# US 2017/0285463 A1 · Pattern forming method as well as production methods for processed substrate, optical component, circuit board, electronic component and imprint mold > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2017/0285463 A1 - Document ID: US20170285463A1 - Status: Published application - Kind: A1 - Application number: 15/453,504 - Filed: 2017-03-08 - Published: 2017-10-05 - Earliest claimed: 2016-03-31 - Assignees: Canon Kabushiki Kaisha - Applicants: Canon Kabushiki Kaisha - Inventors: Toshiki Ito; Weijun Liu; Timothy Brian Stachowiak; Niyaz Khusnatdinov; Tomonori Otani; Masayuki Tanabe - Web page: https://patentgrep.com/patent/US20170285463A1 ## CPC - G03F 7/0002: {Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping} - C09D 133/06: of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical - C09D 135/02: Homopolymers or copolymers of esters (C09D135/06, C09D135/08 take precedence) - 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) - C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D) ## Abstract A pattern is formed on a substrate with forming a layer of a curable composition (A1) containing a component (a1) serving as a polymerizable compound (a1) and a component (b1) serving as a photopolymerization initiator on a surface of the substrate, then dispensing droplets of a curable composition (A2) containing a component (a2) serving as a polymerizable compound (a2) and a component (b2) serving as a photopolymerization initiator dropwise discretely onto the layer of the curable composition (A1), subsequently sandwiching a mixture layer of the curable composition (A1) and the curable composition (A2) between a mold and the substrate, then irradiating the mixture layer with light to cure the mixture layer, and releasing the mold from the mixture layer after the curing. ## Claims ### Claim 1 A pattern forming method, comprising in this order: a first laying step (1) of laying a layer formed of a curable composition (A1) containing at least a component (a1) serving as a polymerizable compound on a surface of a substrate; a second laying step (2) of dispensing droplets of a curable composition (A2) containing at least a component (a2) serving as a polymerizable compound and a component (b2) serving as a photopolymerization initiator dropwise discretely onto the layer formed of the curable composition (A1); a mold contacting step (3) of sandwiching a mixture layer obtained by partially mixing the curable composition (A1) and the curable composition (A2) between a mold having a pattern and the substrate; a light irradiating step (4) of irradiating the mixture layer with light from the side of the mold to cure the layer; and a releasing step (5) of releasing the mold from the mixture layer after the curing, wherein, the curable composition (A1) being laid also around a region where the mold and the mixture layer are brought into contact with each other, a content of a component (b1) serving as the photopolymerization initiator of the curable composition (A1) being 0 parts by weight or more and less than 0.1 part by weight with respect to 100 parts by weight of the component (a1) serving as the polymerizable compound, a polymerization conversion degree of the component (a1) serving as the polymerizable compound at a time of exposure under conditions of an illuminance of 1.00 mW/cm2 and an exposure time of 100.0 seconds being 50% or less. ### Claim 2 (depends on 1) A pattern forming method according to claim 1, wherein the curable composition (A1) contains at least a component (c1) serving as a sensitizer or a component (d1) serving as a non-polymerizable compound serving as a hydrogen donor. ### Claim 3 (depends on 2) A pattern forming method according to claim 2, wherein a polymerization conversion degree of a composition of components of the curable composition (A1) except a component (e1) serving as a solvent is 3% or less at a time of exposure under conditions of an illuminance of 1.00 mW/cm2 and an exposure time of 3.2 seconds. ### Claim 4 (depends on 1) A pattern forming method according to claim 1, wherein a value obtained by subtracting the polymerization conversion ration of a curable composition (A1′) from a polymerization conversion ration of a curable composition (A1″) is positive, wherein the each polymerization conversion ration of the curable composition (A1′) and the curable composition (A1″) is evaluated at a time of exposure under conditions of an illuminance of 1.00 mW/cm2 and an exposure time of 3.2 seconds, in which the curable composition (A1′) is prepared by addition of 0.5 parts by weight of a component (b2) serving as a photopolymerization initiator with respect to 100 parts by weight of the component (a1) serving as the polymerizable compound to a curable composition which a component (e1) serving as the solvent is not included in the curable composition (A1) including a component (c1) serving as the sensitizer, and the curable composition (A1″) is prepared by addition of 0.5 parts by weight of a component (b2) serving as a photopolymerization initiator with respect to 100 parts by weight of the component (a1) serving as the polymerizable compound to a curable composition which the component (c1) serving as the sensitizer and the component (e1) serving as the solvent are not included in the curable composition (A1). ### Claim 5 (depends on 2) A pattern forming method according to claim 2, wherein a blending ratio of the component (c1) serving as a sensitizer in the curable composition (A1) is 0.01 wt % or more and 3 wt % or less with respect to the total weight of a composition of components of the curable composition (A1) except a component (e1) serving as a solvent ### Claim 6 A pattern forming method, comprising in this order: a first laying step (1) of laying a layer formed of a curable composition (A1) containing at least a component (a1) serving as a polymerizable compound and a component (b1) serving as a photopolymerization initiator on a surface of a substrate; a second laying step (2) of dispensing droplets of a curable composition (A2) containing at least a component (a2) serving as a polymerizable compound and a component (b2) serving as a photopolymerization initiator dropwise discretely onto the layer formed of the curable composition (A1); a mold contacting step (3) of sandwiching a mixture layer obtained by partially mixing the curable composition (A1) and the curable composition (A2) between a mold and the substrate; a light irradiating step (4) of irradiating the mixture layer with light from the side of the mold to cure the layer; and a releasing step (5) of releasing the mold from the mixture layer after the curing, wherein, the curable composition (A1) being laid also around a region where the mold and the mixture layer are brought into contact with each other, a content of the component (b1) serving as the photopolymerization initiator of the curable composition (A1) being 0 parts by weight or more and less than 0.1 part by weight with respect to 100 parts by weight of the component (a1) serving as the polymerizable compound, the light irradiated in the light irradiating step (4) does not include a light having a wavelength of 350 nm or less. ### Claim 7 (depends on 6) A pattern forming method according to claim 6, wherein the light is a single-wavelength light having a wavelength of 365 nm or 375 nm. ### Claim 8 (depends on 6) A pattern forming method according to claim 6, wherein a exposure dose required for a polymerization conversion degree of the component (a1) in a composition to be 3% is 14,000 mJ/cm2 or more. ### Claim 9 (depends on 6) A pattern forming method according to claim 6, wherein the component (a1) serving as polymerizable compound is at least one of a monofunctional (meth)acrylic monomer and a polyfunctional (meth)acrylic monomer ### Claim 10 (depends on 1) A pattern forming method according to claim 1, wherein a surface tension of a composition of components of the curable composition (A1) except a component (e1) serving as a solvent is higher than a surface tension of a composition of components of the curable composition (A2) except a component (e2) serving as a solvent. ### Claim 11 (depends on 1) A pattern forming method according to claim 1, wherein a viscosity of a composition of components of the curable composition (A1) except a component (e1) serving as a solvent is 1 mPa·s or more and 1,000 mPa·s or less, and a viscosity of a composition of components of the curable composition (A2) except a component (e2) serving as a solvent is 1 mPa·s or more and 12 mPa·s or less. ### Claim 12 (depends on 1) A pattern forming method according to claim 1, wherein a material for a surface of the mold comprises quartz. ### Claim 13 (depends on 1) A pattern forming method according to claim 1, wherein the mold contacting step is performed under an atmosphere containing a condensable gas. ### Claim 14 (depends on 1) A method of producing a processed substrate, comprising the pattern forming method of claim 1. ### Claim 15 (depends on 1) A method of producing an optical component, comprising the pattern forming method of claim 1. ### Claim 16 (depends on 1) A method of producing a quartz mold replica, comprising the pattern forming method of claim 1. ### Claim 17 (depends on 1) A pattern forming method according to claim 1, wherein the pattern comprises a nanosize groove/land pattern based on a photocured product of the curable compositions (A1) and (A2). ### Claim 18 An imprint pretreatment coating material which forms a liquid film as pretreatment coating on a substrate and promotes spreading of components of liquid droplets in the plane of the substrate when the liquid droplets are dispensed onto the liquid film, wherein the imprint pretreatment coating material contains at least a component (a1) serving as a polymerizable compound and a component (b1) serving as the photopolymerization initiator, the blending ratio of the component (b1) serving as a photopolymerization is 0 weight part or more and less than 0.1 weight parts with respect to 100 weight parts of the component (a1) serving as a polymerizable compound, and the polymerization conversion degree of the component (a1) serving as the polymerizable compound is 50% or less at a time of exposure under the condition having illuminance of 1.00 mW/cm2 and exposure time of 100.0 seconds. ### Claim 19 (depends on 18) A set containing the imprint pretreatment coating material of claim 18 and an imprint resist to be dispensed on the substrate coated with the imprint pretreatment coating material. ### Claim 20 (depends on 19) A set according to claim 19, wherein a surface tension of a composition of components of the imprint pretreatment coating material except a solvent is higher than a surface tension of a composition of components of the imprint resist except a solvent. ### Claim 21 (depends on 19) An imprint resist to be used for the set of claim 19. ### Claim 22 (depends on 18) A pretreatment method for performing imprint processing of a substrate with arranging a curable composition on the substrate, comprising coating a substrate with the imprint pretreatment coating material of claim 18. ### Claim 23 (depends on 18) A pattern forming method for forming a pattern on a substrate, comprising dispensing a resist dropwise discretely on a substrate coated with the imprint pretreatment coating material of claim 18. ### Claim 24 (depends on 3) A pattern forming method according to claim 3, wherein the curable composition (A1) contains at least one of the components (c1) serving as the sensitizer selected from a group consisting of benzophenone derivatives, thioxanthone derivatives, and coumarin derivatives. ### Claim 25 (depends on 3) A pattern forming method according to claim 3, wherein the curable composition (A1) contains at least one of the components (c1) serving as the sensitizer selected from a group consisting of 7-diethylamino-4-methylcoumarin, 4,4′-bis(diethylamino)benzophenone, and 2-isopropylthioxanthone. ### Claim 26 (depends on 18) An imprint pretreatment coating material according to claim 18, wherein the imprint resist contains at least one of sensitizers selected from a group consisting of benzophenone derivatives, thioxanthone derivatives, and coumarin derivatives. ### Claim 27 (depends on 18) An imprint pretreatment coating material according to claim 18, wherein the imprint resist contains at least one of sensitizers selected from a group consisting of 7-diethylamino-4-methylcoumarin, 4,4′-bis(diethylamino)benzophenone, and 2-isopropylthioxanthone.