Novel anthraquinone-based NIR absorbers

Abstract

The invention relates to compounds of formula (I '), in particular of formula (I), to a method for the production thereof, and to the use thereof as nearly colorless IR absorbers for optical filter applications, in particular for plasma display panels or for laser welding of plastics. These compounds can be used in compositions for inks, paints and plastics, especially in a wide variety of printing systems, and are particularly well suited for security applications, or for brand protection; or as a liquid marker. Compounds of formula (I '), in particular compounds of formula (I), represent almost colorless IR absorbers which exhibit high resistance to chemicals and solvents and good light stability and good thermal stability. Due to their unique application properties, they can advantageously be used as IR absorbers, for laser writing, heat shielding, security printing, laser welding of plastics and as markers for liquids.

Description

[0001] The present invention relates to compounds of formula (I'), in particular compounds of formula (I), processes for their preparation, and their use as almost colorless IR absorbers for optical filter applications, in particular for plasma display panels or for laser welding of plastics. These compounds can be used in compositions for inks, paints and plastics, in particular in a wide variety of printing systems, and are particularly well suited for security applications, or for brand protection; or as markers for liquids. Compounds of formula (I'), in particular compounds of formula (I), represent almost colorless IR absorbers that exhibit high resistance to chemicals and solvents and good light stability and good thermal stability. Due to their unique application properties, they can be advantageously used as IR absorbers for laser writing, heat shielding, security printing, laser welding of plastics and as markers for liquids. Background Art

[0002] EP0460496B1 relates to a Anthraquinone dyes, where R 1 and R 2 are each cyano or together have the formula A group wherein n is 0 or 1, X 1 and X 2 are identical or different and are each independently hydrogen, C1-C4-alkyl or halogen, and X 3 is hydrogen or C1-C 26 - alkyl radicals which may be interrupted by one or more oxygen atoms in the form of ether functions and substituted by cyano, halogen, hydroxyl, amino, vinyl, C1-C6-alkanoyloxy, C3-C4-alkenoyloxy or C3-C4-haloalkenoyloxy, and their use for the preparation of liquid-crystalline polymers.

[0003] EP1672052A1 relates to a method for monitoring lubricant degradation; the method comprises the following steps: (a) adding to the lubricant at least one The compound

[0004] Where R 1 and R 2 are independently hydrogen, hydroxyl, OR 11 , amino or NR 11 R 12 ; R 3 and R 5 R is independently alkyl, aryl, aralkyl, heteroalkyl or heterocyclyl; 4 and R 6 are independently hydrogen or alkyl; R 7 , R 8 , R 9 and R10 are independently cyano, nitro, amide, carboxyl, ester, alkyl or hydrogen; R 11 is alkyl, aryl, aralkyl, heteroalkyl, heterocyclyl or alkanoyl; R 12 is hydrogen or alkyl; provided that the at least one compound having formula (I) has at least one substituent selected from cyano, nitro, hydroxy, hydroxyalkyl, amide, carboxyl, ester and unsaturated alkyl; and

[0005] (b) measuring spectroscopic properties of the oil to determine degradation of the at least one compound.

[0006] There is a high demand for nearly colorless NIR absorbers with sufficient stability in the corresponding applications. It has now been surprisingly found that compounds of formula (I'), in particular compounds of formula (I), represent nearly colorless IR absorbers which exhibit high resistance to chemicals and solvents and good light stability and good thermal stability. Due to their unique application properties, they can be advantageously used as IR absorbers for laser writing, heat shielding, security printing, laser welding of plastics and as markers for liquids, in particular oils. Summary of the invention

[0007] Thus, in a first aspect, the present invention relates to compounds having the formula

[0008] in

[0009] Y 1 , Y 2 , Y 3 and Y 4 It is O or Y 1 and Y 2 One of them is O and the other is NR 13 And Y 3 and Y 4 One of them is O and the other is NR 13 , where R 13 With R 1 The meaning of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 The definitions are as follows.

[0010] A compound of formula (I') wherein Y 1 and Y 2 One of them is O and the other is NR13 And Y 3 and Y 4 One of them is O and the other is NR 13 An example of a compound is one having the formula A compound wherein R 1 and R 2 The same and selected from straight chain C1-C 24 -alkyl, branched C3-C 24 -alkyl, C5-C8-cycloalkyl, phenyl and phenyl-C1-C 10 -alkylene, where the cycloalkyl, phenyl and phenyl-alkylene rings in the last three radicals are unsubstituted or substituted by 1, 2 or 3 identical or different substituents R 11 Substitution, where R 11 It is C1-C 12 -alkyl. Compounds of formula (I") can be prepared in a manner analogous to known methods. Reference is made, for example, to US4491666 and JP58219262.

[0011] Preferred are compounds of formula (I') wherein Y 1 , Y 2 , Y 3 and Y 4 is a compound of O, i.e., having the formula of compounds, wherein

[0012] R 1 and R 2 independently selected from hydrogen, C1-C 24 -alkyl, C1-C 24 -haloalkyl, C3-C 24 -Cycloalkyl, C6-C 10 -Aryl and C6-C 10 -Aryl-C1-C 10 -alkylene, where the cycloalkyl, aryl and aryl-alkylene rings in the last three groups are unsubstituted or substituted by one or more substituents R 11 substituted, and wherein C1-C 24 -alkyl, C1-C 24 -haloalkyl and C6-C 10 -Aryl-C1-C 10 The alkylene portion of the -alkylene group may be selected from one or more of O, S and NR 12 The heteroatom or heteroatom group is interrupted;

[0013] R 3 , R 4 , R 5 , R 6 , R 7 , R8 , R 9 and R 10 independently selected from hydrogen, C1-C 24 -alkyl, C1-C 24 -haloalkyl, C3-C 24 -cycloalkyl, heterocycloalkyl, heteroaryl, C6-C 10 -Aryl and C6-C 10 -Aryl-C1-C 10 -alkylene, where the cycloalkyl, aryl and aryl-alkylene rings in the last three groups are unsubstituted or substituted by one or more substituents R 11 'substituted, and wherein C1-C 24 -alkyl, C1-C 24 -haloalkyl and C6-C 10 -Aryl-C1-C 10 The alkylene portion of the -alkylene group may be selected from one or more of O, S and NR 12 ' is interrupted by a heteroatom or heteroatom group;

[0014] Each R 11 Selected from C1-C 24 -alkyl, C1-C 24 -Fluoroalkyl, C1-C 24 - alkoxy, fluorine, chlorine or bromine;

[0015] Each R 11 'Selected from C1-C 24 -alkyl, C1-C 24 -Fluoroalkyl, C1-C 24 - alkoxy, fluorine, chlorine or bromine; and

[0016] R 12 and R 12 'are independently hydrogen, C1-C 20 -alkyl, C3-C 24 -cycloalkyl, heterocycloalkyl, heteroaryl or C6-C 10 -Aryl.

[0017] In another aspect, the present invention provides a printing ink formulation for security printing, the printing ink formulation comprising at least one compound of formula (I'), in particular at least one compound of formula (I), as defined above and below.

[0018] In another aspect, the present invention provides a security document comprising a substrate and at least one compound of formula (I'), in particular at least one compound of formula (I), as defined above and below.

[0019] In another aspect, the present invention provides a security document obtainable by a printing process, wherein a printing ink formulation is used, the printing ink formulation comprising at least one compound of general formula (I'), at least one compound of formula (I), as defined above and below.

[0020] In one embodiment, R 1 and R 2 It's hydrogen.

[0021] In another embodiment, R 1 and R 2 Preferably selected from straight chain C1-C 24 -alkyl, branched C3-C 24 -alkyl, C5-C8-cycloalkyl, phenyl, or phenyl-C1-C 10 -alkylene, where the cycloalkyl, phenyl and phenyl-alkylene rings in the last three radicals are unsubstituted or substituted by 1, 2 or 3 identical or different substituents R 11 Substitution, where R 11 is as defined above and is preferably C1-C 12 -alkyl or C1-C 12 -alkoxy. More preferably R 1 and R 2 Selected from straight chain C1-C 24 -alkyl, branched C3-C 24 -alkyl, C5-C8-cycloalkyl, or phenyl, wherein the last two substituents are substituted by one, two or three C1-C6-alkyl substituents or C1-C6-alkoxy substituents.

[0022] Even more preferably R 1 and R 2 is selected from the group consisting of: C5-C8-cycloalkyl, such as, for example, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl and cyclooctyl, which are unsubstituted or substituted by one, two or three C1-C6-alkyl substituents; straight-chain C4-C 20 -alkyl; a group having formula (A.1); a group having formula (A.2); a group having formula (A.3); a group having formula (B.1); or a group having formula (B.2)

[0023]

[0024] in

[0025] # represents the bonding site to the imide nitrogen atom;

[0026] R in formula (A.1) c , Rd and R e Independently selected from C1-C 17 -alkyl, where R c , R d and R e The total number of carbon atoms in the group is an integer from 3 to 23;

[0027] R in formula (A.2) f and R g Independently selected from C1-C 17 -alkyl, where R f and R g The total number of carbon atoms in the group is an integer from 2 to 22;

[0028] R in formula (A.3) h and R i Independently selected from C1-C 18 -alkyl, where R h and R i The total number of carbon atoms in the group is an integer from 3 to 23;

[0029] When B is present in formula (B.1) and (B.2), it is C1-C 10 - alkylene;

[0030] y is 0, 1, or 2;

[0031] R 11 Independently selected from C1-C 24 -alkyl, C1-C 24 -Fluoroalkyl, C1-C 24 - alkoxy, fluorine, chlorine or bromine;

[0032] In formula (B.2), z is 1, 2 or 3.

[0033] Among the groups having the formulae (A.1), (A.2) and (A.3), the group having the formula (A.3) is preferred. In the context of group (A.3), R h and R i Preferably, independently of one another, they are selected from linear C2-C 10 -alkyl.

[0034] Among the groups of formula (B.1) and (B.2), in one embodiment, those in which y is 0, ie those in which the variable B is absent, are preferred. Regardless of its presence or absence, R 11 Preferably selected from C1-C 24 -alkyl, more preferably straight chain C1-C 10 -alkyl or branched C3-C 10 -alkyl, especially isopropyl or tert-butyl. In particular, groups of formula (B.2) are preferred. Most preferably R1 and R 2 is a group having the formula (B.2), wherein (B) y Absent. Specific examples of groups of formula (B.2) are 2,6-dimethylphenyl, 2,4-di(tert-butyl)phenyl, 2,6-diisopropylphenyl or 2,6-di(tert-butyl)phenyl.

[0035] Among the groups having formula (B.1) and (B.2), in another embodiment, those groups in which y is 1 or 2 are preferred. Regardless of its presence or absence, R 11 Preferably selected from C1-C 12 -alkyl, more preferably C1-C6-alkyl, or C1-C 12 -alkoxy, more preferably straight-chain C1-C6-alkoxy. In particular, groups of the formulae (B.1) and (B.2) are preferred. Specific examples of groups of the formulae (B.1) and (B.2) are benzyl or 4-methoxy-2-phenylethyl.

[0036] In one embodiment, R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 Preferably selected from straight chain C1-C 24 -alkyl, branched C3-C 24 -alkyl, C5-C8-cycloalkyl, phenyl, or phenyl-C1-C 10 -alkylene, where the cycloalkyl, phenyl and phenyl-alkylene rings in the last three radicals are unsubstituted or substituted by 1, 2 or 3 identical or different substituents R 11 'Substitution, where R 11 ' is as defined above and is preferably C1-C 12 -alkyl or C1-C 12 -alkoxy. More preferably R 1 and R 2 Selected from C1-C 24 -alkyl, C5-C8-cycloalkyl, or phenyl, where the last two substituents are substituted by one, two or three C1-C6-alkyl substituents.

[0037] Even more preferably R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10is selected from the group consisting of: C5-C8-cycloalkyl, such as, for example, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl and cyclooctyl, which are unsubstituted or substituted by one, two or three C1-C6-alkyl substituents; C1-C 12 -alkyl;

[0038] in

[0039] When B is present in formula (B.1) and (B.2), it is C1-C 10 - alkylene;

[0040] y is 0, 1, or 2;

[0041] R 11’ Independently selected from C1-C 24 -alkyl, C1-C 24 -Fluoroalkyl, C1-C 24 - alkoxy, fluorine, chlorine or bromine;

[0042] In formula (B.2), z is 1, 2 or 3.

[0043] Among the radicals of formula (B.1) and (B.2), preference is given to those in which y is 0, ie those in which the variable B is absent. Regardless of its presence, R 11 Preferably selected from C1-C 24 -alkyl, more preferably straight chain C1-C 10 -alkyl or branched C3-C 10 -alkyl, especially methyl, isopropyl, n-butyl or tert-butyl. In particular, groups of formula (B.2) are preferred. Most preferably R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 is a group having the formula (B.2), wherein (B) y Absent. Specific examples of groups of formula (B.2) are 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl or 4-n-butylphenyl.

[0044] In another preferred embodiment, R 3 , R 5 , R 7 and R 9 is hydrogen and R 4 , R 6 , R 8 and R 10 Selected from straight chain C1-C 24 -alkyl, branched C3-C24 -alkyl, C5-C8-cycloalkyl, phenyl, or phenyl-C1-C 10 -alkylene, where the cycloalkyl, phenyl and phenyl-alkylene rings in the last three radicals are unsubstituted or substituted by 1, 2 or 3 identical or different substituents R 11 'Substitution, where R 11 ' is as defined above and is preferably C1-C 12 -alkyl or C1-C 12 -alkoxy. More preferably R 1 and R 2 Selected from C4-C 20 -alkyl, C5-C8-cycloalkyl, or phenyl, where the last two substituents are substituted by one, two or three C1-C6-alkyl substituents.

[0045] Even more preferably R 4 , R 6 , R 8 and R 10 is selected from the group consisting of: C5-C8-cycloalkyl, such as, for example, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl and cyclooctyl, which are unsubstituted or substituted by one, two or three C1-C6-alkyl substituents; C1-C 12 -alkyl;

[0046] in

[0047] When B is present in formula (B.1) and (B.2), it is C1-C 10 - alkylene;

[0048] y is 0, 1, or 2;

[0049] R 11’ Independently selected from C1-C 24 -alkyl, C1-C 24 -Fluoroalkyl, C1-C 24 - alkoxy, fluorine, chlorine or bromine;

[0050] In formula (B.2), z is 1, 2 or 3.

[0051] Among the radicals of formula (B.1) and (B.2), preference is given to those in which y is 0, ie those in which the variable B is absent. Regardless of its presence, R 11’ Preferably selected from C1-C 24 -alkyl, more preferably straight chain C1-C 10 -alkyl or branched C3-C 10 -alkyl, especially methyl, isopropyl, n-butyl or tert-butyl. In particular, groups of formula (B.2) are preferred. Most preferably R4 , R 6 , R 8 and R 10 is a group having the formula (B.2), wherein (B) y Absent. Specific examples of groups of formula (B.2) are 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl or 4-n-butylphenyl.

[0052] The compounds of general formula (I) have at least one of the following advantageous properties:

[0053] - good fastness to chemicals, especially to hypochlorite bleach and to solvents like toluene, acetone or methylene chloride,

[0054] -Good boiling water fastness,

[0055] -Good light fastness,

[0056] - Colorlessness (i.e. minimum absorption in the VIS range of the spectrum (400 to 700 nm))

[0057] -Good thermal stability,

[0058] - High compatibility with a wide variety of formulations, in particular printing ink formulations for security printing and thermoplastic polymer formulations for laser welding.

[0059] For definitions and descriptions of fastness requirements in banknote printing, see, for example, "Chemical and Physical Resistance" in "Extract of the ANNEX 13 of the Technical Specification for Euro banknote production" (European Central Bank, July 2004).

[0060] The compounds of the general formula (I) can be used, inter alia, for security printing, brand protection, as markers for liquids (especially oils), invisible and / or IR-readable barcodes, laser welding of plastics, curing of surface coatings using IR radiators, drying and curing of prints, fixing of toners on paper or plastics, optical filters for plasma display panels, laser marking of paper or plastics, heating of plastic preforms, and for heat shielding applications.

[0061] Compounds of formula (I), especially those wherein R 1 and R 2 and / or R 4 , R 6 , R 8and R 10 Compounds of formula (I) which are not hydrogen may provide several benefits, in particular high solubility and / or (light) stability in the application medium. In addition, certain compounds of formula (I) are particularly suitable as IR absorbers for absorbing light having wavelengths of 680 to 1000 nm due to their good solubility and high absorption in the application medium. In addition, compounds of formula (I), especially those in which R 1 and R 2 and / or R 4 , R 6 , R 8 and R 10 Compounds of formula (I) which are not hydrogen are particularly suitable as markers for liquids, especially oils (such as mineral oils), due to their advantageous application properties, such as good solubility in liquids, high absorption, good photostability, good storage stability, and good detectability (even in very small amounts in the correspondingly labeled liquid). DETAILED DESCRIPTION

[0062] Here and throughout the specification, the term "near infrared light" means light in the range of 680 to 1000 nm.

[0063] Here and throughout the specification, the term "visible light" refers to light in the range of approximately 380 nm to 740 nm.

[0064] The term "C1-C n "-alkyl" refers to a group of straight-chain or branched saturated hydrocarbon groups having 1 to n carbon atoms. For example, the term C1-C 24 -alkyl designates the group of straight-chain or branched saturated hydrocarbon radicals having 1 to 24 carbon atoms, while the term C1-C4-alkyl designates the group of straight-chain or branched saturated hydrocarbon radicals having 1 to 4 carbon atoms, and the term C5-C 20 Alkyl designates a group of straight-chain or branched saturated hydrocarbon groups having 5 to 20 carbon atoms, and the term C6-C 20-Alkyl designates the group of straight or branched saturated hydrocarbon radicals having 6 to 20 carbon atoms. Examples of alkyl include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methylpropyl (isopropyl), 1,1-dimethylethyl (tert-butyl), pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylbutyl, Methylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, heptyl, octyl, 2-ethylhexyl, 1,1,3,3-tetramethylbutyl (tert-octyl), nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl and in the case of nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, their isomers, in particular mixtures of isomers, such as "isononyl", "isodecyl". Examples of C1-C4-alkyl are, for example, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl.

[0065] As used herein, the term "C1-C 24 "-haloalkyl" means a straight or branched C1-C 24 C1-C2-haloalkyl is substituted with 1-chloro-2- fluoroethyl, 1-bromo-2- fluoroethyl, 1-chloro ... chloro-2- fluoroethyl, 1- chloro-2- fluoroethyl, 1- chloro-2- fluoroethyl, 1- chloro-2- fluoroethyl, 1- chloro-2- fluoroethyl, 1- chloro-2- fluoroethyl, 1- chloro-2- fluoroethyl, 1- chloro-2- fluoroethyl, 1- chloro-2- fluoroethyl, 1- chloro-2- fluoroethyl, 1- chloro-2- fluoroethyl, 1- chloro-2- fluoroethyl, 1- chloro-2- fluoroethyl, 1- chloro-2- fluoroethyl, 1- chloro-2- fluoroethyl, 1- chloro-2- fluoroethyl, 1- chloro-2- fluoroethyl, 1- chloro-2- fluoroethyl, 1- chloro- 24 "-fluoroalkyl" means a straight or branched C1-C 24Alkyl, wherein some or all of the hydrogen atoms in these groups may be replaced by fluorine as above. Examples of C1-C2-fluoroalkyl are fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl and pentafluoroethyl.

[0066] As used herein, the term "C1-C 24 "-alkoxy" means a straight or branched C1-C1-alkyl group as defined above which is bound to the remainder of the molecule via an oxygen 24 Examples of C1-C4-alkoxy are methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy and 1,1-dimethylethoxy.

[0067] As used herein, the term "C3-C 24 "-cycloalkyl" means a monocyclic, bicyclic or tricyclic cycloalkyl group which is unsubstituted or substituted by one or more radicals R 7 (e.g. 1, 2, 3 or 4 R 7 C3-C 24 Examples of -cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, cyclohexadecyl and norbornyl (=bicyclo[2.2.1]heptyl).

[0068] As used herein, the term "C6-C 10 "-aryl" means phenyl or naphthyl.

[0069] As used herein, the term "C6-C 10 "-Aryloxy" means phenoxy and naphthoxy.

[0070] The term "alkylene" or "alkanediyl" as used herein refers to a straight or branched chain alkyl group as defined above wherein one hydrogen atom at any position of the carbon backbone is replaced by another bonding site, thus forming a divalent moiety.

[0071] As used herein, the term "C6-C 10 -Aryl-C1-C 10 -alkylene" (also referred to as aralkyl) refers to a C6-C8 group as defined herein having at least one unsubstituted or substituted aryl group. 10 - an alkyl group substituted with an aryl group. The alkyl group of the arylalkyl group may be substituted with one or more selected from O, S and NR 12 The non-adjacent groups are interrupted, where R 12 is as defined above. C6-C 10 -Aryl-C1-C 10 -Alkylene is preferably phenyl-C1-C 10-alkylene, more preferably phenyl-C1-C4-alkylene, for example benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylprop-1-yl, 2-phenylprop-1-yl, 3-phenylprop-1-yl, 1-phenylbut-1-yl, 2-phenylbut-1-yl, 3-phenylbut-1-yl, 4-phenylbut-1-yl, 1-phenylbut-2-yl, 2-phenylbut-2-yl, 3-phenylbut-2-yl or 4-phenylbut-2-yl; preferably benzyl and 2-phenylethyl.

[0072] The term "heterocycloalkyl" as used herein refers to a monocyclic or bicyclic saturated or partially unsaturated ring system having 3, 4, 5, 6, 7 or 8 ring members (C3-C8-heterocyclyl) which, in addition to carbon atoms as ring members, contains one, two, three or four heteroatoms or heteroatom-containing groups selected from O, N, S, SO and S(O)2 as ring members.

[0073] As used herein, the term "hetaryl" or "heteroaryl" refers to a heteroaromatic monocyclic, bicyclic or tricyclic fused system having 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 ring members, wherein at least one ring is aromatic and contains 1, 2, 3 or 4 heteroatoms selected from N, S or O. The monocyclic heteroaryl group is preferably a 5- or 6-membered heteroaryl group which contains 1, 2 or 3 heteroatoms selected from O, S or N, such as 2-furyl (furan-2-yl), 3-furyl (furan-3-yl), 2-thienyl (thien-2-yl), 3-thienyl (thien-3-yl), 1H-pyrrol-2-yl, 1H-pyrrol-3-yl, pyrrol-1-yl, imidazol-2-yl, imidazol-1-yl, imidazol-4-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-oxadiazol-2-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,3,4-thiadiazol-2-yl, 4H-[1,2,4]-triazol-3-yl, 1,3,4-triazol-2-yl, 1,2,3-triazol-1-yl, 1,2,4-triazol-1-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl and 1,2,4-triazin-3-yl. Bicyclic fully aromatic heteroaryl is 9- or 10-membered and contains 1, 2, 3 or 4 heteroatoms selected from O, S or N. Examples are quinolyl, isoquinolyl, indolyl, isoindolyl, indolizinyl, benzofuranyl, isobenzofuranyl, benzothiophenyl, benzoxazolyl, benzisoxazolyl, benzothiazolyl, benzoxadiazolyl, benzothiadiazolyl, benzoxazinyl, benzopyrazolyl, benzimidazolyl, benzotriazolyl, benzotriazinyl.

[0074] In a preferred embodiment, the present invention relates to a of compounds, wherein

[0075] R 1 and R 2 is as defined above.

[0076] In the described embodiment, the present invention relates to a of compounds, wherein

[0077] R 1 and R 2is hydrogen, the compound is pigmentary, and has the formula A compound wherein R 1 and R 2 is not hydrogen, and the compound is soluble in the administration medium.

[0078] If R 1 and R 2 are not hydrogen, they are independently selected from linear C1-C 24 -alkyl, branched C3-C 24 -alkyl, C5-C8-cycloalkyl, phenyl and phenyl-C1-C 10 -alkylene, where the cycloalkyl, phenyl and phenyl-alkylene rings in the last three radicals are unsubstituted or substituted by 1, 2 or 3 identical or different substituents R 11 Substitution, where R 11 is as defined above or below, and is preferably C1-C 12 -alkyl.

[0079] More preferably R 1 and R 2 The same, and selected from straight chain C1-C 24 -alkyl, branched C3-C 24 -alkyl, C5-C8-cycloalkyl, phenyl and phenyl-C1-C 10 -alkylene, where the cycloalkyl, phenyl and phenyl-alkylene rings in the last three radicals are unsubstituted or substituted by 1, 2 or 3 identical or different substituents R 11 Substitution, where R 11 It is C1-C 12 -alkyl.

[0080] The most preferred is R 1 and R 2 are preferably the same, and are preferably selected from linear or branched C3-C 24 -alkyl, a group having the formula

[0081] in

[0082] # represents the bonding site to the imide nitrogen atom;

[0083] R in formula (A.3) h and R i Independently selected from C1-C 18 -alkyl, where R h and R i The total number of carbon atoms in the group is an integer from 3 to 25;

[0084] When B is present in formula (B.1) and (B.2), it is C1-C10 - alkylene;

[0085] y is 0 or 1;

[0086] R 11 Independently selected from C1-C 24 -alkyl, C1-C 24 -Fluoroalkyl, C1-C 24 - alkoxy, fluorine, chlorine or bromine;

[0087] In formula (B.2), z is 1, 2 or 3.

[0088] R h and R i Preferably, independently of one another, they are selected from linear C2-C 10 -alkyl.

[0089] Among the radicals of formula (B.1) and (B.2), preference is given to those in which y is 0, ie those in which the variable B is absent. Regardless of its presence, R 11 Preferably selected from C1-C 24 -alkyl, more preferably straight chain C1-C 10 -alkyl or branched C3-C 10 -alkyl, especially isopropyl or tert-butyl. In particular, groups of formula (B.2) are preferred. Most preferably R 1 and R 2 are the same and are groups having the formula (B.2), wherein (B) y Absent. Specific examples of groups of formula (B.2) are 2,6-dimethylphenyl, 2,4-di(tert-butyl)phenyl, 2,6-diisopropylphenyl or 2,6-di(tert-butyl)phenyl.

[0090] Particularly preferred examples of compounds of formula (Ia) are compounds (3), (4) and (4a) to (4h) as described in claim 7.

[0091] In another preferred embodiment, the present invention relates to a of compounds, wherein

[0092] R 4 , R 6 , R 8 , R 10 , R 1 and R 2 is as defined above or below.

[0093] In the described embodiment, the present invention relates to a

[0094]

[0095] A compound wherein R 1 and R 2 Not hydrogen.

[0096] If R 1 and R 2 are not hydrogen, they are independently selected from linear C1-C 24 -alkyl, branched C3-C 24 -alkyl, C5-C8-cycloalkyl, phenyl and phenyl-C1-C 10 -alkylene, where the cycloalkyl, phenyl and phenyl-alkylene rings in the last three radicals are unsubstituted or substituted by 1, 2 or 3 identical or different substituents R 11 Substitution, where R 11 is as defined in claim 1, and preferably C1-C 12 -alkyl.

[0097] More preferably R 1 and R 2 are the same and are selected from hydrogen, straight chain C1-C 24 -alkyl, branched C3-C 24 -alkyl, C5-C8-cycloalkyl, phenyl and phenyl-C1-C 10 -alkylene, where the cycloalkyl, phenyl and phenyl-alkylene rings in the last three radicals are unsubstituted or substituted by 1, 2 or 3 identical or different substituents R 11 Substitution, where R 11 It is C1-C 12 -alkyl.

[0098] The most preferred is R 1 and R 2 are preferably the same, and are preferably selected from linear C1-C 24 -alkyl, a group having the formula

[0099] in

[0100] # represents the bonding site to the imide nitrogen atom;

[0101] R in formula (A.3) h and R i Independently selected from C1-C 18 -alkyl, where R h and R i The total number of carbon atoms in the group is an integer from 3 to 25;

[0102] When B is present in formula (B.1) and (B.2), it is C1-C 10 - alkylene;

[0103] y is 0 or 1;

[0104] R 11 Independently selected from C1-C 24 -alkyl, C1-C 24 -Fluoroalkyl, C1-C 24 - alkoxy, fluorine, chlorine or bromine;

[0105] In formula (B.2), z is 1, 2 or 3.

[0106] R h and R i Preferably, independently of one another, they are selected from linear C2-C 10 -alkyl.

[0107] Among the radicals of formula (B.1) and (B.2), preference is given to those in which y is 0, ie those in which the variable B is absent. Regardless of its presence, R 11 Preferably selected from C1-C 24 -alkyl, more preferably straight chain C1-C 10 -alkyl or branched C3-C 10 -alkyl, especially isopropyl or tert-butyl. In particular, groups of formula (B.2) are preferred. Most preferably R 1 and R 2 are the same and are groups having the formula (B.2), wherein (B) y Absent. Specific examples of groups of formula (B.2) are 2,6-dimethylphenyl, 2,4-di(tert-butyl)phenyl, 2,6-diisopropylphenyl or 2,6-di(tert-butyl)phenyl.

[0108] Preferred R 4 , R 6 , R 8 and R 10 independently selected from hydrogen, C1-C 24 -alkyl, C3-C 24 -Cycloalkyl, C6-C 10 -Aryl and C6-C 10 -Aryl-C1-C 10 -alkylene, where the cycloalkyl, aryl and aryl-alkylene rings in the last three radicals are unsubstituted or substituted with 1, 2 or 3 identical or different substituents R 11 'Substitution, where R 11 ' is as defined in claim 1, and preferably C1-C 12 -alkyl.

[0109] More preferably R 4 , R 6 , R 8 and R 10Same, and selected from C1-C 24 -alkyl, C3-C 24 - cycloalkyl, phenyl and phenyl-C1-C4-alkylene, wherein the cycloalkyl, phenyl and phenyl-alkylene rings are unsubstituted or substituted with 1, 2 or 3 identical or different substituents R 11 'Substitution, where R 11 'It is C1-C 12 -alkyl.

[0110] The most preferred is R 4 , R 6 , R 8 and R 10 are preferably the same, and are preferably selected from linear C1-C 24 -alkyl, a group having the formula

[0111] in

[0112] # represents the bonding site to the imide nitrogen atom;

[0113] R in formula (A.3) h and R i Independently selected from C1-C 18 -alkyl, where R h and R i The total number of carbon atoms in the group is an integer from 3 to 25;

[0114] When B is present in formula (B.1) and (B.2), it is C1-C 10 - alkylene;

[0115] y is 0 or 1;

[0116] R 11 ' are independently selected from C1-C 24 -alkyl, C1-C 24 -Fluoroalkyl, C1-C 24 - alkoxy, fluorine, chlorine or bromine;

[0117] In formula (B.2), z is 1, 2 or 3.

[0118] R h and R i Preferably, independently of one another, they are selected from linear C2-C 10 -alkyl.

[0119] Among the radicals of formula (B.2), preference is given to those in which y is 0, ie those in which the variable B is absent. Regardless of its presence, R 11 'Preferably selected from C1-C 24 -alkyl, more preferably straight chain C1-C 10-alkyl or branched C3-C 10 -alkyl, especially isopropyl or tert-butyl. In particular, groups of formula (B.2) are preferred. Most preferably R 4 , R 6 , R 8 and R 10 are the same and are groups having the formula (B.2), wherein (B) y Absent. Specific examples of groups of formula (B.2) are 2,6-dimethylphenyl, 2,4-di(tert-butyl)phenyl, 2,6-diisopropylphenyl or 2,6-di(tert-butyl)phenyl.

[0120] Particularly preferred examples of the compound having the formula (Ib) are the compounds (5a1) to (5g10) described in claim 7.

[0121] The compounds of the invention can be prepared by using conventional techniques familiar to the skilled person. In particular, compounds of formula (I) can be prepared according to the following routes or as described in the experimental part of the present application.

[0122] Another aspect of the present invention is a method for preparing a The method of producing a compound wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 As defined above, the method comprises the following steps:

[0123] i) Heating in H2SO4 has the formula The compound is preferably at a temperature of 50°C to 200°C for 0.5 to 48 hours to obtain a compound of formula (I) wherein R 1 and R 2 is hydrogen, and

[0124] ii) optionally in the presence of a base, reacting the compound obtained in step i) with a compound R 1 -X 1 Reaction to obtain a compound having formula (I), wherein X 1 is Cl, Br or I, and R 1 and R 2 Not hydrogen.

[0125] Alternatively, the R 1 and R 2 Compound (I) which is hydrogen can be converted by conventional means into a compound having the formula The dianhydride and then with the compound R 1 -NH2 reaction to obtain a compound having formula (I), wherein R 1 and R 2 Not hydrogen.

[0126] With formula The compound is prepared by making a compound having the formula The compound is obtained by reacting with CuCN in a solvent at a high temperature, wherein R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 As defined above or below.

[0127] With formula The compound is prepared by making a compound having the formula The compound of R is obtained by reacting with Br2 in a solvent (such as acetic acid) at an elevated temperature (such as 70° C. to 150° C.) for 2 to 12 h, wherein R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 As defined above or below.

[0128] All reactions are typically carried out in the absence of oxygen and moisture. Usually, the reaction mixture is post-processed in a conventional manner, for example by mixing with water, separating the phases, and (if appropriate) by chromatography of the crude product. If the final product is obtained in solid form, it can be purified by recrystallization.

[0129] The compounds of the formula (I) according to the invention can be incorporated without problems into organic and inorganic materials and are therefore suitable for a whole range of end uses, some of which are listed below by way of example.

[0130] The IR absorbers of formula (I) can also be used in the form of a mixture comprising at least one compound of formula (I) and at least one additional IR absorber different from the compound of formula (I). Suitable additional IR absorbers are in principle all known classes of IR absorbers that are compatible with the compounds of formula (I). Preferred additional IR absorbers are selected from metal dithiols, polymethines, phthalocyanines, naphthalocyanines, quinone-diimmonium salts, ammonium salts, rylene, inorganic IR absorbers and mixtures thereof. Additional polymethine IR absorbers are preferably selected from cyanines, squarylium cyanines, croconaines and mixtures thereof. Additional inorganic IR absorbers are preferably selected from indium tin oxide, antimony tin oxide, lanthanum hexaboride, tungsten bronze, copper salts and the like.

[0131] The abovementioned IR absorbers and IR absorber mixtures of the general formula (I) are particularly suitable for security printing.

[0132] Security printing is the field that deals with the printing of items such as currency, passports, tamper-proof labels, stock certificates, stamps, identity cards, etc. The main purpose of security printing is to prevent forgery, tampering or counterfeiting.

[0133] All security documents need to have good stability and durability. In addition, despite the above conditions, it is necessary that the document should have a reasonable lifespan, ideally several years. During this time, the document and the ink thereon (including invisible security marks) should be resistant to fading or discoloration. Therefore, any ink used for the security printing method should be robust, water-resistant, resistant to various chemicals and flexible when solidified. In addition, since some states are abandoning the use of paper as the substrate of banknotes, the printing ink formulation adopted should be available on plastics and paper. It has now been found that compounds with general formula (I) are particularly suitable for printing ink formulations for security printing and particularly for banknotes due to their unique application characteristics.

[0134] In security printing, IR absorbers are added to the printing ink formulation. Suitable printing inks are water-based, oil-based or solvent-based printing inks based on pigments or dyes for inkjet printing, flexographic printing, screen printing, gravure printing, offset printing, laser printing or letterpress printing and for electrophotography. Printing inks for these printing methods usually contain solvents, binders and also various additives, such as plasticizers, antistatic agents or waxes. Printing inks for offset printing and letterpress printing are usually formulated as high-viscosity pasty printing inks, while printing inks for flexographic printing and gravure printing are usually formulated as liquid printing inks with relatively low viscosity.

[0135] In the context of the present invention, the expression "printing ink" also encompasses formulations which, in addition to at least one IR absorber of the general formula (I), comprise colorants. The expression "printing ink" also encompasses colorant-free printing lacquers.

[0136] The printing ink formulation for security printing according to the invention preferably comprises

[0137] a) at least one compound of the general formula (I) as defined above,

[0138] b) a polymer binder,

[0139] c) a solvent,

[0140] d) optionally at least one colorant, and

[0141] e) optionally at least one further additive.

[0142] Suitable components of printing inks are conventional and are familiar to those skilled in the art. Examples of such components are described in "Printing Ink Manual", 4th edition, Leach RH et al. (eds.), Van Nostrand Reinhold, Wokingham, (1988). Details of printing inks and their formulations are also disclosed in "Printing Inks" - Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, 1999 electronic distribution. The formulation of IR absorbing gravure ink formulations is described in US20080241492 A1. The disclosure of the above document is incorporated herein by reference.

[0143] The printing ink formulations according to the invention generally contain 0.0001 to 25% by weight, preferably 0.001 to 15% by weight, in particular 0.01 to 5% by weight, of component a), based on the total weight of the printing ink formulation.

[0144] The compounds of the general formula (I) are present in the printing ink formulations in dissolved form or in solid form (in finely divided state).

[0145] The printing ink formulations according to the invention generally contain 5 to 74% by weight, preferably 10 to 60% by weight, more preferably 15 to 40% by weight, of component b), based on the total weight of the printing ink formulation.

[0146] Suitable polymeric binders b) for the printing ink formulations according to the invention are, for example, selected from natural resins, phenolic resins, phenol-modified resins, alkyd resins, polystyrene homopolymers and copolymers, terpene resins, silicone resins, polyurethane resins, urea-formaldehyde resins, melamine resins, polyamide resins, polyacrylates, polymethacrylates, chlorinated rubbers, vinyl ester resins, acrylic resins, epoxy resins, nitrocellulose, hydrocarbon resins, cellulose acetate, and mixtures thereof.

[0147] The printing ink formulation according to the present invention may also contain a component that forms a polymeric binder through a curing process. Therefore, the printing ink formulation according to the present invention may also be formulated to be energy curable, for example, capable of being cured by UV light or EB (electron beam) radiation. In this embodiment, the binder comprises one or more curable monomers and / or oligomers. The corresponding formulations are known in the art and can be found in standard textbooks such as the "Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints" series published in 7 volumes by John Wiley & Sons in conjunction with SITA Technology Limited in 1997-1998.

[0148] Suitable monomers and oligomers (also called prepolymers) include epoxy acrylates, acrylated oils, urethane acrylates, polyester acrylates, silicone acrylates, acrylated amines, and acrylic saturated resins. Further details and examples are given in "Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints", Volume II: Prepolymers & Reactive Diluents (Edited by G Webster).

[0149] If a curable polymer binder is employed, it may contain a reactive diluent, i.e., a monomer that acts as a solvent and is incorporated into the polymer binder upon curing. Reactive monomers are typically selected from acrylates or methacrylates and may be monofunctional or multifunctional. Examples of multifunctional monomers include polyester acrylates or methacrylates, polyol acrylates or methacrylates, and polyether acrylates or methacrylates.

[0150] In the case where the printing ink formulation is to be cured by UV radiation, it is generally necessary to include at least one photoinitiator to initiate the curing reaction of the monomers upon exposure to UV radiation. Examples of useful photoinitiators can be found in standard textbooks such as "Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints", Volume III, "Photoinitiators for Free Radical Cationic and Anionic Polymerisation", 2nd edition, JV Crivello and K. Dietliker, edited by G. Bradley and published by John Wiley & Sons in association with SITA Technologies Ltd. in 1998. In order to achieve efficient curing, it may also be advantageous to include a sensitizer together with the photoinitiator.

[0151] The printing ink formulations according to the invention generally contain 1 to 94.9999% by weight, preferably 5 to 90% by weight, in particular 10 to 85% by weight, of solvent c), based on the total weight of the printing ink formulation.

[0152] Suitable solvents are selected from water, organic solvents and mixtures thereof. For the purposes of the present invention, reactive monomers which also act as solvents are considered to be part of the abovementioned binder component b).

[0153] Examples of the solvent include water; alcohols such as ethanol, 1-propanol, 2-propanol, ethylene glycol, propylene glycol, diethylene glycol and ethoxypropanol; esters such as ethyl acetate, isopropyl acetate, n-propyl acetate and n-butyl acetate; hydrocarbons such as toluene, xylene, mineral oil and vegetable oil, and mixtures thereof.

[0154] The printing ink formulation according to the invention may contain additional colorants d). Preferably, the printing ink formulation contains 0 to 25% by weight, more preferably 0.1 to 20% by weight, in particular 1 to 15% by weight, of colorants d), based on the total weight of the printing ink formulation.

[0155] Suitable colorants d) are selected from conventional dyes and in particular conventional pigments. The term "pigment" is used comprehensively in the context of the present invention to identify all pigments and fillers, examples being color pigments, white pigments, and inorganic fillers. These include inorganic white pigments, such as titanium dioxide, preferably in the form of rutile, barium sulfate, zinc oxide, zinc sulfide, basic lead carbonate, antimony trioxide, zinc white (zinc sulfide + barium sulfate), or coloring pigments, examples being iron oxide, carbon black, graphite, zinc yellow, zinc green, ultramarine, manganese black, antimony black, manganese violet, Paris blue or Schweinfurt green. In addition to inorganic pigments, the printing ink formulations of the present invention may also contain organic color pigments, examples being sepia, gamboge, Cassel brown, toluidine red, para red, Hansa yellow, indigo, azo dyes, anthraquinones and indigo dyes, as well as dioxazines, quinacridones, phthalocyanines, isoindolinones, and metal complex pigments. Also suitable are synthetic white pigments with air inclusions to increase light scattering, such as Suitable fillers are, for example, aluminosilicates, such as feldspar, silicates, such as kaolin, talc, mica, magnesite, alkaline earth metal carbonates, such as calcium carbonate, in the form of, for example, calcite or chalk, magnesium carbonate, dolomite, alkaline earth metal sulfates, such as calcium sulfate, silicon dioxide and the like.

[0156] The printing ink formulation according to the invention may contain at least one additive e). Preferably, the printing ink formulation contains 0 to 25% by weight, more preferably 0.1 to 20% by weight, in particular 1 to 15% by weight, of at least one component e), based on the total weight of the printing ink formulation.

[0157] Suitable additives (component e)) are selected from plasticizers, waxes, driers, antistatic agents, chelating agents, antioxidants, stabilizers, adhesion promoters, surfactants, flow control agents, defoamers, biocides, thickeners, etc., and combinations thereof. These additives are used in particular for fine-tuning the application-related properties of the printing ink, examples being adhesion, abrasion resistance, drying rate, or slip.

[0158] In particular, the printing ink formulation for security printing according to the invention preferably contains

[0159] a) 0.0001% to 25% by weight of at least one compound of the general formula (I),

[0160] b) 5 to 74% by weight of at least one polymeric binder,

[0161] c) 1 to 94.9999% by weight of at least one solvent,

[0162] d) 0 to 25% by weight of at least one colorant, and

[0163] e) 0 to 25% by weight of at least one further additive,

[0164] The sum of components a) to e) hereby adds up to 100%.

[0165] The printing ink formulation according to the present invention is advantageously prepared in a conventional manner, for example by mixing separate components. As previously mentioned, the IR absorber (I) is present in the printing ink formulation in the form of a dissolved or finely dispersed solid. Additional colorants may be used in the printing ink formulation of the present invention or in a separate ink formulation. When additional colorants are used in a separate formulation, the application time of the printing ink formulation according to the present invention is generally insignificant. For example, the printing ink formulation according to the present invention may be applied first, and then overprinted with a conventional printing ink. However, this order may also be reversed, or alternatively, the printing ink formulation according to the present invention may be applied in the form of a mixture with a conventional printing ink. In each case, the print is readable under a suitable light source.

[0166] Primer can be applied before the printing ink formulation according to the present invention. For example, primer is applied to improve adhesion to the substrate. Additional printing lacquer can also be applied, for example in the form of a covering, to protect the printed image. Additional printing lacquer can also be applied for aesthetic purposes, or for controlling application-related properties. For example, appropriately formulated additional printing lacquer can be used to influence the roughness, electrical properties, or water vapor condensation properties of the substrate surface. Printing lacquer is usually applied online by a painting system on a printing press for printing the printing ink formulation according to the present invention.

[0167] The printing ink formulations according to the invention are also suitable for multilayer materials. Multilayer materials consist, for example, of two or more plastic foils, such as polyolefin foils, metal foils or metallized plastic foils, which are bonded to one another, for example, via lamination or by means of suitable laminating adhesives. These composite materials may also comprise further functional layers, such as odor barrier layers or water vapor barrier layers.

[0168] The abovementioned IR absorbers and IR absorber mixtures of the general formula (I) are also particularly suitable for laser welding of plastics.

[0169] The concentration of the IR absorber or IR absorber mixture of the general formula (I) is, for example, from 5 to 500 ppm, preferably from 10 to 200 ppm.

[0170] In laser welding, plastic parts are welded to each other. The plastic parts to be melted can have any shape. For example, at least one of the plastic parts can be a film.

[0171] The compounds of formula (I) are suitable for welding transparent or at least translucent plastic materials. The plastic materials used can be colorless or colored. In principle, the plastic parts to be melted can consist of the same polymer or different polymers. Preferably, the plastic parts for laser welding are selected from thermoplastic polymers. However, it is also possible that none of the plastic parts to be melted consists of thermoplastics; however, it is necessary to coat at least one part with a thermoplastic containing at least one compound of formula (I).

[0172] The plastic parts for laser welding preferably contain or consist of at least one polymer selected from the group consisting of polyolefins, polyolefin copolymers, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymers, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl esters, polyvinyl alkanals, polyvinyl ketals, polyamides, polyimides, polycarbonates, polycarbonate blends, polyesters, polyester blends, poly(meth)acrylates, poly(meth)acrylate-styrene copolymer blends, poly(meth)acrylate-polyvinylidene fluoride blends, polyurethanes, polystyrenes, styrene copolymers, polyethers, polyetherketones and polysulfones and mixtures thereof.

[0173] Preferred are matrix polymers from the group of polyolefins, polyolefin copolymers, polyvinyl acetals, polyamides, polycarbonates, polycarbonate-polyester blends, polycarbonate-styrene copolymer blends, polyesters, polyester blends, poly(meth)acrylates, poly(meth)acrylate-styrene copolymer blends, poly(meth)acrylate-polyvinylidene fluoride blends, styrene copolymers and polysulfones and mixtures thereof.

[0174] Particularly preferred polymers are transparent or at least translucent. Examples include: polypropylene, polyvinyl butyral, nylon-[6], nylon-[6,6], polycarbonate, polycarbonate-polyethylene terephthalate blends, polycarbonate-polybutylene terephthalate blends, polycarbonate-acrylonitrile / styrene / acrylonitrile copolymer blends, polycarbonate-acrylonitrile / butadiene / styrene copolymer blends, polymethyl methacrylate-acrylonitrile / butadiene / styrene copolymer blends (MABS), polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, impact-modified polymethyl methacrylate, polybutyl acrylate, polymethyl methacrylate-polyvinylidene fluoride blends, acrylonitrile / butadiene / styrene copolymers (ABS), styrene / acrylonitrile copolymers (SAN), polyphenylsulfone, and mixtures comprising two or more (e.g., two, three, four, five) of the above polymers.

[0175] Suitable polymer formulations for laser welding include

[0176] A) a thermoplastic matrix polymer suitable for forming these plastic parts,

[0177] B) at least one compound of the general formula (I) as defined above,

[0178] C) optionally at least one further additive.

[0179] Those polymer formulations for laser welding are likewise according to the invention and are suitable for producing melt-bonded plastic parts by means of laser radiation having a wavelength outside the visible light region.

[0180] The polymer formulations for laser welding can advantageously be produced by conventional extrusion or kneading methods. Components B) and, if present, component C) can be mixed with the matrix polymer A) from the outset in a weight ratio corresponding to the desired final concentration (direct compounding), or a significantly higher concentration of B) and, if present, component C) can be initially selected and the resulting concentrate (masterbatch) can be subsequently diluted with further matrix polymer A) during the production of the part to be melted.

[0181] Suitable additives C) are UV stabilizers, antioxidants, processing plasticizers and the like.

[0182] Furthermore, the polymer formulations for laser welding may contain at least one colorant as an additive for establishing the desired color tone, in particular transparent organic pigments and in particular dyes, for example CI Pigment Yellow 138, 139, 147, 183, 185, 192 and 196, CI Pigment Orange 70, CI Pigment Red 149, 178 and 179, 181, 263, CI Pigment Violet 19 and 29, CI Pigment Blue 15, 15:1, 15:3 and 15:4, CI Pigment Green 7 and 36, CI Solvent Yellow 14, 21 , 93, 130, 133, 145, 163, CI Solvent Red 52, 135, 195, 213, 214 and 225, CI Solvent Blue 35, 45, 67, 68, 97, 104, 122, 132, CI Solvent Violet 13, 46, 49, CI Solvent Green 3, 5 and 28, CI Solvent Orange 47, 60, 86, 114 and 163, CI Solvent Brown 35, 53, as well as CI Disperse Yellow 54, 87, 201, CI Disperse Orange 30, CI Disperse Red 60 and CI Disperse Violet 57.

[0183] Another possible group of additives is that of additives which likewise modify the visual appearance, the mechanical properties or other tactile properties, for example matting agents, such as titanium dioxide, chalk, barium sulfate, zinc sulfide, fillers, such as nanoparticulate silica, aluminum hydroxide, clay and other phyllosilicates, glass fibers and glass spheres.

[0184] In addition, compounds of formula (I) can also be advantageously used for laser marking and laser lettering. In this case, the laser light absorbed by the compound of formula (I) causes heating of the plastic, which leads to its foaming or conversion of the dye present additionally, and in this way produces the marking or lettering.

[0185] Useful liquids which may be labelled with compounds of formula (I) preferably include oils, such as mineral oils, vegetable and animal fatty oils, and ethereal oils.

[0186] The example of such oil is natural oil, such as olive oil, soybean oil or sunflower oil, or natural or synthetic motor oil, hydraulic oil or transmission oil, such as motor vehicle oil or sewing machine oil, or brake fluid and mineral oil, according to the present invention, these mineral oils include gasoline, kerosene, diesel oil and also thermal fuel oil. Particularly preferred is mineral oil, such as gasoline, kerosene, diesel oil or thermal fuel oil, particularly gasoline, diesel oil or thermal fuel oil. Particularly advantageously, the above-mentioned compound with formula (I) is used as a marker of mineral oil, wherein for example for tax reasons, labeling is required at the same time. In order to minimize the cost of labeling, and in order to minimize the possible interaction of the mineral oil of labeling with any other components present such as polyisobutylene amine (PIBA), efforts are made to minimize the amount of labeling. Another reason for minimizing the amount of labeling can be to prevent their possible harmful effects, such as harmful effects on the fuel intake and exhaust gas outlet area of ​​an internal combustion engine.

[0187] The compound of formula (I) used as a marker is added to the liquid in an amount to ensure reliable detection. Typically, the total content of markers (based on weight) in the marked liquid is about 0.1 ppb to 5000 ppb, preferably 1 ppb to 2000 ppb and more preferably 1 ppb to 1000 ppb.

[0188] If appropriate, the compounds of the formula (I) can also be used in a mixture with other markers / dyes.

[0189] For marking liquids, these compounds are usually added in the form of solutions. Particularly in the case of mineral oils, suitable solvents for providing these stock solutions are preferably aromatic hydrocarbons, such as toluene, xylene or relatively high-boiling aromatic compound mixtures.

[0190] In the field of automatic banknote processing, IR absorption plays an important role. Most of the currency in actual circulation carries not only visible color printing, but also specific features that are only detectable in the infrared part of the spectrum. Typically, these IR features are used in banking and vending applications (ATMs, vending machines, etc.) implemented by automatic currency processing equipment in order to identify a certain currency note and verify its authenticity, in particular to distinguish it from copies made by color copiers.

[0191] Therefore, the present invention also relates to a method of detecting the authenticity of a security document as defined above or below, comprising the following steps:

[0192] a) measuring the absorption spectrum of the security document in the NIR range of the electromagnetic spectrum; and

[0193] b) comparing the spectrum measured under a) and / or information derived therefrom with a corresponding spectrum and / or information having an authentic security element.

[0194] Some examples of three-dimensional (3D) printing can utilize fluxes (including energy absorbers) to pattern polymeric building materials. The fluxes are capable of absorbing radiation and converting the absorbed radiation into thermal energy, which in turn causes the polymeric building materials in contact with the flux to coalesce / melt.

[0195] Therefore, the present invention relates to a flux comprising at least one compound of formula (I). The composition of the flux is described in, for example, WO 2020005200, WO 2019245589, WO 2019245518, WO 2019245517, WO 2019245535, WO2019245534, WO 2019245516 and US2019382429.

[0196] Furthermore, the present invention relates to a consumable for use in an additive manufacturing system, the consumable comprising:

[0197] At least one polymer comprising:

[0198] At least one compound having formula (I).

[0199] Furthermore, the present invention relates to a consumable assembly for use in an extrusion-based additive manufacturing system, the consumable assembly comprising:

[0200] Container part;

[0201] a consumable filament at least partially retained in the container portion, the consumable filament comprising:

[0202] at least one polymer, and

[0203] At least one compound having formula (I).

[0204] The consumable filament may have a core comprising at least one polymer and a coating comprising at least one compound having formula (I) (WO 2015130401).

[0205] The at least one polymer may be a fusible polymer selected from the group consisting of polyurethane, polyester, polyalkylene oxide, plasticized PVC, polyamide, protein, PEEK, PEAK, polypropylene, polyethylene, thermoplastic elastomer, POM, polyacrylate, polycarbonate, polymethyl methacrylate, polystyrene or a combination of at least two of these.

[0206] The method for producing an article from the consumable by an additive manufacturing method comprises at least temporarily exposing the consumable to infrared radiation in a wavelength range between 600 nm and 1700 nm.

[0207] The invention also relates to an article obtainable by this method.

[0208] The different features and aspects of the present invention are further illustrated in the following examples. Although these examples are presented to show how those skilled in the art can operate within the scope of the present invention, they are not intended to be limiting of the scope of the present invention, which scope is defined only in the claims. Unless otherwise indicated in the following examples and elsewhere in the specification and claims, all parts and percentages are by weight, temperatures are in degrees Celsius and pressures are at or near atmospheric pressure.

[0209] Examples

[0210] Example 1

[0211]

[0212] a) 2,3,6,7-Tetrabromo-1,4,5,9-tetraamino-9,10-anthraquinone (1)

[0213] In a 500mL round-bottom flask, bromine (9mL, 176mmol) was added dropwise to a solution of 1,4,5,9-tetraamino-9,10-anthraquinone (3g, 11mmol) in acetic acid (250mL) at room temperature over 5 minutes. After heating at 110°C for 6h, the solution was cooled and poured into 500mL of water. NaHSO3 (1.76g) was added under stirring to quench excess bromine. The resulting solid was then filtered and washed with 200mL of K2CO3 aqueous solution (1mol / L) to neutralize the pH. After oven drying at 100°C for 1h, compound (1) (5.8g, 90%) was collected as a purple solid. HRMS (APPI+) m / z: for C 14Calculated for H8Br4N4O2[M+]: 579.7381; found: 579.7350.

[0214] b) 2,3,6,7-Tetracyano-1,4,5,9-tetraamino-9,10-anthraquinone (2)

[0215] In a 500mL round-bottom flask, compound 1 (600mg, 1mmol) and CuCN (2g, 22mmol) were mixed in NMP (250mL) under continuous N2 bubbling for 15min. The solution was then heated to 150°C for 24h. After cooling to room temperature, 500mL of water was added to precipitate the product. The resulting solid was then filtered and washed with 200mL of water and 100mL of methanol in sequence. After oven drying at 100°C for 1h, compound (2) (4g, 90%) was collected as a green solid. HRMS (MALDI+) m / z: calculated for C18H8N8O2[M+]: 368.0770; measured: 368.0771.

[0216] c) 1,4,5,9-Tetraamino-2,3,6,7-9,10-anthraquinone diimide (3)

[0217] In a 250mL round-bottom flask, compound 2 (2g) was slowly added to concentrated sulfuric acid (100mL) at 80°C with vigorous stirring. The solution was then heated to 150°C and stirred for 1.5h. After cooling to room temperature, 500mL of ice water was added to precipitate the crude product. The resulting solid was then filtered and washed with 200mL of water and methanol in sequence. The resulting solid was dissolved in NMP (200mL) at 150°C and stirred for 15 minutes. The solution was filtered while still hot. 1L of water was added to the filtrate to precipitate the product. After filtering and drying in an oven at 100°C for 1h, compound (3) (1g, 50%) was collected as a blue solid. 1 H NMR (500 MHz, DMSO-d6, 393 K, ppm): δ 10.48 (s, 2H, NH), 7.44 (br, 8H, NH2). HRMS (MALDI+) m / z: for C 18 H 10 Calculated value of N6O6[M+]: 406.0656; measured value: 406.0662. 18 H 10 Elemental analysis calculated for N6O6: C, 53.21; H, 2.48; N, 20.68. Measured: C, 52.21; H, 2.56; N, 20.70. IR (KBr, cm -1 ): 3420s, 1727s, 1649s. UV / Vis(THF):λ 最大=802nm(ε=18390M -1 cm -1 ). Mp>300℃.

[0218] Example 2

[0219]

[0220] N,N'-didodecyl-1,4,5,9-tetraamino-2,3,6,7-9,10-anthraquinone diimide (4)

[0221] In a 100mL round-bottom flask, compound 3 (406mg, 1mmol) and NaH (120mg, 5mmol) were mixed in DMSO (50mL) under continuous N2 bubbling for 15min. At room temperature, 1-iodododecane (1200mg, 4mmol) was added dropwise to the mixture in 5min. After stirring at room temperature for 12h, 100mL water was poured into the solution. The resulting precipitate was then filtered and washed with 100mL water. After oven drying for 1h at 100°C, the title compound (660mg, 90%) as a blue solid was collected. 1 HNMR (400 MHz, THF-d8, 293 K, ppm): δ 10.72 (s, 8H, NH2), 1.24 (5, 36H, J = 6.0 Hz, CH2), 0.80 (m, 6H, CH3). HRMS (MALDI+) m / z: Calculated for C42H58N6O6 [M+]: 742.9465; Measured: 742.9566. Elemental analysis calculated for C42H58N6O6: C, 67.90; H, 7.87; N, 11.31. Measured: C, 68.20; H, 7.91; N, 11.60. IR (KBr, cm-1): 3443s, 2921s, 2851s, 1042s. UV / Vis (THF): λ 最大 =794nm(ε=28600M - 1 cm -1 ). Mp>300℃.

[0222] Compound (4) exhibits good solubility in THF. The solution of compound (4) is colorless due to weak absorption in the visible light region.

Claims

1. A compound having the formula in Y 1 , Y 2 , Y 3 and Y 4 It is O or Y 1 and Y 2 One of them is O and the other is NR 13 And Y 3 and Y 4 One of them is O and the other is NR 13 , where R 13 With R 1 Meaning of; In particular in R 1 and R 2 independently selected from hydrogen, C1-C 24 -alkyl, C1-C 24 -haloalkyl, C3-C 24 -Cycloalkyl, C6-C 10 -Aryl and C6-C 10 -Aryl-C1-C 10 -alkylene, where the cycloalkyl, aryl and aryl-alkylene rings in the last three groups are unsubstituted or substituted by one or more substituents R 11 substituted, and wherein C1-C 24 -alkyl, C1-C 24 -haloalkyl and C6-C 10 -Aryl-C1-C 10 The alkylene portion of the -alkylene group may be selected from one or more of O, S and NR 12 The heteroatom or heteroatom group is interrupted; R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 independently selected from hydrogen, C1-C 24 -alkyl, C1-C 24 -haloalkyl, C3-C 24 -cycloalkyl, heterocycloalkyl, heteroaryl, C6-C 10 -Aryl and C6-C 10 -Aryl-C1-C 10 -alkylene, where the cycloalkyl, aryl and aryl-alkylene rings in the last three groups are unsubstituted or substituted by one or more substituents R 11 'substituted, and wherein C1-C 24 -alkyl, C1-C 24 -haloalkyl and C6-C 10 -Aryl-C1-C 10 The alkylene portion of the -alkylene group may be selected from one or more of O, S and NR 12 ' is interrupted by a heteroatom or heteroatom group; Each R 11 Selected from C1-C 24 -alkyl, C1-C 24 -Fluoroalkyl, C1-C 24 - alkoxy, fluorine, chlorine or bromine; Each R 11 'Selected from C1-C 24 -alkyl, C1-C 24 -Fluoroalkyl, C1-C 24 - alkoxy, fluorine, chlorine or bromine; and R 12 and R 12 'are independently hydrogen, C1-C 20 -alkyl, C3-C 24 -cycloalkyl, heterocycloalkyl, heteroaryl or C6-C 10 -Aryl.

2. The compound according to claim 1, which is a compound having the formula Where R 4 , R 6 , R 8 , R 10 , R 1 and R 2 As defined in claim 1.

3. The compound according to claim 1 or 2, wherein R 1 and R 2 independently selected from hydrogen, straight chain C1-C 24 -alkyl, branched C3-C 24 -alkyl, C5-C8-cycloalkyl, phenyl and phenyl-C1-C 10 -alkylene, where the cycloalkyl, phenyl and phenyl-alkylene rings in the last three radicals are unsubstituted or substituted by 1, 2 or 3 identical or different substituents R 11 Substitution, where R 11 is as defined in claim 1, and preferably C1-C 12 -alkyl or C1-C 12 -alkoxy.

4. A compound according to any one of claims 1 to 3, wherein R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 independently selected from hydrogen, C1-C 24 -alkyl, C3-C 24 -Cycloalkyl, C6-C 10 -Aryl and C6-C 10 -Aryl-C1-C 10 -alkylene, where the cycloalkyl, aryl and aryl-alkylene rings in the last three radicals are unsubstituted or substituted with 1, 2 or 3 identical or different substituents R 11 'Substitution, where R 11 ' is as defined in claim 1, and preferably C1-C 12 -alkyl or C1-C 12 -alkoxy.

5. The compound according to any one of claims 1 to 4, which is a compound having the formula Where R 1 and R 2 are the same and are selected from hydrogen, straight chain C1-C 24 -alkyl, branched C3-C 24 -alkyl, C5-C8-cycloalkyl, phenyl and phenyl-C1-C 10 -alkylene, where the cycloalkyl, phenyl and phenyl-alkylene rings in the last three radicals are unsubstituted or substituted by 1, 2 or 3 identical or different substituents R 11 Substitution, where R 11 It is C1-C 12 -alkyl or C1-C 12 -alkoxy.

6. A compound according to any one of claims 1 to 4, which is a compound having the formula in R 1 and R 2 are the same and are selected from hydrogen, straight chain C1-C 24 -alkyl, branched C3-C 24 -alkyl, C5-C8-cycloalkyl, phenyl and phenyl-C1-C 10 -alkylene, where the cycloalkyl, phenyl and phenyl-alkylene rings in the last three radicals are unsubstituted or substituted by 1, 2 or 3 identical or different substituents R 11 Substitution, where R 11 is C1-C6-alkyl or C1-C6-alkoxy; and R 4 , R 6 , R 8 and R 10 Same, and selected from C1-C 24 -alkyl, C3-C 24 - cycloalkyl, phenyl and phenyl-C1-C4-alkylene, wherein the cycloalkyl, phenyl and phenyl-alkylene rings are unsubstituted or substituted with 1, 2 or 3 identical or different substituents R 11 'Substitution, where R 11 ' is C1-C6-alkyl or C1-C6-alkoxy.

7. A compound according to any one of claims 1 to 6, which is The compound having the formula or a compound having the formula 8. Use of the compound according to any one of claims 1 to 7 as IR absorber for light filter applications, for plasma display panels, for laser marking of paper or plastics, for laser welding of plastics, for 3D printing, for curing surface coatings using IR radiators, for drying and curing of prints, for fixing toners on paper or plastics, for heat shielding applications, for invisible and / or IR-readable barcodes, as IR absorber in security printing or for brand protection, or as a marker for liquids, especially oils.

9. A printing ink formulation comprising at least one compound according to any one of claims 1 to 7.

10. The printing ink formulation according to claim 9, comprising a) at least one compound according to any one of claims 1 to 7, b) a polymer binder, c) a solvent, d) optionally at least one colorant, and e) optionally at least one further additive.

11. A method for producing a security document, comprising the step of printing a printing ink formulation according to claim 9 or 10 on a substrate.

12. A security document comprising a substrate and at least one compound according to any one of claims 1 to 7, or obtainable by a process according to claim 11, the security document preferably being selected from the group consisting of banknotes, passports, checks, vouchers, ID or transaction cards, stamps and tax labels.

13. A method of detecting the authenticity of a security document as defined in claim 12, the method comprising the steps of: a) measuring the absorption, reflection or transmission spectrum of the security document in the NIR range of the electromagnetic spectrum; and b) comparing the spectrum measured under a) and / or information derived therefrom with a corresponding spectrum and / or information having an authentic security element.

14. A method for preparing a compound having the formula Where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 As defined in claim 1, the method comprises the following steps: i) Heating in H2SO4 has the formula The compound is preferably at a temperature of 50°C to 200°C for 0.5 to 48 hours to obtain a compound of formula (I) wherein R 1 and R 2 is hydrogen, and ii) optionally in the presence of a base, reacting the compound obtained in step i) with a compound R 1 -X 1 Reaction to obtain a compound having formula (I), wherein X 1 is Cl, Br or I, and R 1 and R 2 Not hydrogen.

15. The method according to claim 14, wherein the The compound is prepared by making a compound having the formula The compound is obtained by reacting with CuCN in a solvent at a high temperature, wherein R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 As defined in claim 1.

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