IP Library Granted Patent US 12,287,574
Granted Patent B2
US 12,287,574 · App. 17/624,216 · Granted Apr 29, 2025

Resin composition and flow cells incorporating the same

Inventors: Yekaterina Rokhlenko (San Diego, CA); Timothy J. Merkel (San Diego, CA)
Assignee: Illumina, Inc.
G03F7/0217G01N21/05G01N21/6428G03F7/0002G03F7/0045G03F7/038G03F7/0757B82Y40/00
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 12,287,574
App. No.
17/624,216
Granted
Apr 29, 2025
Kind
B2
Abstract

An example resin composition includes an epoxy resin matrix, a first photoacid generator, and a second photoacid generator. The first photoacid generator includes an anion having a molecular weight less than about 250 g/mol. The second photoacid generator includes an anion having a molecular weight greater than about 300 g/mol. In an example, i) a cation of the first photoacid generator has, or ii) a cation of the second photoacid generator has, or iii) the cations of the first and second photoacid generators have a mass attenuation coefficient of at least 0.1 L/(g*cm) at a wavelength of incident light to cure the resin composition.

Claims (74)

1. A resin composition, comprising:

an epoxy resin matrix;

a first photoacid generator including an anion having a molecular weight less than 250 g/mol; and

a second photoacid generator including an anion having a molecular weight greater than about 300 g/mol;

wherein i) a cation of the first photoacid generator has, or ii) a cation of the second photoacid generator has, or iii) the cations of the first and second photoacid generators have a mass attenuation coefficient of at least 0.1 L/(g*cm) at a wavelength of incident light to cure the resin composition;

and wherein the epoxy resin matrix comprises an epoxy material selected from the group consisting of an epoxy functionalized silsesquioxane; trimethylolpropane triglycidyl ether; tetrakis(epoxycyclohexyl ethyl)tetramethyl cyclotetrasiloxane; a copolymer of (epoxycyclohexylethyl)methylsiloxane and dimethylsiloxane; 1,3-bis[2-(3,4-epoxycyclohexyl) ethyl]tetramethyl disiloxane; 1,3-bis(glycidoxypropyl) tetramethyl disiloxane; 3,4-epoxycyclohexylmethyl-3,4-epoxycyclo-hexanecarboxylate; bis((3,4-epoxycyclohexyl)methyl) adipate; 4-vinyl-1-cyclohexene 1,2-epoxide; vinylcyclohexene dioxide; 4,5-epoxytetrahydrophthalic acid diglycidylester; 1,2-epoxy-3-phenoxypropane; glycidyl methacrylate; 1,2-epoxyhexadecane; poly(ethylene glycol) diglycidylether; pentaerythritol glycidyl ether; diglycidyl 1,2-cyclohexanedicarboxylate; tetrahydrophthalic acid diglycidyl ester; and combinations thereof.

2. A resin composition, comprising:

an epoxy resin matrix;

a first photoacid generator including an anion having a molecular weight less than 250 g/mol; and

a second photoacid generator including an anion having a molecular weight greater than about 300 g/mol;

wherein i) a cation of the first photoacid generator has, or ii) a cation of the second photoacid generator has, or iii) the cations of the first and second photoacid generators have a mass attenuation coefficient of at least 0.1 L/(g*cm) at a wavelength of incident light to cure the resin composition;

and wherein the first photoacid generator is selected from the group consisting of bis-(4-methylphenyl) iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, diaryliodonium hexafluorophosphate, and diaryliodonium hexafluoroantimonate.

3. The resin composition as defined in claim 2 , wherein the epoxy resin matrix comprises an epoxy material selected from the group consisting of an epoxy functionalized silsesquioxane; trimethylolpropane triglycidyl ether; tetrakis(epoxycyclohexyl ethyl)tetramethyl cyclotetrasiloxane; a copolymer of (epoxycyclohexylethyl)methylsiloxane and dimethylsiloxane; 1,3-bis[2-(3,4-epoxycyclohexyl)ethyl]tetramethyl disiloxane; 1,3-bis(glycidoxypropyl) tetramethyl disiloxane; 3,4-epoxycyclohexylmethyl-3,4-epoxycyclo-hexanecarboxylate; bis((3,4-epoxycyclohexyl)methyl) adipate; 4-vinyl-1-cyclohexene 1,2-epoxide; vinylcyclohexene dioxide; 4,5-epoxytetrahydrophthalic acid diglycidylester; 1,2-epoxy-3-phenoxypropane; glycidyl methacrylate; 1,2-epoxyhexadecane; poly(ethylene glycol) diglycidylether; pentaerythritol glycidyl ether; diglycidyl 1,2-cyclohexanedicarboxylate; tetrahydrophthalic acid diglycidyl ester; and combinations thereof.

4. The resin composition as defined in claim 1 , wherein the second photoacid generator is selected from the group consisting of triphenylsulfonium tetrakis(perfluorophenyl) borate, tetrakis(pentafluorophenyl) gallate, and tris[(trifluoromethyl) sulfonyl]methanide.

5. The resin composition as defined in claim 1 , wherein the cation of the first photoacid generator is, or the cation of the second photoacid generator is, or the cations of the first and second photoacid generators are selected from the group consisting of a diaryliodonium cation having a maximum absorption wavelength (λ max ) of about 350 nm and a triphenylsulfonium cation.

6. The resin composition as defined in claim 1 , wherein:

the cation of the second photoacid generator has the mass attenuation coefficient of at least 0.1 L/(g*cm) at the wavelength of incident light to cure the resin composition; and

the cation of the first photoacid generator has a mass attenuation coefficient less than 0.1 L/(g*cm) at the wavelength of incident light to cure the resin composition.

7. The resin composition as defined in claim 6 , wherein:

the cation of the second photoacid generator is selected from the group consisting of a diaryliodonium cation having a maximum absorption wavelength (λ max ) of about 350 nm and a triphenylsulfonium cation; and

the cation of the first photoacid generator is selected from the group consisting of a bis-(4-methylphenyl) iodonium cation, a (cumene)cyclopentadienyliron (II) cation, a ferrocene cation, a 1-naphthyl diphenyl sulfonium cation, a (4-phenylthiophenyl)diphenylsulfonium, a bis(2,4,6-trimethylphenyl) iodonium cation, a bis(4-tert-butylphenyl) iodonium cation, a N-hydroxy-5-norbornene-2,3-dicarboximide perfluoro-1-butanesulfonate cation, and a triarylsulfonium cation.

8. The resin composition as defined in claim 1 , wherein the cation of the first photoacid generator and the cation of the second photoacid generator have respective mass attenuation coefficients of at least 0.1 L/(g*cm) at the wavelength of incident light to cure the resin composition.

9. The resin composition as defined in claim 1 , wherein:

the first photoacid generator is present in an amount ranging from about 1 mass % to about 5 mass % of total solids in the resin composition; and

the second photoacid generator is present in an amount ranging from about 0.1 mass % to about 2 mass % of total solids in the resin composition.

10. The resin composition as defined in claim 1 , wherein the molecular weight of the anion of the second photoacid generator ranges from greater than about 300 g/mol to about 1,000 g/mol.

11. A resin composition, comprising:

an epoxy resin matrix including an epoxy functionalized polyhedral oligomeric silsesquioxane;

a first photoacid generator including an anion having a molecular weight less than about 250 g/mol; and

a second photoacid generator including an anion having a molecular weight ranging from about 300 g/mol to about 1,000 g/mol;

wherein i) a cation of the first photoacid generator has, or ii) a cation of the second photoacid generator has, or iii) the cations of the first and second photoacid generators have a mass attenuation coefficient of at least 0.1 L/(g*cm) at the wavelength of incident light to cure the resin composition.

12. The resin composition as defined in claim 11 , wherein the epoxy functionalized polyhedral oligomeric silsesquioxane is selected from the group consisting of a glycidyl functionalized polyhedral oligomeric silsesquioxane, an epoxycyclohexyl ethyl functionalized polyhedral oligomeric silsesquioxane, and combinations thereof.

13. The resin composition as defined in claim 11 , wherein the epoxy resin matrix further includes an additional epoxy material selected from the group consisting of trimethylolpropane triglycidyl ether; tetrakis(epoxycyclohexyl ethyl)tetramethyl cyclotetrasiloxane; a copolymer of (epoxycyclohexylethyl)methylsiloxane and dimethylsiloxane; 1,3-bis[2-(3,4-epoxycyclohexyl)ethyl]tetramethyl disiloxane; 1,3-bis(glycidoxypropyl) tetramethyl disiloxane; 3,4-epoxycyclohexylmethyl-3,4-epoxycyclo-hexanecarboxylate; bis((3,4-epoxycyclohexyl)methyl) adipate; 4-vinyl-1-cyclohexene 1,2-epoxide; vinylcyclohexene dioxide; 4,5-epoxytetrahydrophthalic acid diglycidylester; 1,2-epoxy-3-phenoxypropane; glycidyl methacrylate; 1,2-epoxyhexadecane; poly(ethylene glycol) diglycidylether; pentaerythritol glycidyl ether; diglycidyl 1,2-cyclohexanedicarboxylate; tetrahydrophthalic acid diglycidyl ester; and combinations thereof.

14. The resin composition as defined in claim 11 , wherein the first photoacid generator is present in an amount ranging from about 1 mass % to about 5 mass % of total solids in the resin composition.

15. The resin composition as defined in claim 11 , wherein the second photoacid generator is present in an amount ranging from about 0.1 mass % to about 2 mass % of total solids in the resin composition.

16. The resin composition as defined in claim 11 , wherein the first photoacid generator is selected from the group consisting of bis-(4-methylphenyl) iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, diaryliodonium hexafluorophosphate, and diaryliodonium hexafluoroantimonate.

17. The resin composition as defined in claim 11 , wherein the second photoacid generator is selected from the group consisting of triphenylsulfonium tetrakis(perfluorophenyl) borate, tetrakis(pentafluorophenyl) gallate, and tris[(trifluoromethyl) sulfonyl]methanide.

18. The resin composition as defined in claim 11 , wherein the cation of the first photoacid generator is, or the cation of the second photoacid generator is, or both the cations of the first and second photoacid generators are selected from the group consisting of a diaryliodonium cation having a maximum absorption wavelength (λ max ) of about 350 nm and a triphenylsulfonium cation.

19. The resin composition as defined in claim 11 , wherein:

the cation of the second photoacid generator has the mass attenuation coefficient of at least 0.1 L/(g*cm) at the wavelength of incident light to cure the resin composition; and

the cation of the first photoacid generator has a mass attenuation coefficient less than 0.1 L/(g*cm) at the wavelength of incident light to cure the resin composition.

20. The resin composition as defined in claim 19 , wherein:

the cation of the second photoacid generator is selected from the group consisting of a diaryliodonium cation having a maximum absorption wavelength (λ max ) of about 350 nm and a triphenylsulfonium cation; and

the cation of the first photoacid generator is selected from the group consisting of a bis-(4-methylphenyl) iodonium cation, a (cumene)cyclopentadienyliron (II) cation, a ferrocene cation, a 1-naphthyl diphenyl sulfonium cation, a (4-phenylthiophenyl)diphenylsulfonium, a bis(2,4,6-trimethylphenyl) iodonium cation, a bis(4-tert-butylphenyl) iodonium cation, a N-hydroxy-5-norbornene-2,3-dicarboximide perfluoro-1-butanesulfonate cation, and a triarylsulfonium cation.

21. The resin composition as defined in claim 11 , wherein the cation of the first photoacid generator and the cation of the second photoacid generator have respective mass attenuation coefficients of at least 0.1 L/(g*cm) at the wavelength of incident light to cure the resin composition.

22. A flow cell, comprising:

a substrate; and

a cured, patterned resin on the substrate, the cured, patterned resin including depressions separated by interstitial regions, and the cured, patterned resin including a cured form of a resin composition including:

an epoxy resin matrix;

a first photoacid generator including an anion having a molecular weight less than about 250 g/mol; and

a second photoacid generator including an anion having a molecular weight greater than about 300 g/mol;

wherein i) a cation of the first photoacid generator has, or ii) a cation of the second photoacid generator has, or iii) the cations of the first and second photoacid generators have a mass attenuation coefficient of at least 0.1 L/(g*cm) at a wavelength of incident light to cure the resin composition.

23. The flow cell as defined in claim 22 , further comprising:

a hydrogel in the depressions; and

amplification primers attached to the hydrogel.

24. The flow cell as defined in claim 22 , wherein the epoxy resin matrix comprises an epoxy material selected from the group consisting of an epoxy functionalized silsesquioxane; trimethylolpropane triglycidyl ether; tetrakis(epoxycyclohexyl ethyl)tetramethyl cyclotetrasiloxane; a copolymer of (epoxycyclohexylethyl)methylsiloxane and dimethylsiloxane; 1,3-bis[2-(3,4-epoxycyclohexyl)ethyl]tetramethyl disiloxane; 1,3-bis(glycidoxypropyl) tetramethyl disiloxane; 3,4-epoxycyclohexylmethyl-3,4-epoxycyclo-hexanecarboxylate; bis((3,4-epoxycyclohexyl)methyl) adipate; 4-vinyl-1-cyclohexene 1,2-epoxide; vinylcyclohexene dioxide; 4,5-epoxytetrahydrophthalic acid diglycidylester; 1,2-epoxy-3-phenoxypropane; glycidyl methacrylate; 1,2-epoxyhexadecane; poly(ethylene glycol) diglycidylether; pentaerythritol glycidyl ether; diglycidyl 1,2-cyclohexanedicarboxylate; tetrahydrophthalic acid diglycidyl ester; and combinations thereof.

25. The flow cell as defined in claim 22 , wherein:

the first photoacid generator is selected from the group consisting of bis-(4-methylphenyl) iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, diaryliodonium hexafluorophosphate, and diaryliodonium hexafluoroantimonate; and

the second photoacid generator is selected from the group consisting of triphenylsulfonium tetrakis(perfluorophenyl) borate, tetrakis(pentafluorophenyl) gallate, and tris[(trifluoromethyl) sulfonyl]methanide.

26. A method of making a flow cell, comprising:

depositing a resin composition on a substrate, the resin composition including:

an epoxy resin matrix;

a first photoacid generator including an anion having a molecular weight less than about 250 g/mol; and

a second photoacid generator including an anion having a molecular weight greater than about 300 g/mol;

wherein i) a cation of the first photoacid generator has, or ii) a cation of the second photoacid generator has, or iii) the cations of the first and second photoacid generators have a mass attenuation coefficient of at least 0.1 L/(g*cm) at a wavelength of incident light to cure the resin composition;

nanoimprinting the deposited resin composition using a working stamp; and

exposing the nanoimprinted, deposited resin composition to the incident light at an energy dose ranging from about 0.5 J to about 10 J for 30 seconds or less to form a cured, patterned resin.

27. A resin composition, comprising:

an epoxy resin matrix;

a first photoacid generator including a first anion having a first molecular weight; and

a second photoacid generator including a second anion having a second molecular weight that is at least 50 g/mol greater than the first molecular weight;

wherein i) a cation of the first photoacid generator has, or ii) a cation of the second photoacid generator has, or iii) the cations of the first and second photoacid generators have a mass attenuation coefficient of at least 0.1 L/(g*cm) at the wavelength of incident light to cure the resin composition;

and wherein the epoxy resin matrix comprises an epoxy material selected from the group consisting of an epoxy functionalized silsesquioxane; trimethylolpropane triglycidyl ether; tetrakis(epoxycyclohexyl ethyl)tetramethyl cyclotetrasiloxane; a copolymer of (epoxycyclohexylethyl)methylsiloxane and dimethylsiloxane; 1,3-bis[2-(3,4-epoxycyclohexyl) ethyl]tetramethyl disiloxane; 1,3-bis(glycidoxypropyl) tetramethyl disiloxane; 3,4-epoxycyclohexylmethyl-3,4-epoxycyclo-hexanecarboxylate; bis((3,4-epoxycyclohexyl)methyl) adipate; 4-vinyl-1-cyclohexene 1,2-epoxide; vinylcyclohexene dioxide; 4,5-epoxytetrahydrophthalic acid diglycidylester; 1,2-epoxy-3-phenoxypropane; glycidyl methacrylate; 1,2-epoxyhexadecane; poly(ethylene glycol) diglycidylether; pentaerythritol glycidyl ether; diglycidyl 1,2-cyclohexanedicarboxylate; tetrahydrophthalic acid diglycidyl ester; and combinations thereof.

28. The resin composition as defined in claim 3 , wherein the second photoacid generator is selected from the group consisting of triphenylsulfonium tetrakis(perfluorophenyl) borate, tetrakis(pentafluorophenyl) gallate, and tris[(trifluoromethyl) sulfonyl]methanide.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 28, 2022
From: ROKHLENKO, YEKATERINA; MERKEL, TIMOTHY J.
To: ILLUMINA, INC.
Reel/Frame 059418/0405 →
Continuity (2)
Provisional Application 62952821 · Dec 23, 2019
Related Publication 20220404699A1 · Dec 22, 2022
References Cited (19)
US 7378455B2 · Lu et al. · 2008 [cited by applicant]
US 8944580B2 · Ikegame · 2015 [cited by examiner]
US 9061499B2 · Takahashi · 2015 [cited by examiner]
US 9096712B2 · Qiu · 2015 [cited by examiner]
US 11884976B2 · Merkel · 2024 [cited by examiner]
US 20040234898A1 · Batishko et al. · 2004 [cited by applicant]
US 20120040288A1 · Adams · 2012 [cited by examiner]
US 20120107732A1 · Qiu · 2012 [cited by applicant]
US 20120229556A1 · Ikegame · 2012 [cited by examiner]
US 20120288796A1 · Katayama et al. · 2012 [cited by applicant]
US 20120306961A1 · Takahashi et al. · 2012 [cited by applicant]
US 20160136873A1 · Chouiki · 2016 [cited by applicant]
CN 101111530A · 2008 [cited by applicant]
CN 109844638A · 2019 [cited by applicant]
EP 1794655B1 · 2011 [cited by applicant]
EP 2530098A1 · 2012 [cited by applicant]
EP 2717097A1 · 2014 [cited by applicant]
EP 3006484A1 · 2016 [cited by examiner]
Pai, Jeng-Ho, et al., “A Photoresist with Low Fluorescence for Bioanalytical Applications”, Anal Chem. Nov. 15, 2007; 79(22): 8774-8780, Nov. 15, 2007. [cited by applicant]