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

1. 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 R a and R b 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 R 8 selected from the group consisting of benzimidazole, indoline, indole, dihydroquinoline, and tetrahydroquinoline; wherein Z is selected from N or CR 4 ; wherein R 3 to R 8 are independently selected from the group consisting of H; D; halogen; NO 2 ; CN; OH; SH; substituted or unsubstituted C 1 -C 20 -alkyl; substituted or unsubstituted C 3 -C 20 -cycloalkyl; substituted or unsubstituted C 6 -C 48 -aryl; substituted or unsubstituted C 2 -C 42 -heteroaryl; substituted or unsubstituted C 2 -C 49 -alkyl acyl; substituted or unsubstituted C 2 -C 49 -aryl acyl; substituted or unsubstituted C 1 -C 20 -alkoxy; substituted or unsubstituted C 6 -C 48 -aryloxy, and NH 2 ; substituted or unsubstituted C 1 -C 20 -alkyl ester; substituted or unsubstituted C 6 -C 48 -aryl ester; substituted or unsubstituted C 1 -C 20 alkyl amide; substituted or unsubstituted C 6 -C 48 -aryl amide; NR′ 2 , SiR′ 3 , —O—SiR′ 3 wherein R′ is independently selected from the group consisting of substituted or unsubstituted C 1 -C 20 -alkyl and substituted or unsubstituted C 6 -C 48 -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 C 2 -C 20 -alkynyl and substituted or unsubstituted C 2 -C 20 -alkenyl; wherein the one or more substituents, if present in one or more of R 3 -R 8 , are independently selected from the group consisting of D; halogen; NO 2 ; CN, C 2 -C 49 -alkyl acyl; substituted or unsubstituted C 1 -C 20 -alkoxy; substituted or unsubstituted C 6 -C 48 -aryloxy; substituted or unsubstituted C 2 -C 49 -aryl acyl; (meth) acrylate; tosyl; NH 2 ; and OH; and/or wherein two adjacent groups of R 5 -R 8 may be linked to each other to form a fused ring structure; and

wherein at least one of R 3 -R 8 , is selected from one of the following structures:

wherein R 14 to R 25 are independently selected from the group consisting of H; D; halogen; NO 2 ; CN; OH; SH; substituted or unsubstituted C 1 -C 20 -alkyl; substituted or unsubstituted C 3 -C 20 -cycloalkyl; substituted or unsubstituted C 6 -C 48 -aryl; substituted or unsubstituted C 2 -C 42 -heteroaryl; substituted or unsubstituted C 2 -C 49 -alkyl acyl; substituted or unsubstituted C 2 -C 49 -aryl acyl; substituted or unsubstituted C 1 -C 20 -alkoxy; substituted or unsubstituted C 6 -C 48 -aryloxy, and NH 2 ; substituted or unsubstituted C 1 -C 20 -alkyl ester; substituted or unsubstituted C 6 -C 48 -aryl ester; substituted or unsubstituted C 1 -C 20 alkyl amide; substituted or unsubstituted C 6 -C 48 -aryl amide; NR′ 2 , SiR′ 3 , —O—SiR′ 3 wherein R′ is independently selected from the group consisting of substituted or unsubstituted C 1 -C 20 -alkyl and substituted or unsubstituted C 6 -C 48 -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 C 2 -C 20 -alkynyl and substituted or unsubstituted C 2 -C 20 -alkenyl; wherein the one or more substituents, if present in one or more of R 14 -R 25 , are independently selected from the group consisting of D; halogen; NO 2 ; CN, C 2 -C 49 -alkyl acyl; substituted or unsubstituted C 1 -C 20 -alkoxy; substituted or unsubstituted C 6 -C 48 -aryloxy; substituted or unsubstituted C 2 -C 49 -aryl acyl; (meth) acrylate; tosyl; NH 2 ; and OH; and R 15 and R 16 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, CR 1 R 2 , or NR 1 ; Y is selected from O, S, or NR c ; when Y is N, the substituent R c contains the atoms necessary to complete a cyclic structure with R 8 selected from the group consisting of benzimidazole, indoline, indole, dihydroquinoline, and tetrahydroquinoline; Z is selected from N or CR 4 ; and R 1 to R 13 are independently selected as defined in R 3 to R 8 regarding formula (I) above.

2. A process according to claim 1 , characterized in that the light of the first wavelength and the light of the second wavelength are simultaneously irradiated into the local volume.

3. A process according to claim 1 , characterized in that the light of the second wavelength is irradiated into the local volume after the irradiation of the light of the first wavelength in the local volume has ended, the light of the second wavelength being irradiated before the end of a decay time of the intermediate state of the photoinitiator molecules.

4. A process according to claim 1 , characterized in that the photoinitiator molecules in the intermediate state substantially do not absorb the light of the first wavelength.

5. A process according to claim 1 , characterized in that the photoinitiator molecules are converted from the intermediate state to the initial state due to the absorption of light of a third wavelength in volumes where no polymerization is desired.

6. A process according to claim 1 , characterized in that the photoinitiator molecules are converted into a reactive state due to the sequential absorption of light of the second wavelength which triggers a polymerization in the local volume.

7. A process according to claim 1 , characterized in that the photoinitiator molecules are converted into a reactive state due to the absorption of the light of the second wavelength, which triggers a radical polymerization in the local volume.

8. A process according to claim 1 , characterized in that R 14 , R 15 , and R 16 are independently selected from H, D, CN, halogen, substituted or unsubstituted C 1 -C 10 -alkyl; substituted or unsubstituted C 3 -C 10 -cycloalkyl; substituted or unsubstituted C 6 -C 32 -aryl; or substituted or unsubstituted C 2 -C 28 -heteroaryl.

9. A process according to claim 1 , characterized in that R 19 is selected from substituted or unsubstituted C 1 -C 10 -alkyl; substituted or unsubstituted C 3 -C 10 -cycloalkyl; substituted or unsubstituted C 6 -C 32 -aryl; substituted or unsubstituted C 2 -C 28 -heteroaryl, substituted or unsubstituted C 2 -C 20 -alkynyl and substituted or unsubstituted C 2 -C 20 -alkenyl, the substituent may contain the atoms necessary to complete a cyclic structure with one of R 5 -R 8 or R 10 -R 13 forming an anthracene, thioxanthone or fluorenone.

10. A process according to one of claim 1 , characterized in that R 14 is NR′ 2 , wherein R′ is independently selected from the group consisting of H, D, substituted or unsubstituted C 1 -C 10 -alkyl and substituted or unsubstituted C 6 -C 32 -aryl, and two R′ may form a ring structure; or OR′, wherein R′ is selected from the group consisting of H, D, substituted or unsubstituted C 1 -C 10 -alkyl; substituted or unsubstituted C 3 -C 10 -cycloalkyl; substituted or unsubstituted C 6 -C 32 -aryl; substituted or unsubstituted C 2 -C 28 -heteroaryl, SiR “3, wherein R” is independently selected from the group consisting of substituted or unsubstituted C 1 -C 10 -alkyl and substituted or unsubstituted C 6 -C 32 -aryl; and R 15 and R 16 are independently selected from H, D, CN, substituted or unsubstituted C 1 -C 10 -alkyl; substituted or unsubstituted C 3 -C 10 -cycloalkyl; substituted or unsubstituted C 6 -C 32 -aryl; substituted or unsubstituted C 2 -C 28 -heteroaryl.

11. A process according to claim 1 , characterized in that R 14 and R 15 are OR′, wherein R′ is independently selected from the group consisting of H, D, substituted or unsubstituted C 1 -C 10 -alkyl; substituted or unsubstituted C 3 -C 10 -cycloalkyl; substituted or unsubstituted C 6 -C 32 -aryl; substituted or unsubstituted C 2 -C 28 -heteroaryl; and R 16 is selected from H, D, CN, substituted or unsubstituted C 1 -C 10 -alkyl; substituted or unsubstituted C 3 -C 10 -cycloalkyl; substituted or unsubstituted C 6 -C 32 -aryl; substituted or unsubstituted C 2 -C 28 -heteroaryl.

12. A process according to claim 1 , characterized in that R 10 -R 13 are independently selected from the group consisting of H and electron withdrawing groups (EWG), and one of R 5 -R 8 is selected from unsubstituted or substituted arylacyl; or unsubstituted or substituted alkylacyl;

and/or at least one of R 5 -R 8 is independently selected from the group consisting of electron donating groups (EDG), and at least one of R 5 -R 8 , R 10 -R 13 is selected from unsubstituted or substituted arylacyl; or unsubstituted or substituted alkylacyl;

or at least one of R 6 , R 7 and R 12 is selected from the group consisting of CF 3 , SO 2 Me, SO 2 NH 2 , CN, F, NO 2 , C 6 -aryl, unsubstituted C 6 -arylacyl of the following formula

dimethoxy-substituted arylacyl of the formula

methoxy-substituted arylacyl of the formula

fluorine-substituted arylacyl of the following formula

alternatively of the formula

and C 6 -aryl.

13. A process according to claim 1 ,

characterized in that the photoinitiator molecules comprise one or more of the following compounds:

14. A process according to claim 1 , characterized in that the polymerizable starting material further contains a co-initiator and/or a sensitizer.

15. A process according to claim 1 , characterized in that the polymerizable starting material further contains an additive, an acid and/or a base.

16. 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;

characterized in that a light beam of light of the first wavelength and a light beam of light of the second wavelength are irradiated at least partially overlapping in the local volume.

17. A process according to claim 1 , characterized in that the starting material is polymerized in several local volumes by means of photopolymerization and thus a three-dimensional shaped body is produced in the starting material.

18. A process for 3D-printing a shaped body, wherein the shaped body is produced by means of a process according to claim 1 .

19. 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.