was heated up slowly, with a heating rate of 10 °C / 10 min to a temperature of 250 °C, and then maintained at 250 °C for 2.5 h. Afterwards, heating is reduced to 50 °C and the reaction mixture was allowed to cool down. Formed copper phthalocyanine was filtered, washed with trichlorobenzene, 5 % sodium hydroxide solution, then water.

[0173] Copper phthalocyanine was purified by suspending the crude product in sulphuric acid (350 ml, 5 %), and stirring the mixture for 1 h at 90 °C. Afterwards, the solids were filtered off and washed with water. Then the washed solids were suspended in sodium hydroxide solution (350 ml, 5 %) and stirred for 1 h at 90 °C. Afterwards, the solids were filtered off and washed with water. The washed solids were suspended in methanol (350 ml), refluxed for 1 h and then filtered. The filtrate was washed with methanol. The resulting dark blue solid was dried in a vacuum oven. 28 g of copper phthalocyanine was obtained.

[0174] Copper phthalocyanine was analysed using powder XRD and exhibited the beta crystal form (Figure 8). The biobased carbon percentage of copper phthalocyanine was determined following ASTM D6866-22 and was 73 %.

[0175] Conversion of copper phthalocyanine from beta to alfa form was done as described in Example 5. Copper phthalocyanine was mixed with 5 % sulphuric acid and stirred at 90 °C overnight. Then, the obtained copper phthalocyanine in beta form was filtered and washed with water. The blue solid was then dried within a vacuum oven. Alfa form of copper phthalocyanine was confirmed using powder XRD (Figure 9).

[0176] Example 8

[0177] Biobased chlorinated methyl copper phthalocyanine was prepared as follows using the mixture of methyl copper phthalocyanines of Example 5 as a starting material.

[0178] Methylated copper phthalocyanine of Example 5 (15 g), aluminium chloride (63 g), sodium chloride (28 g), and trichlorobenzene (40 ml), were mixed in a vessel, equipped with an oil bath, stirrer, an inlet for an inert gas, and a gas outlet. The reaction mixture was heated at 115 °C for 0.5 h, then iron(III)chloride (1.9 g) was added. The reaction mixture was subsequently heated at 190 °C for 19 h under argon atmosphere. Then, the hot reaction mixture was poured into room temperature water (approx. 700 ml) and stirred overnight. The formed chlorinated methyl copper phthalocyanine was filtered and washed with methanol, then water, then isopropanol, and then acetone. 15 g of chlorinated methyl copper phthalocyanine was obtained with 68 % yield.

[0179] The biobased carbon percentage of chlorinated dimethyl copper phthalocyanine was determined following ASTM D6866-22 and was 54 %. Example 9

[0180] The following biobased chlorinated dimethyl copper phthalocyanine was prepared as follows using the mixture of methyl copper phthalocyanines of Example 6 as a starting material.

[0181] Dimethylated copper phthalocyanine of Example 6 (15 g), aluminum chloride (58 g), sodium chloride (25 g), and trichlorobenzene (40 ml), were mixed in a vessel, equipped with an oil bath, stirrer, an inlet for an inert gas, and a gas outlet. The reaction mixture was heated at 115 °C for 0.5 h, then iron(III) chloride (1.8 g) was added. The reaction mixture was subsequently heated at 190 °C for 19 h under argon atmosphere. Then, the hot reaction mixture was poured into room temperature water (approx. 700 ml) and stirred overnight. The formed chlorinated dimethyl copper phthalocyanine was filtered and washed with methanol, then water, then isopropanol, and then acetone. 14 g of chlorinated dimethyl copper phthalocyanine was obtained with 67 % yield.

[0182] The biobased carbon percentage of chlorinated dimethyl copper phthalocyanine was determined following ASTM D6866-22 and was 33%.

[0183] Example 10

[0184] A paint Mueller grinding device was used to create dispersions of phthalocyanine of Example 5 in a vegetable oil carrier and of Pigment Blue 15:1, obtained from Sun Chemical, in the same vegetable oil carrier.

[0185] Methyl copper phthalocyanine of Example 5 (0.5 g) and the vegetable oil carrier (2.1 g) were added to a Muller glass plate and grinded for 4 min 45 s. A particle size was determined using a Hegeman gauge after 9-14 days after grinding. The mixture exhibited a particle size in the range of 65-70 pm.

[0186] The biobased carbon percentage of the dispersion was determined following ASTM D6866-22 and was 92 %. The dispersion of methyl copper phthalocyanine of Example 5 and the vegetable oil carrier is denoted herein as “Me4CuPC”.

[0187] Pigment Blue 15:1 (0.5 g, copper phthalocyanine in the alpha form, CAS number 147-14-8) and the same vegetable oil carrier (2.1 g) were added to a Muller glass plate and grinded for 4 min 45 s. The dispersion of Pigment Blue 15:1 and the vegetable oil carrier is denoted herein as “Pigment Blue 15:1”.

[0188] Example 11

[0189] Dispersions of Example 10 were used to prepare coloured PVC articles. PVC used in this example was 9 % TiO2 tin stabilised rigid PVC.

[0190] An article comprising 0.1 parts methyl copper phthalocyanine of Example 5 per 100 parts of PVC was obtained by dispersing by using 0.5 parts of Me4CuPC dispersion from Example 10 per 100 parts of PVC.

[0191] An article comprising 0.1 parts Pigment Blue 15:1 per 100 parts of PVC was obtained by dispersing by using 0.5 parts of Pigment Blue 15:1 dispersion from Example 10 per 100 parts of PVC.

[0192] The PVC articles were subjected to outdoor exposure during the period of May-Oct 2024 in Indiana, USA. Colour of the corresponding PVC articles was determined using a Minolta CM-3600A spectrophotometer utilising Colibri software. Colour measurements are taken with the following settings: Specular component included, D65 illuminant, 10 degree observer, 30 mm aperture and using the CIE Lab colour space. Results are shown in Figure 10.

[0193] Figure 10 shows that the PVC article comprising methyl copper phthalocyanine of Example 5 surprisingly exhibited improved resistance to weathering compared to the PVC article comprising Pigment Blue 15:1, as seen by smaller AL, Aa, Ab, AE. Example 12

[0194] Phthalocyanines of Examples 4 and 6 were used to prepare coloured silicone. 0.25 part of phthalocyanine of Examples 4 and or phthalocyanine of Examples 6 was dispersed into 100 parts of silicone sealant (Dow 795, white filled alkoxy sealant) used as a carrier material to prepare coloured silicone sealants.

[0195] Both coloured silicones sealants exhibited uniform dispersions based on a visual inspection.

Claims

Claims1. Phthalocyanine complex of general formula (I):wherein Rx-R16are the same or different and each R1to R16is individually selected from the group consisting of hydrogen, C1-C22 alkyl, C3-C22 alkenyl, C3-C22 alkynyl, chlorine, bromine, fluorine, iodine, sulphonate, and- [(CH2)n- O- (CH2)m]o_CH3, wherein n = 0-16, m = 1-16, o = 1-20, wherein M is selected from the group consisting of Cu, Ni, Zn, Co, Fe, Mn, and Al, and wherein the phthalocyanine complex has a biobased carbon content of at least 10 % relative to the total mass of carbon in the phthalocyanine complex, as determined according to ASTM D 6866-22.

2. Phthalocyanine complex according to claim 1, wherein at least one of Rx-R16is not hydrogen,.

3. Phthalocyanine complex according to claim 1, wherein one of R1and R4is methyl and one of R1and R4is hydrogen, wherein one of R5and R8is methyl and one of R5and R8is hydrogen, wherein one of R9and R12is methyl and one of R9and R12is hydrogen, wherein one of R13and R16is methyl and one of R13and R16is hydrogen, and wherein each of R2, R3, R6, R7, R10, R11, R14, and R15is hydrogen.

4. Phthalocyanine complex according to claim 1, wherein each of R1, R4, R5, R8, R9, R12, R13, and R16is methyl, and wherein each of R2, R3, R6, R7, R10, R11, R14, and R15is hydrogen.

5. Phthalocyanine complex according to claim 1, wherein at least one of R1to R16is chlorine, bromine, fluorine, and / or iodine, preferably at least one of R2, R3, R6, R7, R10, R11, R14, and R15is chlorine, bromine, fluorine, and / or iodine, more preferably at least one of R2, R3, R6, R7, R10, R11, R14, and R15is chlorine or bromine.

6. Phthalocyanine complex according to claim 5, wherein one of R1and R4is methyl and one of R1and R4is chlorine, one of R5and R8is methyl and one of R5and R8chlorine, one of R9and R12is methyl and one of R9and R12is chlorine, one of R13and R16is methyl and one of R13and R16is chlorine, and each of R2, R3, R6, R7, R10, R11, R14, and R15is chlorine; or wherein one of R1and R4is methyl and one of R1and R4is bromine, one of R5and R8is methyl and one of R5and R8bromine, one of R9and R12is methyl and one of R9and R12is bromine, one of R13and R16is methyl and one of R13and R16is bromine, and each of R2, R3, R6, R7, R10, R11, R14, and R15is bromine.

7. Phthalocyanine complex according to claim 5, wherein each of R1, R4, R5, R8, R9, R12, R13, and R16is methyl, and each of R2, R3, R6, R7, R10, R11, R14, and R15is chlorine or each of R2, R3, R6, R7, R10, R11, R14, and R15is bromine.

8. Phthalocyanine complex according to any one of claims 1-7, wherein at least 50 % of the number of the phthalocyanine complex particles is in a crystal form, as determined by X-ray diffraction, preferably at least 50 % of the number of the phthalocyanine complexes is in an a crystal form, as determined by X-ray diffraction, preferably at least 50 % of the number ofthe phthalocyanine complexes is in an 0 crystal form, as determined by X-ray diffraction.

9. Phthalocyanine complex according to any one of claims 1-8, wherein the phthalocyanine complex is in particulate form having D90 of 50 pm or less, preferably 5-30 pm, more preferably 5-25 pm, as determined by optical microscopy.

10. Phthalocyanine complex according to any of claims 1-9, wherein the phthalocyanine complex has a biobased carbon content of 40-80 % relative to the total mass of carbon in the phthalocyanine complex, preferably 45-75 %, more preferably 50-70 %, as determined according to ASTM D 6866-22.

11. Method of preparing a phthalocyanine complex according to any one of claims 1 or 8-10, comprising:- oxidising biobased o-xylene to obtain phthalic anhydride or a derivative thereof, and- reacting urea or a derivative thereof, phthalic anhydride or a derivative thereof, and a metal salt, optionally in a solvent, optionally in the presence of a catalyst to obtain particles of the phthalocyanine complex, wherein the biobased o-xylene has a biobased carbon content of at least 10 % relative to the total mass of carbon in the o-xylene, and wherein the phthalic anhydride or derivative thereof has a biobased carbon content of at least 10 % relative to the total mass of carbon in phthalic anhydride or derivative thereof, as determined according to ASTM D 6866-22.

12. Method of preparing a phthalocyanine complex according to any one of claims 2-10, comprising:- reacting biobased furan or substituted biobased furan with maleic anhydride to obtain a phthalic anhydride or a derivative thereof, and- reacting urea or a derivative thereof, phthalic anhydride or a derivative thereof, and a metal salt, optionally in a solvent, optionally in the presence of a catalyst to obtain particles of the phthalocyanine complex, wherein the biobased furan or the substituted biobased furan has a biobased carbon content of at least 10 % relative to the total mass of carbon in the furan or the substituted furan, as determined according to ASTM D 6866-22, and preferably wherein the maleic anhydride has a biobased carbon content of at least 10 % relative to the total mass of carbon in the maleic anhydride, as determined according to ASTM D 6866-22, and wherein the phthalic anhydride or derivative thereof has a biobased carbon content of at least 10 % relative to the total mass of carbon in the phthalic anhydride or derivative thereof, as determined according to ASTM D 6866-22.

13. Method according to claim 12, further comprising oxidising biobased levulinic acid to obtain biobased maleic anhydride, wherein the biobased levulinic acid has a biobased carbon content of at least 10 % relative to the total mass of carbon in the levulinic acid, as determined according to ASTM D 6866-22.

14. Method according to any one of claims 11-13, further comprising:- recrystallising the particles of the phthalocyanine complex to obtain crystalline particles of the phthalocyanine complex, and / or- reducing the size of the particles of the phthalocyanine complex or crystalline particles of the phthalocyanine complex to obtain size reduced particles of the phthalocyanine complex or size reduced particles of the crystalline phthalocyanine complex.

15. Method according to any one of claims 11-14, further comprising halogenating the phthalocyanine complex.

16. Method of preparing a phthalocyanine complex according to any one of claims 1-10, comprising:- reacting urea or a derivative thereof, phthalic anhydride or a derivative thereof, and a metal salt, optionally in a solvent, optionally in the presence of a catalyst to obtain particles of the phthalocyanine complex, and- halogenating the phthalocyanine complex, wherein the phthalic anhydride or derivative thereof has a biobased carbon content of at least 10 % relative to the total mass of carbon in the phthalic anhydride or derivative thereof, as determined according to ASTM D 6866-22.

17. Colour composition comprising a phthalocyanine complex according to any one of claims 1-10 and a carrier, preferably a biobased carrier, wherein the colour composition preferably has a biobased carbon content of at least 1 % relative to the total mass of carbon in the colour composition, more preferably at least 10 %, as determined according to ASTM D 6866-22.

18. Colour composition according to claim 17, wherein the colour composition further comprises one or more optional additives selected from the group consisting of dyes and pigments, scavengers, stabilisers, antioxidants, visible light screening agents, UV light screening agents, extrusion aids, drying agents, fillers, anti-clogging agents, crystallisation aids, impact modifiers, and additives designed to make the polymer more (bio-)degradable or combustible.

19. Method of producing a colour composition according to claim 17 or 18, comprising mixing the phthalocyanine complex according to any one of claims 1-10 and the carrier.

20. Method according to claim 19, wherein the mixing comprises stirring, agitation, tumbling, kneading, milling, shear mixing, extrusion, blending, ultrasonic mixing, and / or homogenisation.

21. Article comprising a colour composition according to claim 17 or18, and a base material.

22. Use of a phthalocyanine complex according to any one of claims 1-10 as a dye or a pigment, preferably in cosmetics, colour compositions, or printing inks.

Images