# US 10,766,169 B2 · Resin mold > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,766,169 B2 - Document ID: US10766169B2 - Status: Granted - Kind: B2 - Application number: 15/925,342 - Filed: 2018-03-19 - Published: 2018-07-26 - Granted: 2020-09-08 - Earliest claimed: 2010-03-10 - Assignees: Asahi Kasei E-Materials Corporation - Applicants: Asahi Kasei E-Materials Corporation - Inventors: Shinji Matsumoto; Jun Koike - Web page: https://patentgrep.com/patent/US10766169B2 ## CPC - B29C 33/58: Applying the releasing agents - B82Y 10/00: Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic - B82Y 40/00: Manufacture or treatment of nanostructures - G03F 7/0002: {Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping} - B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00) - B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES - G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G) ## Abstract To provide a resin mold which is excellent in adhesion to a substrate, excellent in release properties from a transfer material resin, further excellent in durability of the resin mold itself, and which endures repetition transfer to the transfer material resin, a resin mold of the invention is a resin mold having a fine concavo-convex structure on the surface, and is characterized in that the fluorine element concentration (Es) in a resin mold surface portion is the average fluorine element concentration (Eb) in the resin forming the resin mold or more. ## Claims ### Claim 1 A method of manufacturing a resin mold containing a substrate and a cured material deposited on said substrate and having a fine concavo-convex structure on a surface of the cured material, comprising: coating said substrate or a master mold with a photopolymerizable mixture containing fluorine-non-containing (meth)acrylate, fluorine-containing (meth)acrylate, and a photoinitiator, migrating or diffusing the fluorine-containing (meth) acrylate to the surface of the photopolymerizable mixture coated on said substrate or the master mold by performing pre-baking after coating the substrate with the resin composition; pressing the photopolymerizable mixture between said substrate and the master mold; obtaining the cured material by curing the photopolymerizable mixture by exposure; applying pre-peeling heating treatment to the cured material during the time between curing and peeling; peeling off the cured material with said substrate from the master mold at a certain velocity to obtain the resin mold; and performing post-peeling heat treatment to the resin mold after peeling, wherein the fluorine element concentration (Es) in a resin mold surface portion is more than an average fluorine element concentration (Eb) in the resin mold, wherein said resin mold surface portion means a portion in the range of 2 nm to 20 nm in the thickness direction perpendicular to the surface of the resin mold, and a ratio between Eb and Es satisfies equation (1): 30≤Es/Eb≤160. Eq.(1) ### Claim 2 A method of manufacturing an (n)th generation resin mold, in which n is more than two, containing a substrate and a cured material deposited on said substrate and having a fine concavo-convex structure on a surface of the cured material, comprising: coating said substrate or an (n−1)th generation resin mold with a photopolymerizable mixture containing fluorine-non-containing (meth)acrylate, fluorine-containing (meth)acrylate, and a photoinitiator, migrating or diffusing the fluorine-containing (meth) acrylate to the surface of the photopolymerizable mixture coated on said substrate or the (n−1)th generation resin mold; pressing the photopolymerizable mixture between said substrate and the (n−1)th generation resin mold by performing pre-baking after coating the substrate with the resin composition; obtaining the cured material by curing the photopolymerizable mixture by exposure; applying pre-peeling heating treatment to the cured material during the time between curing and peeling; peeling off the cured material with the (n−1)th generation resin mold from the (n−1)th generation resin at a certain velocity to obtain the resin mold, wherein the fluorine element concentration (Es) in a resin mold surface portion is more than an average fluorine element concentration (Eb) in the resin mold; and performing post-peeling heat treatment to the resin mold after peeling, wherein said resin mold surface portion means a portion in the range of 2 nm to 20 nm in the thickness direction perpendicular to the surface of the (n)th generation resin mold, and a ratio between Eb and Es satisfies equation (1): 30≤Es/Eb≤160. Eq.(1) ### Claim 3 (depends on 1) The method according to claim 1, wherein temperature of the pre-baking ranges from 50° C. to 105° C. and its time ranges from 1 minute to 15 minutes. ### Claim 4 (depends on 3) The method according to claim 3, temperature of the pre-peeling heating treatment ranges from 50° C. to 105° C. and its heating time ranges from 30 seconds to 15 minutes. ### Claim 5 (depends on 4) The method according to claim 4, temperature of the post-peeling heating treatment ranges from 50° C. to 105° C. and its heating time ranges from 30 seconds to 15 minutes. ### Claim 6 (depends on 5) A method of manufacturing another resin mold containing another substrate and another cured material deposited on said another substrate by using the resin mold manufactured by the method according to claim 5, comprising: coating said another substrate or the resin mold with the photopolymerizable mixture; migrating or diffusing the fluorine-containing (meth) acrylate to the surface of the photopolymerizable mixture coated on said another substrate or the resin mold; pressing the photopolymerizable mixture between said another substrate and the resin mold; obtaining said another cured material by curing the photopolymerizable mixture by exposure; and peeling off said another cured material with said another substrate from the resin mold to obtain said another resin mold. ### Claim 7 (depends on 5) A method of manufacturing a transfer material containing another substrate and another cured material deposited on said another substrate by using the resin mold manufactured by the method according to claim 5, comprising: coating said another substrate or the resin mold with the photopolymerizable mixture; migrating or diffusing the fluorine-containing (meth) acrylate to the surface of the photopolymerizable mixture coated on said another substrate or the resin mold; pressing the photopolymerizable mixture between said another substrate and the resin mold; obtaining said another cured material by curing the photopolymerizable mixture by exposure; and peeling off said another cured material with said another substrate from the resin mold to obtain the transfer material. ### Claim 8 (depends on 5, 6, 7) The method according to any one of claims 5-7, wherein the photopolymerizable mixture containing 100 parts by weight of the fluorine-non-containing (meth)acrylate and 0.8 part by weight to 6 parts by weight of the fluorine-containing (meth)acrylate. ### Claim 9 (depends on 5, 6, 7) The method according to any one of claims 5-7, wherein the fluorine-containing (meta)acrylate is expressed by following chemical formula (1); where R1 represents following chemical formula (2), and R2 represents following chemical formula (3), where n is an integer of from 1 to 6, where R is H or CH3. ### Claim 10 (depends on 9) The method according to claim 9, wherein the photopolymerizable mixture containing 100 parts by weight of the fluorine-non-containing (meth)acrylate and 0.8 part by weight to 6 parts by weight of the fluorine-containing (meth)acrylate. ### Claim 11 (depends on 2) The method according to claim 2, wherein temperature of the pre-baking ranges from 50° C. to 105° C. and its time ranges from 1 minute to 15 minutes. ### Claim 12 (depends on 11) The method according to claim 11, temperature of the pre-peeling heating treatment ranges from 50° C. to 105° C. and its time ranges from 30 seconds to 15 minutes. ### Claim 13 (depends on 12) The method according to claim 12, temperature of the post-peeling heating treatment ranges from 50° C. to 105° C. and its heating time ranges from 30 seconds to 15 minutes. ### Claim 14 (depends on 13) A method of manufacturing a transfer material containing another substrate and another cured material deposited on said another substrate by using the (n)th generation resin mold manufactured by the method according to claim 13, comprising: coating said another substrate or the (n)th generation resin with the photopolymerizable mixture; migrating or diffusing the fluorine-containing (meth) acrylate to the surface of the photopolymerizable mixture coated on said another substrate or the (n)th generation resin mold; pressing the photopolymerizable mixture between said another substrate and the resin mold; obtaining said another cured material by curing the photopolymerizable mixture by exposure; and peeling off said another cured material with said another substrate from the (n)th generation resin mold to obtain the transfer material. ### Claim 15 (depends on 13, 14) The method according to claim 13 or 14, wherein the photopolymerizable mixture containing 100 parts by weight of the fluorine-non-containing (meth)acrylate and 0.8 part by weight to 6 parts by weight of the fluorine-containing (meth)acrylate. ### Claim 16 (depends on 13, 14) The method according to claim 13 or 14, wherein the fluorine-containing (meta)acrylate is expressed by following chemical formula (1); where R1 represents following chemical formula (2), and R2 represents following chemical formula (3), where n is an integer of from 1 to 6, where R is H or CH3. ### Claim 17 (depends on 16) The method according to claim 16, wherein the photopolymerizable mixture containing 100 parts by weight of the fluorine-non-containing (meth)acrylate and 0.8 part by weight to 6 parts by weight of the fluorine-containing (meth)acrylate. ### Claim 18 (depends on 1, 2) The method according to claim 1 or 2, wherein the certain velocity is more than 0 m/min. and not greater than 5 m/min.