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US-20260125513-A1 - CURABLE RESIN COMPOSITIONS

US20260125513A1US 20260125513 A1US20260125513 A1US 20260125513A1US-20260125513-A1

Abstract

Some of the resin compositions are ultraviolet light or thermally curable, while others are ultraviolet light curable. One example of the ultraviolet light or thermally curable resin composition consists of a predetermined mass ratio of a (meth)acrylate cyclosiloxane monomer and a non-siloxane (meth)acrylate based monomer ranging from about >0:<100 to about 80:20; from 0 mass % to about 10 mass %, based on a total solids content of the resin composition, of an initiator selected from the group consisting of an azo-initiator, an acetophenone, a phosphine oxide, a brominated aromatic acrylate, and a dithiocarbamate; a surface additive; and a solvent.

Inventors

  • Alexandra Szemjonov
  • Phillippa K. Edge
  • Alexandre Richez

Assignees

  • ILLUMINA, INC.

Dates

Publication Date
20260507
Application Date
20251231

Claims (20)

  1. 1 .- 7 . (canceled)
  2. 8 . An ultraviolet light or thermally curable resin composition, comprising: a predetermined mass ratio of a (meth)acrylate cyclosiloxane monomer and a non-siloxane (meth)acrylate based monomer ranging from about >0:<100 to about 80:20; from greater than 0 mass % to about 5 mass %, based on a total solids content of the resin composition, of an azo-initiator; a surface additive; and a solvent; wherein the resin composition is free of a photosensitizer.
  3. 9 . The ultraviolet light or thermally curable resin composition as defined in claim 8 , wherein: the (meth)acrylate cyclosiloxane monomer is 2,4,6,8-tetramethyl-2,4,6,8-tetrakis[3-acryloyloxypropyl]cyclotetrasiloxane; and the non-siloxane (meth)acrylate based monomer is selected from the group consisting of glycerol dimethacrylate, mixture of isomers; glycerol 1,3-diglycerolate diacrylate; pentaerythritol triacrylate; pentaerythritol tetraacrylate; bisphenol A glycerolate diacrylate; trimethylpropane triacrylate; 3-(acryloyloxy)-2-hydroxypropyl methacrylate; poly(ethylene glycol) dimethacrylate; and ethylene glycol dimethacrylate.
  4. 10 . The ultraviolet light or thermally curable resin composition as defined in claim 8 , wherein the azo-initiator is selected from the group consisting of azobisisobutyronitrile; 2,2′-azobis(2,4-dimethylvaleronitrile); 1,1′-azobis(cyclohexanecarbonitrile); 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile); dimethyl 2,2′-azobis(2-methylpropionate); and 2,2′-Azobis(N-butyl-2-methylpropionamide.
  5. 11 .- 16 . (canceled)
  6. 17 . An ultraviolet light curable resin composition, comprising: a predetermined mass ratio of a first epoxy cyclosiloxane monomer having a 1:1 ratio of Si:O in the cyclosiloxane and a second epoxy cyclosiloxane monomer having a 1:1 ratio of Si:O in the cyclosiloxane, wherein the first and second epoxy cyclosiloxane monomers are different, and wherein the predetermined mass ratio ranges from about 3:7 to about 7:3; bis-(4-methylphenyl)iodonium hexafluorophosphate as a first initiator; a second initiator selected from the group consisting of a free radical initiator and a cationic initiator other than bis-(4-methylphenyl)iodonium hexafluorophosphate; a surface additive; and a solvent.
  7. 18 . The ultraviolet light curable resin composition as defined in claim 17 , wherein: the first epoxy cyclosiloxane monomer is epoxycyclohexyl tetramethylcyclotetrasiloxane; and the second epoxy cyclosiloxane monomer is glycidyl cyclotetrasiloxane.
  8. 19 . The ultraviolet light curable resin composition as defined in claim 17 , wherein: the second initiator is the free radical initiator; and the free radical initiator is selected from the group consisting of 1,1,2,2-tetraphenyl-1,2-ethanediol; ethyl pyruvate; 4-cyano-4-(phenylcarbonothioylthio)pentanoic acid; and ethyl-3-methyl-2-oxobutanoate.
  9. 20 . The ultraviolet light curable resin composition as defined in claim 17 , wherein: the second initiator is the cationic initiator; and the cationic initiator is selected from the group consisting of bis[4-(tert-butyl)phenyl]iodonium tetra(nonafluoro-tert-butoxy)aluminate; and tris(4-((4-acetylphenyl)thio)phenyl)-sulfonium tetrakis(perfluoro-phenyl)borate.
  10. 21 . The ultraviolet light curable resin composition as defined in claim 17 , wherein: the bis-(4-methylphenyl)iodonium hexafluorophosphate is present in an amount ranging from about 3 mass % to about 10 mass %, based on a total solids content of the resin composition; and the second initiator is present in an amount ranging from about 1 mass % to about 26 mass %, based on the total solids content of the resin composition.
  11. 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: a predetermined mass ratio of a (meth)acrylate cyclosiloxane monomer and a non-siloxane (meth)acrylate based monomer ranging from about >0:<100 to about 80:20; from 0 mass % to about 10 mass %, based on a total solids content of the resin composition, of an initiator selected from the group consisting of an azo-initiator, an acetophenone, a phosphine oxide, a brominated aromatic acrylate, and a dithiocarbamate; a surface additive; and a solvent; wherein the cured, patterned resin has low or no autofluorescence when exposed to violet or blue excitation wavelengths ranging from about 375 nm to about 500 nm.
  12. 23 . The flow cell as defined in claim 22 , wherein the substrate is silanized glass or silanized silicon.
  13. 24 . The flow cell as defined in claim 22 , wherein: the (meth)acrylate cyclosiloxane monomer is 2,4,6,8-tetramethyl-2,4,6,8-tetrakis[3-acryloyloxypropyl]cyclotetrasiloxane; and the non-siloxane (meth)acrylate based monomer is selected from the group consisting of glycerol dimethacrylate, mixture of isomers; glycerol 1,3-diglycerolate diacrylate; pentaerythritol triacrylate; pentaerythritol tetraacrylate; bisphenol A glycerolate diacrylate; trimethylpropane triacrylate; 3-(acryloyloxy)-2-hydroxypropyl methacrylate; poly(ethylene glycol) dimethacrylate; and ethylene glycol dimethacrylate.
  14. 25 . The flow cell as defined in claim 22 , wherein: the resin composition includes the initiator; the initiator is the azo-initiator; and the azo-initiator is selected from the group consisting of azobisisobutyronitrile; 2,2′-azobis(2,4-dimethylvaleronitrile); 1,1′-azobis(cyclohexanecarbonitrile); 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile); dimethyl 2,2′-azobis(2-methylpropionate); and 2,2′-Azobis(N-butyl-2-methylpropionamide.
  15. 26 . The flow cell as defined in claim 22 , wherein: the resin composition includes the initiator; the initiator is the acetophenone; and the acetophenone is selected from the group consisting of 2,2-dimethoxy-2-phenylacetophenone and 2-hydroxy-2-methylpriophenone.
  16. 27 . The flow cell as defined in claim 22 , wherein: the resin composition includes the initiator; the initiator is the phosphine oxide; and the phosphine oxide is selected from the group consisting of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and combinations thereof.
  17. 28 . The flow cell as defined in claim 22 , wherein: the resin composition includes the initiator; the initiator is the brominated aromatic acrylate; and the brominated aromatic acrylate is pentabromobenzyl acrylate.
  18. 29 . The flow cell as defined in claim 22 , wherein: the resin composition includes the initiator; the initiator is the dithiocarbamate; and the dithiocarbamate is benzyl diethyldithiocarbamate.
  19. 30 . 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: a predetermined mass ratio of a first epoxy cyclosiloxane monomer having a 1:1 ratio of Si:O in the cyclosiloxane and a second epoxy cyclosiloxane monomer having a 1:1 ratio of Si:O in the cyclosiloxane, wherein the first and second epoxy cyclosiloxane monomers are different, and wherein the predetermined mass ratio ranges from about 3:7 to about 7:3; bis-(4-methylphenyl)iodonium hexafluorophosphate as a first initiator; a second initiator selected from the group consisting of a free radical initiator and a cationic initiator other than bis-(4-methylphenyl)iodonium hexafluorophosphate; a surface additive; and a solvent; wherein the cured, patterned resin has low or no autofluorescence when exposed to violet or blue excitation wavelengths ranging from about 375 nm to about 500 nm.
  20. 31 . The flow cell as defined in claim 30 , wherein: the first epoxy cyclosiloxane monomer is epoxycyclohexyl tetramethylcyclotetrasiloxane; and the second epoxy cyclosiloxane monomer glycidyl cyclotetrasiloxane.

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application is a division of U.S. application Ser. No. 17/934,394, filed Sep. 22, 2022, which itself claims the benefit of U.S. Provisional Application Ser. No. 63/248,179, filed Sep. 24, 2021, the contents of which is incorporated by reference herein in its entirety. REFERENCE TO SEQUENCE LISTING The Sequence Listing submitted herewith is hereby incorporated by reference in its entirety. The name of the file is IL1222B_IP-2196-US_Sequence_Listing_ST26.xml, the size of the file is 10,092 bytes, and the date of creation of the file is Sep. 7, 2022. BACKGROUND Nanoimprinting technology enables the economic and effective production of nanostructures. Nanoimprint lithography employs direct mechanical deformation of material by a stamp having nanostructures. The material is cured while the stamp is in place to lock the shape of the nanostructures in the material. Nanoimprint lithography has been used to manufacture patterned substrates, which may be used in a variety of applications. Some patterned substrates include fluidic channels and discrete depressions. These patterned substrates may be built into flow cells. In some flow cells, active surface chemistry is introduced into the discrete depressions, while interstitial regions surrounding the discrete depressions remain inert. These flow cells may be particularly useful for detection and evaluation of a wide range of molecules (e.g., DNA), families of molecules, genetic expression levels, or single nucleotide polymorphisms. SUMMARY Disclosed herein are several resin compositions, which are suitable for use in nanoimprint lithography. The cured resins generated with examples of the resin composition may exhibit no or low autofluorescence at fluorescent detection wavelengths of interest when exposed to violet or blue excitation wavelengths ranging from about 375 nm to about 500 nm. With no or low autofluorescence, the cured resins do not contribute, or contribute minimally, to background fluorescence. A reduction in the background intensity increases the signal to noise ratio (SNR), which enables signals at the fluorescent detection wavelengths to be readily resolved. Thus, the cured resin compositions, and the resulting cured resins, may be particularly suitable for use in a variety of fluorescent-based bioanalytical applications, such as DNA sequencing, detection of immobilized proteins, cells or enzyme-binding molecules, drug screening, toxicity testing, etc. BRIEF DESCRIPTION OF THE DRAWINGS Features of examples of the present disclosure will become apparent by reference to the following detailed description and drawings, in which like reference numerals correspond to similar, though perhaps not identical, components. For the sake of brevity, reference numerals or features having a previously described function may or may not be described in connection with other drawings in which they appear. FIG. 1A through 1E are schematic perspective views which together depict an example of a method, where FIG. 1A illustrates a substrate, FIG. 1B illustrates nanoimprinting of a resin composition deposited on the substrate of FIG. 1A, FIG. 1C illustrates a cured, patterned resin formed from the nanoimprinting illustrated in FIG. 1B, FIG. 1D illustrates a polymeric hydrogel deposited in depressions of the cured, patterned resin of FIG. 1C, and FIG. 1E illustrates primers grafted to the polymeric hydrogel in the depressions of the cured, patterned resin of FIG. 1D; FIG. 2 is a schematic, cross-sectional view taken along line 2-2 of the flow cell surface of FIG. 1E; FIG. 3 is a graph depicting the autofluorescence data (in violet, blue, and green channels), in terms of FilterArea (integrated fluorescence intensity (AU) using a selected collection band, Y axis) versus excitation wavelength (nm, X axis), for a control example, a cured comparative example resin, and two cured initiator free (meth)acrylate based example resins; FIG. 4 is a graph depicting the autofluorescence data (in violet, blue, and green channels), in terms of FilterArea (integrated fluorescence intensity (AU) using a selected collection band, Y axis) versus excitation wavelength (nm, X axis), for a control example, a cured comparative example resin, and a cured (meth)acrylate based example resin containing an azo-initiator; FIG. 5A and FIG. 5B are graphs depicting the Fourier-transform infrared spectroscopy (FTIR) intensity at 1636 cm−1 (CH2═CH—R stretching) (FIG. 5A) and 1406 cm−1 (C═C—H in-plane deformation) (FIG. 5B) for a control example, a cured initiator free (meth)acrylate based example resin, and a cured (meth)acrylate based example resin containing an azo-initiator; FIG. 6 is a graph depicting the autofluorescence data (in the violet channel), in terms of FilterArea (integrated fluorescence intensity (AU) using a selected collection band, Y axis) at the 405 nm excitation wavelength, for a control example, a cured comparative example resin, and cured (m