Process and apparatus for locally polymerizing a starting material by dual color photopolymerization and method for volumetric printing of a shaped body

A process for locally polymerizing a starting material by dual color photopolymerization, comprising:

• providing a polymerizable starting material containing photoinitiator molecules which can be converted by sequential optical excitation into a reactive state in which the photoinitiator molecules locally trigger polymerization of the starting material;
• and
• photopolymerizing the starting material in a local volume by irradiating light of a first wavelength and light of a second wavelength, different from the first wavelength, into the local volume, 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;
• (A) characterized in that the photoinitiator molecule is 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-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 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;
• or
• (B) characterized in that 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 to R13 are independently selected as defined in R3 to R8 regarding formula (I) above.