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US 11,993,005 B1Granted
Process, apparatus and photoswitchable photoinitiators for locally polymerizing a starting material by dual color photopolymerization
Assigneexolo GmbH
InventorsYves Garmshausen, Marcus Reuter, Marin Regehly, Dirk Radzinski
Life of this patent
Estimating the term…
Abstract
A process, an apparatus, and photoswitchable photoinitiators for polymerizing a starting material by dual color photopolymerization. In particular, photoinitiators are provided, which cause curing of photopolymerizable formulations upon illumination with two different wavelengths.
Claims19
A method to form a three-dimensional shape, the method comprising dual color photopolymerization, comprising:
- taking up a polymerizable starting material in a container for the polymerizable starting material, said polymerizable starting material containing photoinitiator molecules which can be excited by sequential optical excitation into a reactive state in which the photoinitiator molecules locally initiate polymerization of the starting material;
- and
- photopolymerizing in a 3d printing process the starting material in a local volume of the container by illuminating the light of the first wavelength and the light of the second wavelength into the local volume of the container, whereby in the local volume the photoinitiator molecules, due to the absorption of the light of the first wavelength, are converted from an initial state in which the photoinitiator molecules substantially do not absorb the light of the second wavelength into an intermediate state with changed optical properties compared to the initial state, such that the photoinitiator molecules in the intermediate state absorb the light of the second wavelength;
- and the photoinitiator molecules are transferred from the intermediate state to the reactive state due to the absorption of the light of the second wavelength, which triggers the polymerization locally;
- wherein the photoinitiator molecules are represented by the following formula (I)
- wherein Ra and Rb are selected independently from unsubstituted or substituted aryl, unsubstituted or substituted alkyne or a linked to each other to form a unsubstituted or substituted ring structure, Y is selected from O, S, or N;
- where Y is N, the substituent contains the atoms necessary to complete a cyclic structure with R8 selected from the group consisting of benzimidazole, indoline, indole, dihydroquinoline, and tetrahydroquinoline;
- wherein Z is selected from N or CR4;
- wherein R3 to R8 are independently selected from the group consisting of H;
- D;
- halogen;
- NO2;
- CN;
- OH;
- SH;
- substituted or unsubstituted C1-C2M-alkyl;
- substituted or unsubstituted C3-C20-cycloalkyl;
- substituted or unsubstituted C6-C48-aryl;
- substituted or unsubstituted C2-C42-heteroaryl;
- substituted or unsubstituted C2-C49-alkyl acyl;
- substituted or unsubstituted C2-C49-aryl acyl;
- substituted or unsubstituted C1-C20-alkoxy;
- substituted or unsubstituted C6-C48-aryloxy, and NH2;
- substituted or unsubstituted C1-C20-alkyl ester;
- substituted or unsubstituted C6-C48-aryl ester;
- substituted or unsubstituted C1-C20 alkyl amide;
- substituted or unsubstituted C6-C48-aryl amide;
- NR′2, SiR′3, —O—SiR′3 wherein R′ is independently selected from the group consisting of substituted or unsubstituted C1-C20-alkyl and substituted or unsubstituted C6-C48-aryl, two R′ may form a ring structure;
- substituted or unsubstituted carboxylic acids and salts thereof;
- substituted or unsubstituted sulfonic acids and salts thereof;
- substituted or unsubstituted sulfonic esters;
- substituted or unsubstituted sulfonic amides;
- formyl;
- ether, thioether;
- carbonate;
- carbonate ester;
- sulfates;
- boronic acids;
- boronic esters;
- phosphonic acids;
- phosphonic esters;
- phosphines;
- phosphates;
- peroxycarbonic acids;
- thiocarbonic acids;
- sulfinic acids;
- sulfinic esters;
- sulfonates;
- thiolesters, sulfoxides;
- sulfones;
- hydrazides;
- thioaldehydes;
- ketones;
- thioketones;
- oximes;
- hydrazines;
- nitroso;
- azo;
- diazo;
- diazonium;
- isocyanides;
- cyanate;
- isocyanate;
- thiocyanate;
- isothiocyanate;
- hydroperoxide;
- peroxide;
- acetals;
- ketal;
- orthoester;
- orthocarbonate esters;
- ammonium;
- imines;
- imides;
- azide;
- nitrate;
- isonitrile;
- nitrosoxy;
- substituted or unsubstituted carbamates;
- substituted or unsubstituted ethers;
- substituted or unsubstituted polyether carbamates;
- substituted or unsubstituted arylazo;
- substituted or unsubstituted C2-C20-alkynyl and substituted or unsubstituted C2-C20-alkenyl;
- wherein the one or more substituents, if present in one or more of R3-R8, are independently selected from the group consisting of D;
- halogen;
- NO2;
- CN, C2-C49-alkyl acyl;
- substituted or unsubstituted C1-C20-alkoxy;
- substituted or unsubstituted C6-C48-aryloxy;
- substituted or unsubstituted C2-C49-aryl acyl;
- (meth)acrylate;
- tosyl;
- NH2;
- and OH;
- and/or wherein two adjacent groups of R5-R8 may be linked to each other to form a fused ring structure;
- and
- wherein at least one of R3-R8, is selected from one of the following structures:
- wherein R14 to R25 are independently selected from the group consisting of H;
- D;
- halogen;
- NO2;
- CN;
- OH;
- SH;
- substituted or unsubstituted C1-C2M-alkyl;
- substituted or unsubstituted C3-C20-cycloalkyl;
- substituted or unsubstituted C6-C48-aryl;
- substituted or unsubstituted C2-C42-heteroaryl;
- substituted or unsubstituted C2-C49-alkyl acyl;
- substituted or unsubstituted C2-C49-aryl acyl;
- substituted or unsubstituted C1-C20-alkoxy;
- substituted or unsubstituted C6-C48-aryloxy, and NH2;
- substituted or unsubstituted C1-C20-alkyl ester;
- substituted or unsubstituted C6-C48-aryl ester;
- substituted or unsubstituted C1-C20 alkyl amide;
- substituted or unsubstituted C6-C48-aryl amide;
- NR′2, SiR′3, —O—SiR′3 wherein R′ is independently selected from the group consisting of substituted or unsubstituted C1-C20-alkyl and substituted or unsubstituted C6-C48-aryl, two R′ may form a ring structure;
- substituted or unsubstituted carboxylic acids and salts thereof;
- substituted or unsubstituted sulfonic acids and salts thereof;
- substituted or unsubstituted sulfonic esters;
- substituted or unsubstituted sulfonic amides;
- formyl;
- ether, thioether;
- carbonate;
- carbonate ester;
- sulfates;
- boronic acids;
- boronic esters;
- phosphonic acids;
- phosphonic esters;
- phosphines;
- phosphates;
- peroxycarbonic acids;
- thiocarbonic acids;
- sulfinic acids;
- sulfinic esters;
- sulfonates;
- thiolesters, sulfoxides;
- sulfones;
- hydrazides;
- thioaldehydes;
- ketones;
- thioketones;
- oximes;
- hydrazines;
- nitroso;
- azo;
- diazo;
- diazonium;
- isocyanides;
- cyanate;
- isocyanate;
- thiocyanate;
- isothiocyanate;
- hydroperoxide;
- peroxide;
- acetals;
- ketal;
- orthoester;
- orthocarbonate esters;
- ammonium;
- imines;
- imides;
- azide;
- nitrate;
- isonitrile;
- nitrosoxy;
- substituted or unsubstituted carbamates;
- substituted or unsubstituted ethers;
- substituted or unsubstituted polyether carbamates;
- substituted or unsubstituted arylazo;
- substituted or unsubstituted C2-C20-alkynyl and substituted or unsubstituted C2-C20-alkenyl;
- wherein the one or more substituents, if present in one or more of R14-R25, are independently selected from the group consisting of D;
- halogen;
- NO2;
- CN, C2-C49-alkyl acyl;
- substituted or unsubstituted C1-C20-alkoxy;
- substituted or unsubstituted C6-C48-aryloxy;
- substituted or unsubstituted C2-C49-aryl acyl;
- (meth)acrylate;
- tosyl;
- NH2;
- and OH;
- and R15 and R16 may be linked to each other to form a unsubstituted or substituted ring structure.
181 more elements
A 3d printing process to form a three-dimensional shape for locally polymerizing a starting material by dual color photopolymerization, comprising:
- photopolymerizing in the 3d printing process a polymerizable starting material in a local volume by illuminating light of a first wavelength and light of a second wavelength, different from the first wavelength, into the local volume, the polymerizable starting material containing photoinitiator molecules configured to be converted by sequential optical excitation into a reactive state in which the photoinitiator molecules locally trigger polymerization of the starting material, whereby in the local volume
- the photoinitiator molecules are converted, due to the absorption of the light of the first wavelength, from an initial state in which the photoinitiator molecules substantially do not absorb the light of the second wavelength, into an intermediate state with changed optical properties compared to the initial state, such that the photoinitiator molecules in the intermediate state absorb the light of the second wavelength;
- and
- the photoinitiator molecules are transferred from the intermediate state to the reactive state due to the absorption of the light of the second wavelength, which triggers the polymerization locally;
- wherein the photoinitiator molecules are represented by the following formula (I)
- wherein Ra and Rb are selected independently from unsubstituted or substituted aryl, unsubstituted or substituted alkyne or a linked to each other to form a unsubstituted or substituted ring structure, Y is selected from O, S, or N;
- where Y is N, the substituent contains the atoms necessary to complete a cyclic structure with R8 selected from the group consisting of benzimidazole, indoline, indole, dihydroquinoline, and tetrahydroquinoline;
- wherein Z is selected from N or CR4;
- wherein R3 to R8 are independently selected from the group consisting of H;
- D;
- halogen;
- NO2;
- CN;
- OH;
- SH;
- substituted or unsubstituted C1-C2M-alkyl;
- substituted or unsubstituted C3-C20-cycloalkyl;
- substituted or unsubstituted C6-C48-aryl;
- substituted or unsubstituted C2-C42-heteroaryl;
- substituted or unsubstituted C2-C49-alkyl acyl;
- substituted or unsubstituted C2-C49-aryl acyl;
- substituted or unsubstituted C1-C20-alkoxy;
- substituted or unsubstituted C6-C48-aryloxy, and NH2;
- substituted or unsubstituted C1-C20-alkyl ester;
- substituted or unsubstituted C6-C48-aryl ester;
- substituted or unsubstituted C1-C20 alkyl amide;
- substituted or unsubstituted C6-C48-aryl amide;
- NR′2, SiR′3, —O—SiR′3,
- wherein R′ is independently selected from the group consisting of substituted or unsubstituted C1-C20-alkyl and substituted or unsubstituted C6-C48-aryl, two R′ may form a ring structure;
- substituted or unsubstituted carboxylic acids and salts thereof, substituted or unsubstituted sulfonic acids and salts thereof;
- substituted or unsubstituted sulfonic esters;
- substituted or unsubstituted sulfonic amides;
- formyl;
- ether, thioether;
- carbonate;
- carbonate ester;
- sulfates;
- boronic acids;
- boronic esters;
- phosphonic acids;
- phosphonic esters;
- phosphines;
- phosphates;
- peroxycarbonic acids;
- thiocarbonic acids;
- sulfinic acids;
- sulfinic esters;
- sulfonates;
- thiolesters, sulfoxides;
- sulfones;
- hydrazides;
- thioaldehydes;
- ketones;
- thioketones;
- oximes;
- hydrazines;
- nitroso;
- azo;
- diazo;
- diazonium;
- isocyanides;
- cyanate;
- isocyanate;
- thiocyanate;
- isothiocyanate;
- hydroperoxide;
- peroxide;
- acetals;
- ketal;
- orthoester;
- orthocarbonate esters;
- ammonium;
- imines;
- imides;
- azide;
- nitrate;
- isonitrile;
- nitrosoxy;
- substituted or unsubstituted carbamates;
- substituted or unsubstituted ethers;
- substituted or unsubstituted polyether carbamates;
- substituted or unsubstituted arylazo;
- substituted or unsubstituted C2-C20-alkynyl and substituted or unsubstituted C2-C20-alkenyl;
- wherein the one or more substituents, if present in one or more of R3-R8, are independently selected from the group consisting of D;
- halogen;
- NO2;
- CN, C2-C49-alkyl acyl;
- substituted or unsubstituted C1-C20-alkoxy;
- substituted or unsubstituted C6-C48-aryloxy;
- substituted or unsubstituted C2-C49-aryl acyl;
- (meth)acrylate;
- tosyl;
- NH2;
- and OH;
- and/or wherein two adjacent groups of R5-R8 may be linked to each other to form a fused ring structure;
- and
- wherein at least one of R3-R8, is selected from one of the following structures:
- wherein R14 to R25 are independently selected from the group consisting of H;
- D;
- halogen;
- NO2;
- CN;
- OH;
- SH;
- substituted or unsubstituted C1-C2M-alkyl;
- substituted or unsubstituted C3-C20-cycloalkyl;
- substituted or unsubstituted C6-C48-aryl;
- substituted or unsubstituted C2-C42-heteroaryl;
- substituted or unsubstituted C2-C49-alkyl acyl;
- substituted or unsubstituted C2-C49-aryl acyl;
- substituted or unsubstituted C1-C20-alkoxy;
- substituted or unsubstituted C6-C48-aryloxy, and NH2;
- substituted or unsubstituted C1-C20-alkyl ester;
- substituted or unsubstituted C6-C48-aryl ester;
- substituted or unsubstituted C1-C20 alkyl amide;
- substituted or unsubstituted C6-C48-aryl amide;
- NR′2, SiR′3, —O—SiR′3 wherein R′ is independently selected from the group consisting of substituted or unsubstituted C1-C20-alkyl and substituted or unsubstituted C6-C48-aryl, two R′ may form a ring structure;
- substituted or unsubstituted carboxylic acids and salts thereof;
- substituted or unsubstituted sulfonic acids and salts thereof;
- substituted or unsubstituted sulfonic esters;
- substituted or unsubstituted sulfonic amides;
- formyl;
- ether, thioether;
- carbonate;
- carbonate ester;
- sulfates;
- boronic acids;
- boronic esters;
- phosphonic acids;
- phosphonic esters;
- phosphines;
- phosphates;
- peroxycarbonic acids;
- thiocarbonic acids;
- sulfinic acids;
- sulfinic esters;
- sulfonates;
- thiolesters, sulfoxides;
- sulfones;
- hydrazides;
- thioaldehydes;
- ketones;
- thioketones;
- oximes;
- hydrazines;
- nitroso;
- azo;
- diazo;
- diazonium;
- isocyanides;
- cyanate;
- isocyanate;
- thiocyanate;
- isothiocyanate;
- hydroperoxide;
- peroxide;
- acetals;
- ketal;
- orthoester;
- orthocarbonate esters;
- ammonium;
- imines;
- imides;
- azide;
- nitrate;
- isonitrile;
- nitrosoxy;
- substituted or unsubstituted carbamates;
- substituted or unsubstituted ethers;
- substituted or unsubstituted polyether carbamates;
- substituted or unsubstituted arylazo;
- substituted or unsubstituted C2-C20-alkynyl and substituted or unsubstituted C2-C20-alkenyl;
- or
- wherein R19 is selected from substituted or unsubstituted C1-C10-alkyl;
- substituted or unsubstituted C3-C10-cycloalkyl;
- substituted or unsubstituted C6-C32-aryl:
- substituted or unsubstituted C2-C28-heteroaryl, substituted or unsubstituted C2-C20-alkynyl and substituted or unsubstituted C2-C20-alkenyl, the substituent may contains the atoms necessary to complete a cyclic structure with one of R5—R8 or R10—R13 forming an anthracene, thioxanthone or fluorenone;
- wherein the one or more substituents, if present in one or more of R14-R25, are independently selected from the group consisting of D;
- halogen;
- NO2;
- CN, C2-C49-alkyl acyl;
- substituted or unsubstituted C1-C20-alkoxy;
- substituted or unsubstituted C6-C48-aryloxy;
- substituted or unsubstituted C2-C49-aryl acyl;
- (meth)acrylate;
- tosyl;
- NH2;
- and OH;
- and R15 and R16 may be linked to each other to form a unsubstituted or substituted ring structure.
186 more elements
A 3d printing process to form a three-dimensional shape for locally polymerizing a starting material by dual color photopolymerization, comprising:
- photopolymerizing in the 3d printing process a polymerizable starting material in a local volume by illuminating light of a first wavelength and light of a second wavelength, different from the first wavelength, into the local volume, the polymerizable starting material containing photoinitiator molecules configured to be converted by sequential optical excitation into a reactive state in which the photoinitiator molecules locally trigger polymerization of the starting material, whereby in the local volume
- the photoinitiator molecules are converted, due to the absorption of the light of the first wavelength, from an initial state in which the photoinitiator molecules substantially do not absorb the light of the second wavelength, into an intermediate state with changed optical properties compared to the initial state, such that the photoinitiator molecules in the intermediate state absorb the light of the second wavelength;
- and
- the photoinitiator molecules are transferred from the intermediate state to the reactive state due to the absorption of the light of the second wavelength, which triggers the polymerization locally;
- wherein the photoinitiator molecules are represented by the following formula (I)
- wherein Ra and Rb are selected independently from unsubstituted or substituted aryl, unsubstituted or substituted alkyne or a linked to each other to form a unsubstituted or substituted ring structure, Y is selected from O, S, or N;
- where Y is N, the substituent contains the atoms necessary to complete a cyclic structure with R8 selected from the group consisting of benzimidazole, indoline, indole, dihydroquinoline, and tetrahydroquinoline;
- wherein Z is selected from N or CR4;
- wherein R3 to R8 are independently selected from the group consisting of H;
- D;
- halogen;
- NO2;
- CN;
- OH;
- SH;
- substituted or unsubstituted C1-C2M-alkyl;
- substituted or unsubstituted C3-C20-cycloalkyl;
- substituted or unsubstituted C6-C48-aryl;
- substituted or unsubstituted C2-C42-heteroaryl;
- substituted or unsubstituted C2-C49-alkyl acyl;
- substituted or unsubstituted C2-C49-aryl acyl;
- substituted or unsubstituted C1-C20-alkoxy;
- substituted or unsubstituted C6-C48-aryloxy, and NH2;
- substituted or unsubstituted C1-C20-alkyl ester;
- substituted or unsubstituted C6-C48-aryl ester;
- substituted or unsubstituted C1-C20 alkyl amide;
- substituted or unsubstituted C6-C48-aryl amide;
- NR′2, SiR′3, —O—SiR′3,
- wherein R′ is independently selected from the group consisting of substituted or unsubstituted C1-C20-alkyl and substituted or unsubstituted C6-C48-aryl, two R′ may form a ring structure;
- substituted or unsubstituted carboxylic acids and salts thereof, substituted or unsubstituted sulfonic acids and salts thereof;
- substituted or unsubstituted sulfonic esters;
- substituted or unsubstituted sulfonic amides;
- formyl;
- ether, thioether;
- carbonate;
- carbonate ester;
- sulfates;
- boronic acids;
- boronic esters;
- phosphonic acids;
- phosphonic esters;
- phosphines;
- phosphates;
- peroxycarbonic acids;
- thiocarbonic acids;
- sulfinic acids;
- sulfinic esters;
- sulfonates;
- thiolesters, sulfoxides;
- sulfones;
- hydrazides;
- thioaldehydes;
- ketones;
- thioketones;
- oximes;
- hydrazines;
- nitroso;
- azo;
- diazo;
- diazonium;
- isocyanides;
- cyanate;
- isocyanate;
- thiocyanate;
- isothiocyanate;
- hydroperoxide;
- peroxide;
- acetals;
- ketal;
- orthoester;
- orthocarbonate esters;
- ammonium;
- imines;
- imides;
- azide;
- nitrate;
- isonitrile;
- nitrosoxy;
- substituted or unsubstituted carbamates;
- substituted or unsubstituted ethers;
- substituted or unsubstituted polyether carbamates;
- substituted or unsubstituted arylazo;
- substituted or unsubstituted C2-C20-alkynyl and substituted or unsubstituted C2-C20-alkenyl;
- wherein the one or more substituents, if present in one or more of R3-R8, are independently selected from the group consisting of D;
- halogen;
- NO2;
- CN, C2-C49-alkyl acyl;
- substituted or unsubstituted C1-C20-alkoxy;
- substituted or unsubstituted C6-C48-aryloxy;
- substituted or unsubstituted C2-C49-aryl acyl;
- (meth)acrylate;
- tosyl;
- NH2;
- and OH;
- and/or wherein two adjacent groups of R5—R8 may be linked to each other to form a fused ring structure;
- and
- wherein at least one of R3—R8, is selected from one of the following structures:
- wherein R14 to R25 are independently selected from the group consisting of H;
- D;
- halogen;
- NO2;
- CN;
- OH;
- SH;
- substituted or unsubstituted C1-C20-alkyl;
- substituted or unsubstituted C3-C20-cycloalkyl;
- substituted or unsubstituted C6-C48-aryl;
- substituted or unsubstituted C2-C42-heteroaryl;
- substituted or unsubstituted C2-C49-alkyl acyl;
- substituted or unsubstituted C2-C49-aryl acyl;
- substituted or unsubstituted C1-C20-alkoxy;
- substituted or unsubstituted C6-C48-aryloxy, and NH2;
- substituted or unsubstituted C1-C20-alkyl ester;
- substituted or unsubstituted C6-C48-aryl ester;
- substituted or unsubstituted C1-C20 alkyl amide;
- substituted or unsubstituted C6-C48-aryl amide;
- NR′2, SiR′3, —O—SiR′3,
- wherein R′ is independently selected from the group consisting of substituted or unsubstituted C1-C20-alkyl and substituted or unsubstituted C6-C48-aryl, two R′ may form a ring structure;
- substituted or unsubstituted carboxylic acids and salts thereof, substituted or unsubstituted sulfonic acids and salts thereof;
- substituted or unsubstituted sulfonic esters;
- substituted or unsubstituted sulfonic amides;
- formyl;
- ether, thioether;
- carbonate;
- carbonate ester;
- sulfates;
- boronic acids;
- boronic esters;
- phosphonic acids;
- phosphonic esters;
- phosphines;
- phosphates;
- peroxycarbonic acids;
- thiocarbonic acids;
- sulfinic acids;
- sulfinic esters;
- sulfonates;
- thiolesters, sulfoxides;
- sulfones;
- hydrazides;
- thioaldehydes;
- ketones;
- thioketones;
- oximes;
- hydrazines;
- nitroso;
- azo;
- diazo;
- diazonium;
- isocyanides;
- cyanate;
- isocyanate;
- thiocyanate;
- isothiocyanate;
- hydroperoxide;
- peroxide;
- acetals;
- ketal;
- orthoester;
- orthocarbonate esters;
- ammonium;
- imines;
- imides;
- azide;
- nitrate;
- isonitrile;
- nitrosoxy;
- substituted or unsubstituted carbamates;
- substituted or unsubstituted ethers;
- substituted or unsubstituted polyether carbamates;
- substituted or unsubstituted arylazo;
- substituted or unsubstituted C2-C20-alkynyl and substituted or unsubstituted C2-C20-alkenyl;
- wherein the one or more substituents, if present in one or more of R14-R25, are independently selected from the group consisting of D;
- halogen;
- NO2;
- CN, C2-C49-alkyl acyl;
- substituted or unsubstituted C1-C20-alkoxy;
- substituted or unsubstituted C6-C48-aryloxy;
- substituted or unsubstituted C2-C49-aryl acyl;
- (meth)acrylate;
- tosyl;
- NH2;
- and OH;
- and R15 and R16 may be linked to each other to form a unsubstituted or substituted ring structure;
- wherein the photoinitiator molecule is represented by the following formula (II)
- wherein X is selected from S, CR1R2, or NR1;
- Y is selected from O, S, or NRc;
- when Y is N, the substituent Rc contains the atoms necessary to complete a cyclic structure with R8 selected from the group consisting of benzimidazole, indoline, indole, dihydroquinoline, and tetrahydroquinoline;
- Z is selected from N or CR4;
- and R1, R2 and R9 are independently selected as defined in R3 to R8 regarding formula (I) above;
- wherein R10-R13 of the photoinitiator molecule represented by the following formula (II) are independently selected from the group consisting of H and electron withdrawing groups (EWG) and R3-R8 are independently selected from the group consisting of H and substituents belonging to the following formulae:
- and wherein R14-R25 are independently selected as defined in R14 to R25 regarding formula (I) above;
- or
- wherein R3-R8 and R10-R13 of the photoinitiator molecule represented by the following formula (II) are independently selected from the group consisting of H and electron withdrawing groups (EWG);
- or
- wherein R10-R13 of the photoinitiator molecule represented by the following formula (II) are independently selected from the group consisting of H and electron withdrawing groups (EWG), and one of R5-R8 is selected from unsubstituted or substituted arylacyl;
- or unsubstituted or substituted alkylacyl, wherein the other of R5-R8 and R3 and R4 are independently selected as defined in R3 to R8 regarding formula (I) above;
- or
- at least one of R6, R7 and R12 is selected from the group consisting of CF3, SO2Me, SO2NH2, CN, F, NO2, C6-aryl, unsubstituted C6-arylacyl of the following formulae:
- dimethoxy-substituted arylacyl of the formula
- methoxy-substituted arylacyl of the formula
- fluorine-substituted arylacyl of the following formula
- alternatively of the formula
- and C6-aryl, wherein R1-R5, R8-R11 and R13 are independently selected as defined in R3 to R8 regarding formula (I) above.
201 more elements
Dependencies are inferred from the claim text.