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US 2025/0179306 A1Published application
Naphthopyran photoswitchable photoinitiators for locally polymerizing a starting material by dual color photopolymerization
Assigneexolo GmbH
InventorYves GARMSHAUSEN
Life of this patent
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Abstract
The present invention relates to a process for locally polymerizing a starting material by dual color photopolymerization using photoinitiator molecule which is represented by one of the following formula (Ib)
Claims17
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;
- wherein
- the photoinitiator molecule is represented by one of the following formula (Ib)
- wherein
- R1, R2, R4 to R9, and R11 to R20 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, substituted or unsubstituted C1-C20-hetero 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, substituted or unsubstituted C2-C20-alkenyl;
- and the following structures (i) to (viii)
- wherein R21 to R36 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;
- or
- R15 and R16 form together a single bond and the remaining R1, R2, R4 to R9, and R11 to R14 and R17 to R36 are selected as defined above;
- wherein
- the one or more substituents, if present in one or more of R1, R2, R4 to R9, and R11 to R36, 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;
- substituted or unsubstituted C2-C49-aryl ester, (meth)acrylate;
- tosyl;
- NH2;
- and OH;
- and
- two adjacent groups of R1, R2, R4 to R9, and R11 to R36 may be linked to each other to form a substituted or unsubstituted fused ring structure, wherein the one or more substituents, if present in one or more of R1, R2, R4 to R9, and R11 to R36, 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;
- substituted or unsubstituted C2-C49-aryl ester, (meth)acrylate;
- tosyl;
- NH2;
- and OH.
181 more elements
A process comprising using a photoinitiator molecule for locally polymerizing a starting material by dual color photopolymerization;
- wherein
- the photoinitiator molecule is represented by one of the following formula (Ib)
- wherein
- R1, R2, R4 to R9, and R11 R20 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, substituted or unsubstituted C1-C20-hetero 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, substituted or unsubstituted C2-C20-alkenyl;
- and the following structures (i) to (viii)
- wherein R21 to R36 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;
- or
- R15 and R16 form together a single bond and the remaining R1, R2, R4 to R9, and R11 to R14 and R17 to R36 are selected as defined above;
- wherein
- the one or more substituents, if present in one or more of R1, R2, R4 to R9, and R11 to R36, 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;
- substituted or unsubstituted C2-C49-aryl ester, (meth)acrylate;
- tosyl;
- NH2;
- and OH;
- and
- two adjacent groups of R1, R2, R4 to R9, and R11 to R36 may be linked to each other to form a substituted or unsubstituted fused ring structure, wherein the one or more substituents, if present in one or more of R1, R2, R4 to R9, and R11 to R36, 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;
- substituted or unsubstituted C2-C49-aryl ester, (meth)acrylate;
- tosyl;
- NH2;
- and OH.
175 more elements
An apparatus for locally polymerizing a starting material by dual color photopolymerization, comprising:
- an intake for a polymerizable starting material;
- light generating means arranged to generate light of a first wavelength and light of a second wavelength, the second wavelength being different from the first wavelength;
- and
- a light guide device arranged to irradiate the light of the first wavelength and the light of the second wavelength into a local volume;
- said device being adapted to perform the following procedure:
- taking up the polymerizable starting material by said intake, said 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 the starting material in a local volume by irradiating the light of the first wavelength and the light of the second wavelength into the local volume, 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 molecule is represented by one of the following formula (Ib)
- wherein
- R1, R2, R4 to R9, and R11 R20 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, substituted or unsubstituted C1-C20-hetero 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, substituted or unsubstituted C2-C20-alkenyl;
- and the following structures (i) to (viii)
- wherein R21 to R36 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;
- or
- R15 and R16 form together a single bond and the remaining R1, R2, R4 to R9, and R11 to R14 and R17 to R36 are selected as defined above;
- wherein
- the one or more substituents, if present in one or more of R1, R2, R4 to R9, and R11 to R36, 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;
- substituted or unsubstituted C2-C49-aryl ester, (meth)acrylate;
- tosyl;
- NH2;
- and OH;
- and
- two adjacent groups of R1, R2, R4 to R9, and R11 to R36 may be linked to each other to form a substituted or unsubstituted fused ring structure, wherein the one or more substituents, if present in one or more of R1, R2, R4 to R9, and R11 to R36, 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;
- substituted or unsubstituted C2-C49-aryl ester, (meth)acrylate;
- tosyl;
- NH2;
- and OH.
186 more elements
Dependencies are inferred from the claim text.