# US 2019/0169495 A1 · Optically upconverting liquid-filled polymeric materials > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2019/0169495 A1 - Document ID: US20190169495A1 - Status: Published application - Kind: A1 - Application number: 15/780,922 - Filed: 2016-12-02 - Published: 2019-06-06 - Earliest claimed: 2015-12-02 - Assignees: Adolphe Merkle Institute, University of Fribourg - Applicants: Adolphe Merkle Institute, University of Fribourg - Inventors: Roberto VADRUCCI; Yoan C. SIMON; Christoph WEDER - Web page: https://patentgrep.com/patent/US20190169495A1 ## CPC - C09K 11/025: {non-luminescent particle coatings or suspension media} - C08F 220/20: of polyhydric alcohols or phenols {, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate} - C08K 5/0041: {Optical brightening agents, organic pigments} - C08K 5/01: Hydrocarbons {(C08K5/0091 takes precedence)} - C08K 5/053: Polyhydroxylic alcohols - C08K 5/19: Quaternary ammonium compounds - C08K 5/56: Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond - C09K 11/06: containing organic luminescent materials - C08F 220/281: {and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate} - C08F 2800/20: as weight or mass percentages - C08F 2810/20: leading to a crosslinking, either explicitly or inherently - C08L 33/066: {containing -OH groups} - C09K 2211/1007: Non-condensed systems - C09K 2211/1011: Condensed systems - C09K 2211/1022: bridged by heteroatoms, e.g. N, P, Si or B - C09K 2211/1029: containing one nitrogen atom as the heteroatom - C09K 2211/185: of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd - C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) ## Abstract Optically upconverting liquid-filled polymeric materials that are made by curing a curable composition. The materials include a substantially liquid phase that serves to dissolve upconverting chromophores, optionally surfactants and an optionally cross-linked polymer matrix that retains or houses the liquid phase, provides mechanical stability, and offers some protection from oxygen. The optically upconverting liquid-filled polymeric materials have a phase-separated morphology. In preferred embodiments, the domains formed by the two phases are so small that light scattering is largely suppressed, which renders the upconverting liquid-filled polymeric materials largely transparent. The liquid phase provides a high mobility of the dissolved chromophores and the photophysical properties, such as the high upconversion quantum efficiency and the low excitation intensity threshold required to achieve upconversion, are thus more reminiscent of conventional or oxygen-free solutions than polymeric solids. These photophysical properties can be achieved by preparing the polymers under oxygen-free or, in preferred embodiments, under ambient conditions. The design principle introduced here to create upconverting liquid-filled polymeric materials is versatile and general; the liquid phase, the surfactants, the polymer matrix, and the upconverting chromophores can all readily be varied. Importantly, the optically upconverting liquid-filled polymeric materials can be prepared in a one-step process, which makes them preferable over other liquid-containing polymers that enable upconversion. ## Claims ### Claim 1 A light upconverting phase-separated material made by curing a curable composition, comprising: at least one solid phase that comprises, by majority, a polymer; and containing at least one liquid phase, wherein said at least one liquid phase contains at least a dye system that is capable of optical upconversion. ### Claim 2 (depends on 1) The light upconverting phase-separated material according to claim 1, wherein said curing involves a polymerization reaction. ### Claim 3 (depends on 2) The light upconverting phase-separated material according to claim 2, wherein said polymerization reaction is a radical polymerization reaction. ### Claim 4 (depends on 1) The light upconverting phase-separated material according to claim 1, wherein said light-upconverting phase-separated material is substantially transparent, wherein preferably the phase-separated material displays a transmission of at least 50% measured over a path length of 1 cm at any wavelength between 415 and 670 nm. ### Claim 5 (depends on 1) The light upconverting phase-separated material according to claim 1, in which the liquid phase or phases forms or form domains with a dimensions of maximally 100 nm. ### Claim 6 (depends on 1) The light upconverting phase-separated material according to claim 1, wherein said solid phase contains at least one polymer in an amount of at least about 50 wt %, for example 50-99 wt. % based on the total weight of the solid phase. ### Claim 7 (depends on 1) The light upconverting phase-separated material according to claim 1, wherein said at least one liquid phase is present in an amount of up to 70 wt. %, for example 1-70% based on the combined total weight of the material. ### Claim 8 (depends on 1) The light upconverting phase-separated material according to claim 1, wherein said at least one liquid phase includes at least one hydrophobic liquid in an amount of at least about 1 wt. %, for example 1-70% based on the combined total weight of the material, and wherein said at least one hydrophobic liquid has a boiling temperature of more than 100° C., and wherein said at least one hydrophobic liquid has a solidification temperature of less than 100° C. ### Claim 9 (depends on 1) The light upconverting phase-separated material according to claim 1, wherein said light-upconverting phase-separated material contains at least one cationic, nonionic or anionic surfactant preferably in an amount of less than 30 wt. % based on the total weight of the material, wherein an especially preferred embodiment comprises cetyltrimethylammonium bromide as surfactant. ### Claim 10 (depends on 1) The light upconverting phase-separated material according to claim 1, wherein said light-upconverting phase-separated material contains at least one plasticizer. ### Claim 11 (depends on 1) The light upconverting phase-separated material according to claim 1, wherein said at least one solid phase includes a polymer formed by radical polymerization, wherein especially preferred embodiments comprise one or more of acrylates, methacrylates, acrylamides, methacrylamides, acrylic acids, methacrylic acids, and their salts, vinylpyridines, oxazolines. ### Claim 12 (depends on 1) The light upconverting phase-separated material according to claim 1, wherein said at least one liquid phase is not liquid crystalline. ### Claim 13 (depends on 1) The light upconverting phase-separated material according to claim 1, which is characterized by an upconversion quantum efficiency of at least 0.001. ### Claim 14 A method for producing a light upconverting phase-separated material, containing at least one solid phase that comprises, by majority, a polymer, and containing at least one liquid phase, wherein said at least one liquid phase contains at least a dye system that is capable of optical upconversion, comprising the steps of: providing a curable composition and curing said curable composition to form said light upconverting phase-separated material, wherein said curable composition is a liquid containing at least one polymerizable monomer, a non-polymerizable liquid, and at least one dye pair that is capable of optical upconversion, wherein preferably the polymerizable monomer is selected from hydrophilic monomers, and the non-polymerizable liquid is selected from hydrophobic liquids. ### Claim 15 (depends on 14) The method according to claim 14, where said curable composition contains at least one cationic, nonionic or anionic surfactant in an amount of less than 30 wt. % based on the total weight of the curable composition, wherein the surfactant is preferably cetyltrimethylammonium bromide. ### Claim 16 (depends on 15) The method according to claim 15, wherein said curing involves a radical polymerization reaction and preferably a free radical polymerization reaction, wherein said solid phase contains at least one polymer in an amount of about 1 wt. % to about 99 wt. % based on the total weight of the composition and wherein said at least one liquid phase includes at least one hydrophobic liquid in an amount of about 1 wt. % based on the combined total weight of the material, and wherein said at least one hydrophobic liquid has a boiling temperature of more than 100° C., and wherein said at least one hydrophobic liquid has a solidification temperature of less than 100° C. ### Claim 17 A liquid curable composition, comprising: at least one monomer polymerizable by radical polymerization, at least one non-polymerizable liquid, and at least one dye pair that is capable of optical upconversion, and one or more auxiliary components selected from surfactants, plasticizers, stabilizers, wherein said liquid curable composition can be cured into a light upconverting phase-separated material that comprises at least one solid phase and at least one liquid phase. ### Claim 18 (depends on 17) The liquid curable composition according to claim 17, consisting of a) 30-90 wt. % of the monomer or monomers, b) 1-70 wt % of the hydrophobic non-polymerizable liquid, c) 0.0001-20 wt. % of dyes capable of optical upconversion, and d) 0.5-40 wt. % of at least one auxiliary component selected from surfactants, plasticizers and stabilizers. ### Claim 19 (depends on 17) The liquid curable composition according to claim 17, wherein said at least one monomer is hydrophilic and said at least one non-polymerizable liquid is hydrophobic. ### Claim 20 (depends on 3) The light upconverting phase-separated material according to claim 3, wherein said polymerization reaction is a free radical polymerization reaction. ### Claim 21 (depends on 1) The light upconverting phase-separated material according to claim 1, wherein said light-upconverting phase-separated material is substantially transparent, wherein the phase-separated material displays a transmission of at least 70% measured over a path length of 1 cm at any wavelength between 415 and 670 nm; in which the liquid phase or phases forms or form domains with dimensions of maximally 50 nm; wherein said solid phase contains at least one polymer in an amount of at least about 70 wt. % based on the total weight of the solid phase; wherein said at least one liquid phase is present in an amount of up to 40 wt. % based on the combined total weight of the material; wherein said at least one liquid phase includes at least one hydrophobic liquid in an amount of at least about 5 wt. %, based on the combined total weight of the material; wherein said at least one hydrophobic liquid has a boiling temperature of more than 200° C.; wherein said at least one hydrophobic liquid has a solidification temperature of less than 20° C.; wherein said light-upconverting phase-separated material contains at least one cationic, nonionic or anionic surfactant preferably in an amount about 0.5 wt. % to about 20 wt. % based on the total weight of the material and which is characterized by an upconversion quantum efficiency of at least 0.01. ### Claim 22 (depends on 1) The light upconverting phase-separated material according to claim 1, wherein said light-upconverting phase-separated material is substantially transparent, wherein preferably the phase-separated material displays a transmission of at least 85% measured over a path length of 1 cm at any wavelength between 415 and 670 nm; in which the liquid phase or phases forms or form domains with dimensions of maximally 30 nm; wherein said solid phase contains at least one polymer in an amount of at least about 80 wt % based on the total weight of the solid phase; wherein said at least one liquid phase is present in an amount of up to 30 wt % based on the combined total weight of the material; wherein said at least one liquid phase includes at least one hydrophobic liquid in an amount of at least about 10 wt %, based on the combined total weight of the material; wherein said at least one hydrophobic liquid has a boiling temperature of more than 250° C.; wherein said at least one hydrophobic liquid has a solidification temperature of less than 0° C.; wherein said light-upconverting phase-separated material contains at least one cationic, nonionic or anionic surfactant preferably in an amount of from about 2 wt. % to about 15 wt. % based on the total weight of the material and which is characterized by an upconversion quantum efficiency of at least 0.05. ### Claim 23 (depends on 13) The light upconverting phase-separated material according to claim 13, which is characterized by an upconversion quantum efficiency of 0.14 or more. ### Claim 24 (depends on 15) The method according to claim 15, where said curable composition contains at least one cationic, nonionic or anionic surfactant in an amount from about 0.5 wt. % to about 20 wt. % based on the total weight of the curable composition, wherein said curing involves a radical polymerization reaction, wherein said solid phase contains at least one polymer in an amount of about 30 wt. % to about 90 wt. % based on the total weight of the composition and wherein said at least one liquid phase includes at least one hydrophobic liquid in an amount of at least 5 wt. % based on the combined total weight of the material, wherein said at least one hydrophobic liquid has a boiling temperature of more than 200° C., and wherein said at least one hydrophobic liquid has a solidification temperature of less than 20° C. ### Claim 25 (depends on 24) The method according to claim 24, where said curable composition contains at least one cationic, nonionic or anionic surfactant in an amount from about 2 wt. % to about 15 wt. % based on the total weight of the curable composition, and wherein said curing involves a radical polymerization reaction, wherein said solid phase contains at least one polymer in an amount of about 35 wt. % to about 75 wt. % based on the total weight of the composition, wherein said at least one liquid phase includes at least one hydrophobic liquid in an amount of about 10 wt. % based on the combined total weight of the material, wherein said at least one hydrophobic liquid has a boiling temperature of more than 250° C., and wherein said at least one hydrophobic liquid has a solidification temperature of less than 0° C.