# US 12,215,210 B2 · Fluorine resin surface modification method, surface-modified fluorine resin production method, joining method, material having surface-modified fluorine resin, and joined body > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,215,210 B2 - Document ID: US12215210B2 - Status: Granted - Kind: B2 - Application number: 18/006,961 - Filed: 2021-07-20 - Published: 2023-10-26 - Granted: 2025-02-04 - Earliest claimed: 2020-07-27 - Assignees: Ushio Denki Kabushiki Kaisha - Applicants: Ushio Denki Kabushiki Kaisha - Inventors: Akihiro Shimamoto - Web page: https://patentgrep.com/patent/US12215210B2 ## CPC - C08J 7/123: {Treatment by wave energy or particle radiation (C08J7/18 takes precedence)} - B01J 19/12: employing electromagnetic waves - B32B 7/12: using interposed adhesives or interposed materials with bonding properties - B32B 9/045: {of synthetic resin} - B32B 15/082: comprising vinyl resins; comprising acrylic resins - B32B 15/20: comprising aluminium or copper {(B32B15/016 and B32B15/017 take precedence)} - B32B 27/08: of synthetic resin - B32B 27/16: specially treated, e.g. irradiated - B32B 27/304: {comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF} - C08J 5/124: {using adhesives based on a macromolecular component} - C08J 7/056: Forming hydrophilic coatings - C08J 7/12: Chemical modification - H05K 1/034: {containing halogen} - H05K 3/381: {by special treatment of the substrate} - B32B 2250/40: Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA - B32B 2327/18: PTFE, i.e. polytetrafluoroethylene - B32B 2457/08: PCBs, i.e. printed circuit boards - C08J 2327/18: Homopolymers or copolymers of tetrafluoroethylene - C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29) - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS - B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM - H05K: PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS ## Abstract Provided is a fluorine resin surface modification method wherein an object to be processed and a processing device and the like are not readily damaged, wherefrom the risk of harmfully impacting a human body is small, and which can be carried out with simple equipment. The fluorine resin surface modification method including the steps of: irradiating an organic compound containing an oxygen atom with ultraviolet light having at least an intensity in a wavelength range of 205 nm or less to generate a radical; and bringing the radical into contact with a surface of a fluorine resin to form a hydrophilized layer on the surface. ## Claims ### Claim 1 A fluorine resin surface modification method comprising the steps of: irradiating an organic compound containing an oxygen atom with ultraviolet light having at least an intensity in a wavelength range of 205 nm or less, while the organic compound containing the oxygen atom is continuously supplied in gaseous form, to generate a radical; and bringing the radical into contact with a surface of a fluorine resin to form a hydrophilized layer on the surface, wherein the fluorine resin, after the process of forming the hydrophilized layer on the surface, has the surface which has a peak intensity of carbon atoms and a peak intensity of oxygen atoms that are higher than a peak intensity of fluorine atoms in a photoelectron spectrum by XPS survey analysis. ### Claim 2 (depends on 1) The fluorine resin surface modification method according to claim 1, wherein the organic compound contains at least one of a hydroxy group, a carbonyl group, and an ether bond. ### Claim 3 (depends on 2) The fluorine resin surface modification method according to claim 2, wherein the organic compound contains at least one selected from the group consisting of an alcohol, a ketone, an aldehyde, and a phenol. ### Claim 4 (depends on 3) The fluorine resin surface modification method according to claim 3, wherein the organic compound contains at least one selected from the group consisting of an alcohol having 10 or less carbon atoms and a ketone having 10 or less carbon atoms. ### Claim 5 (depends on 4) The fluorine resin surface modification method according to claim 4, wherein the organic compound contains at least one selected from the group consisting of an alcohol having 2 or more and 4 or less carbon atoms and acetone. ### Claim 6 (depends on 1) The fluorine resin surface modification method according to claim 1, wherein the hydrophilized layer is a layer substantially composed of a carbon atom, a hydrogen atom, and an oxygen atom. ### Claim 7 (depends on 6) The fluorine resin surface modification method according to claim 6, wherein the organic compound brought into contact with the surface of the fluorine resin is irradiated with the ultraviolet light. ### Claim 8 (depends on 6) The fluorine resin surface modification method according to claim 6, wherein the generated radical is sprayed onto the surface of the fluorine resin. ### Claim 9 (depends on 6) The fluorine resin surface modification method according to claim 6, wherein the ultraviolet light is generated by a xenon excimer lamp. ### Claim 10 (depends on 6) A surface-modified fluorine resin production method comprising the steps of: preparing a material having a surface having a fluorine resin provided thereon; and modifying the surface of the fluorine resin by the fluorine resin surface modification method according to claim 6. ### Claim 11 (depends on 6) A joining method comprising the step of joining a material containing at least one selected from the group consisting of a metal, a resin, and a ceramic to the hydrophilized layer modified by the fluorine resin surface modification method according to claim 6. ### Claim 12 A material having a surface-modified fluorine resin, the material comprising: a fluorine resin provided on a surface of the material; and a hydrophilized layer provided on at least a part of a surface of the fluorine resin, the hydrophilized layer composed of a functional group composed of a carbon atom, a hydrogen atom, and an oxygen atom, wherein the hydrophilized layer is made by a method comprising: irradiating an organic compound containing an oxygen atom with ultraviolet light having at least an intensity in a wavelength range of 205 nm or less, while the organic compound containing the oxygen atom is continuously supplied in gaseous form, to generate a radical, and bringing the radical into contact with the surface of the fluorine resin to form the hydrophilized layer on the at least the part of the surface of the fluorine resin; and wherein the at least the part of the surface of the fluorine resin including the hydrophilized layer provided thereon has a peak intensity of carbon atoms and a peak intensity of oxygen atoms that are higher than a peak intensity of fluorine atoms in a photoelectron spectrum by XPS survey analysis. ### Claim 13 (depends on 12) A joined body comprising: the material having a surface-modified fluorine resin according to claim 12; and a material containing at least one selected from the group consisting of a metal, a resin, and a ceramic, and joined to the hydrophilized layer directly or with an adhesive layer interposed therebetween. ### Claim 14 (depends on 13) The joined body according to claim 13, wherein the material to be joined to the hydrophilized layer is a metal, and the fluorine resin is a circuit board material.