Photoresist composition, system comprising a photoresist composition, method for producing a three-dimensional structure, and use of a photoresist composition in 3d-printing

Patent metadata

Field	Value
Publication number	US-2024408815-A1
Application number	US-202218703452-A
Country	US
Kind code	A1
Filing date	Oct 26, 2022
Priority date	Oct 28, 2021
Publication date	Dec 12, 2024
Grant date	—

Abstract

An aspect of the present invention relates to a photoresist composition, comprising: (A) a polymerizable monomer, (B) a photoinitiator, and optionally (C) a polymerization inhibitor, wherein the photoinitiator has at least the following electronic quantum me-chanical energy states: (i) a ground state, (ii) a substantially optically excitable first intermediate state, and (iii) an optically excitable polymerization-inducing state, wherein the first intermediate state is energetically located above the ground state and below the polymerization-inducing state and has a lifetime of about 100 ps to 10 s, and the polymerization-inducing state is optically excitable from the first intermediate state by a single-photon excitation of a predetermined wavelength. Further aspects relate to a system comprising a photoresist composition, a method for producing a three-dimen-sional structure and a use of a photoresist composition in 3D-printing.

First claim

1 . A system for 3D-printing, comprising:
a photoresist composition comprising a polymerizable monomer and a photoinitiator, wherein the photoinitiator has at least the following electronic quantum mechanical energy states: (i) a ground state, (ii) a substantially optically excitable first intermediate state, and (iii) an optically excitable polymerization-inducing state, wherein the first intermediate state is energetically located above the ground state and below the polymerization-inducing state and has a lifetime of about 100 ps to 10 s, and wherein the polymerization-inducing state is optically excitable from the first intermediate state by a single-photon excitation of a predetermined wavelength; and at least one continuous-wave light source for irradiating the photoresist composition adapted to excite the polymerization-inducing state of the photoinitiator by at least two sequential single-photon excitations of substantially the same predetermined wavelength.

2 . The system according to claim 1 , further comprising:
a focusing unit for focusing the light emitted by the at least one continuous-wave light source on the photoresist composition; and a positioning unit for controlling the position of the focusing unit with respect to the position of the photoresist composition.

3 . The system according to claim 1 , wherein the predetermined wavelength is between about 300 nm and about 900 nm.

4 . The system according to claim 1 , wherein the first intermediate state is a relaxed state with respect to an energetically higher state being optically excitable from the ground state by a single-photon excitation.

5 . The system according to claim 1 , wherein the photoinitiator is selected from the group consisting of alpha-diketones, beta-diketones, gamma-diketones, spiropyrans, merocyanines, carbazoles, thiophenes, polycyclic aromatic hydrocarbons, triketones, photoenoles, (di-)acylgermanes, bis(germyl)ketones, and thioxanthones.

6 . The system according to claim 1 , wherein the photoresist composition comprise a polymerization inhibitor, the polymerization inhibitor is selected from the group consisting of 2,2,6,6-tetramethyl-4-piperidyl-1-oxyl (TEMPO) and derivatives thereof, bis(2,2,6,6-tetramethyl-4-piperidyl-1-oxyl) sebacate (BTPOS) and derivatives thereof, other hindered amine light stabilizers (HALS), 1,4-diazabicyclo[2.2.2]octane (DABCO), n-propyl gallate (NPG), p-phenylenediamine (PPD), cyclodextrines, phenothiazines, hydroxylamines, quinones, mequinol, 4-tert-butylcatechol (TBC), butylated hydroxytoluene (BHT), nitrobenzenes, phenol, p-nitrophenol, stilbenes, galvinoxyl, and azulene.

7 . The system according to claim 6 , wherein the content of the photoinitiator is 0.1% to 10% by weight based on the photoresist composition and/or the content of the polymerization inhibitor is 0.05% to 10% by weight based on the photoresist composition.

8 . The system according to claim 1 , wherein the at least one continuous-wave light source comprises a laser and/or a light emitting diode.

9 . The system according to claim 1 , wherein the at least one continuous-wave light source has an optical power of about 1 mW or larger.

10 . A method for producing a three-dimensional structure, wherein the method comprises the following steps:
providing a photoresist composition comprising a polymerizable monomer and a photoinitiator, wherein the photoinitiator has at least the following electronic quantum mechanical energy states: (i) a ground state, (ii) a substantially optically excitable first intermediate state, and (iii) an optically excitable polymerization-inducing state, wherein the first intermediate state is energetically located above the ground state and below the polymerization-inducing state and has a lifetime of about 100 ps to 10 s, and wherein the polymerization-inducing state is optically excitable from the first intermediate state by a single-photon excitation of a predetermined wavelength; and exciting the polymerization-inducing state of the photoinitiator by at least two sequential single-photon excitations of substantially the same predetermined wavelength to cause polymerization in at least a partial volume of the photoresist composition by irradiating the at least partial volume by means of at least one continuous-wave light source.

11 . The method according to claim 10 , wherein the method further comprises:
removing an unpolymerized and/or incompletely polymerized remaining volume of the photoresist composition, wherein the polymerized at least partial volume of the photoresist composition corresponds to the three-dimensional structure.

12 . A photoresist composition comprising an acrylic monomer, as a polymerizable monomer, an alpha-diketone as a photoinitiator, and a nitroxide as a polymerization inhibitor,
wherein the photoinitiator has at least the following electronic quantum mechanical energy states: (i) a ground state, (ii) a substantially optically excitable first intermediate state, and (iii) an optically excitable polymerization-inducing state, wherein the first intermediate state is energetically located above the ground state and below the polymerization-inducing state and has a lifetime of about 100 ps to 10 s, and wherein the polymerization-inducing state is optically excitable from the first intermediate state by a single-photon excitation of a predetermined wavelength.

13 . The method according to claim 10 , wherein the photoresist composition further comprises a polymerization inhibitor.

14 . The method according to claim 13 , wherein the content of the photoinitiator is 0.1% to 10% by weight based on the photoresist composition and/or the content of the polymerization inhibitor is 0.05% to 10% by weight based on the photoresist composition.

15 . The method according to claim 13 , wherein the polymerization inhibitor is selected from the group consisting of 2,2,6,6-tetramethyl-4-piperidyl-1-oxyl (TEMPO) and derivatives thereof, bis(2,2,6,6-tetramethyl-4-piperidyl-1-oxyl) sebacate (BTPOS) and derivatives thereof, other hindered amine light stabilizers (HALS), 1,4-diazabicyclo[2.2.2]octane (DABCO), n-propyl gallate (NPG), p-phenylenediamine (PPD), cyclodextrines, phenothiazines, hydroxylamines, quinones, mequinol, 4-tert-butylcatechol (TBC), butylated hydroxytoluene (BHT), nitrobenzenes, phenol, p-nitrophenol, stilbenes, galvinoxyl, and azulene.

16 . The method according to claim 10 , wherein the photoinitiator is selected from the group consisting of alpha-diketones, beta-diketones, gamma-diketones, spiropyrans, merocyanines, carbazoles, thiophenes, polycyclic aromatic hydrocarbons, triketones, photoenoles, (di-)acylgermanes, bis(germyl)ketones, and thioxanthones.

17 . The photoresist composition according to claim 12 , wherein the acrylic monomer is pentaerythritol triacrylate or trimethylolpropane triacrylate.

18 . The photoresist composition according to claim 12 , wherein the alpha-diketone is benzil.

19 . The photoresist composition according to claim 12 , wherein the nitroxide is bis(2,2,6,6-tetramethyl-4-piperidyl-1-oxyl) sebacate,

20 . The photoresist composition according to claim 12 , wherein the content of the alpha-diketone is 0.1% to 10% by weight based on the photoresist composition and/or the content of the nitroxide is 0.05% to 10% by weight based on the photoresist composition.

Assignees

• Karlsruher Inst Technologie

Inventors

• Hahn Vincent
• Wegener Martin
• Messer Tobias

Classifications

• G03F7/029

  Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur · CPC title

• B29K2105/0005

  containing compounding ingredients (releasing, lubricating or separating agents B29C33/56, fibers B29K2105/08, B29K2105/12; fillers B29K2105/16, recycled material B29K2105/26) · CPC title

• B29K2105/0002

  monomers or prepolymers · CPC title

• B29K2033/04

  Polymers of esters · CPC title

• B29C64/268

  using laser beams; using electron beams [EB] · CPC title