WO2016039327A1 - 凹パターンを有する構造体の製造方法、樹脂組成物、導電膜の形成方法、電子回路及び電子デバイス - Google Patents
凹パターンを有する構造体の製造方法、樹脂組成物、導電膜の形成方法、電子回路及び電子デバイス Download PDFInfo
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- WO2016039327A1 WO2016039327A1 PCT/JP2015/075441 JP2015075441W WO2016039327A1 WO 2016039327 A1 WO2016039327 A1 WO 2016039327A1 JP 2015075441 W JP2015075441 W JP 2015075441W WO 2016039327 A1 WO2016039327 A1 WO 2016039327A1
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- 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
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/16—Surface shaping of articles, e.g. embossing; Apparatus therefor by wave energy or particle radiation, e.g. infrared heating
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
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- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/10—Homopolymers or copolymers of unsaturated ethers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
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- G—PHYSICS
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- 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
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0011—Working of insulating substrates or insulating layers
- H05K3/0017—Etching of the substrate by chemical or physical means
- H05K3/0023—Etching of the substrate by chemical or physical means by exposure and development of a photosensitive insulating layer
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
- C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0166—Polymeric layer used for special processing, e.g. resist for etching insulating material or photoresist used as a mask during plasma etching
Definitions
- the present invention relates to a method for producing a structure having a concave pattern, a resin composition, a method for forming a conductive film, an electronic circuit, and an electronic device.
- Electronic devices such as liquid crystal displays, mobile phones, tablets, and other mobile information devices, digital cameras, organic EL displays, organic EL lighting, and sensors are required to have higher performance in addition to being smaller and thinner. .
- printed electronics that directly prints wiring has attracted attention.
- it is possible to skip a multi-step process including exposure and development and a vacuum process such as a vapor deposition method, and a great simplification of the process is expected.
- Printing methods such as inkjet, screen printing, gravure printing, and gravure offset printing can be used as a simple and low-cost process because a desired pattern of wiring can be formed directly on a substrate.
- the wiring forming material to be used flows, and as a result, these wet spread and bleeding occur, and there is a limit in forming a fine pattern with excellent linearity.
- Patent Document 1 a technique for patterning a wiring forming material by printing and forming a metal wiring by thermal firing or light firing has been actively studied (see, for example, Patent Document 1). In addition to the problem of bleeding, there was a problem in the adhesion of the resulting wiring to the substrate.
- the base treatment for providing the base layer is performed for the purpose of improving the printability by suppressing the wetting and spreading of the wiring forming material applied on the substrate.
- Examples of such a surface treatment method include a method of grafting an epoxy group on a substrate (see, for example, Patent Document 2 and Patent Document 3), and a method of applying a photocatalyst on a substrate (for example, Patent Document 4). And Patent Document 5), and a method of applying an acrylic copolymer on a substrate is known (see, for example, Patent Document 6 and Patent Document 7).
- the conventional base treatment in which the base layer is provided it is difficult to suppress the spread and spread of the wiring forming material and to form a high-definition wiring.
- the characteristics of the surface of the base layer on which the wiring forming material is applied are uniform.
- the wiring forming material is printed in a predetermined pattern, it has not been possible to sufficiently suppress the material from spreading out immediately after printing.
- the underlayer is formed on a structure having a non-flat surface, the wiring forming material tends to spread and spread easily.
- a portion where a wiring is to be formed is a concave portion in advance, and that a desired wiring can be formed by applying a wiring forming material thereto.
- the present invention has been made in view of the above problems, and an object thereof is to provide a method for easily forming a desired concave pattern on a structure having a non-flat surface.
- a configuration example of the present invention is as follows.
- a structure comprising the following steps (i) and (ii) and having a concave pattern with a thickness of 5% or more and less than 90% thinner than the thickness of the coating film obtained in the following step (i): Production method.
- (I) A step of forming a coating film on a non-flat surface of the structure using a resin composition containing a polymer having an acid-dissociable group and an acid generator.
- (Ii) A predetermined portion of the coating film The step of forming a recess by performing radiation irradiation
- R 1 and R 2 each independently represents a hydrogen atom or a methyl group, and Rf independently represents an organic group having a fluorine atom. Indicates a binding site.
- R 3 independently represents a hydrogen atom or a methyl group.
- R 4 independently represents a methylene group, an alkylene group having 2 to 12 carbon atoms, or 2 to 12 carbon atoms. A group in which a part of the alkenylene group, the alkylene group or the alkenylene group is substituted with —O—, — (C ⁇ O) O— or —O (C ⁇ O) —, a substitution of 6 to 13 carbon atoms, or An unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted alicyclic hydrocarbon group having 4 to 12 carbon atoms, or a group in which one or more hydrogen atoms of these groups are substituted with a fluorine atom.
- R 5 independently represents a group in which one or more hydrogen atoms of a hydrocarbon group are substituted with a fluorine atom, m represents 0 or 1, and n represents an integer of 0 to 12 independently.
- a resin composition comprising a polymer having an acid dissociable group containing a fluorine atom, and an acid generator.
- a resin composition comprising a polymer having an acid dissociable group containing at least one bond selected from the group consisting of an acetal bond and a hemiacetal ester bond, and an acid generator.
- a method for forming a conductive film comprising a step of forming a conductive film on the concave pattern formed by the manufacturing method according to any one of [1] to [9] using a composition for forming a conductive film .
- a conductive film that prevents spread and bleeding, has high definition, and has excellent adhesion to a structure having a non-flat surface can be easily formed.
- FIG. 1A is a schematic diagram of the three-dimensional structure a used in the example
- FIG. 1B is a schematic diagram of the three-dimensional structure b used in the example
- FIG. FIG. 3 is a schematic view of a three-dimensional structure c used in the examples.
- 2A is a schematic diagram of a three-dimensional structure a having a concave pattern or silver wiring obtained in the example
- FIG. 2B is a concave pattern or silver wiring obtained in the example
- FIG. 2C is a schematic view of a three-dimensional structure c having a concave pattern or a silver wiring obtained in the example.
- the method for producing a structure having a concave pattern according to the present invention includes the following steps (i) and (ii), wherein the concave pattern is 5 with respect to the film thickness of the coating film obtained in the following step (i). % Or less and less than 90%.
- (I) A step of forming a coating film on a non-flat surface of the structure using a resin composition containing a polymer having an acid-dissociable group and an acid generator.
- a predetermined portion of the coating film The step of forming a recess by performing radiation irradiation
- a desired concave pattern can be easily formed on a structure having a non-flat surface, and further, a composition for forming a conductive film can be formed by using the structure having this concave pattern. It is possible to easily form a conductive film that prevents wetting and spreading of an object, has high definition, and has excellent adhesion to a structure having a non-flat surface.
- the manufacturing method of the present invention is capable of producing a structure having a desired concave pattern easily, inexpensively, while greatly simplifying the process and reducing the process load. It is preferably not included.
- the concave pattern is formed through radiation irradiation, the development process is not performed, and there is not much variation by irradiating the radiation intensively to a place where it is difficult to hit the radiation or excessively radiating the radiation.
- a uniform concave pattern can be formed.
- the lower limit of the concave pattern formed by the production method of the present invention is such that the film thickness of the concave pattern is the film thickness of the coating film obtained in the step (i) (the film thickness of the unirradiated portion).
- the upper limit is preferably 85% or less, more preferably 80% or less, and even more preferably 12 to 70%, preferably 10% or more thin, more preferably 11% or more thin.
- a conductive film (conductive film (pattern) having a film width of 50 ⁇ m or less) can be obtained.
- the film thickness of the non-irradiated part and the concave pattern can be measured by the method described in the following examples.
- the difference in contact angle with respect to tetradecane between the concave pattern part (surface) and the non-irradiated part (surface) is preferably 30 ° or more, More preferably, it is 40 ° or more, and further preferably 50 ° or more.
- contact angle difference is in the above range, when a conductive film or the like is formed on the structure having a concave pattern, a liquid conductive film forming composition is applied to the surface of the radiation non-irradiated part.
- the composition when the composition is repelled in the radiation non-irradiated part that is the liquid repellent part and the composition easily moves to the concave pattern part that is the lyophilic part, the formation of the conductive film along the concave pattern is achieved. It becomes possible. Specifically, the contact angle difference can be measured by the method described in the Examples below.
- a radiation non-irradiation part surface and a concave pattern part surface mean the surface on the opposite side to the side which touches a structure of the coating film formed on the structure.
- the reason why tetradecane was used when measuring the contact angle is that tetradecane is generally used in the composition for forming a conductive film and is not easily evaporated, and is suitable for measuring the contact angle. .
- the thickness of the obtained concave pattern portion is 5% or more and less than 90% thinner than the thickness of the non-irradiated portion, and the contact angle difference with respect to tetradecane between the concave pattern portion surface and the non-radiated portion surface is 30 ° or more. If this condition is satisfied, a large amount of the composition for forming a conductive film can be easily provided only on the concave pattern for the same reason as described above.
- the structure having a concave pattern obtained by the manufacturing method of the present invention is different from the structure having a semiconductor resist.
- the semiconductor resist a portion where the film is completely removed by development coexists with a portion where the film remains even during development to form a pattern.
- the film once formed is completely removed. Since there is no portion, it is different from a structure having a semiconductor resist.
- the use of the structure obtained by the production method of the present invention is not particularly limited.
- the structure is particularly preferably used for a structure having a conductive film, particularly a wiring, and further a structure having a conductive film (wiring) having a high-definition pattern, a structure used in a bioprocess, and the like. Is done.
- Step (i) is a step of forming a coating film on the non-planar surface of the structure using a resin composition containing a polymer having an acid-dissociable group and an acid generator, and preferably the resin composition is structured. It is a step of forming a coating film by providing the composition on a non-flat surface and then heating (pre-baking) the composition. In step (i), by using the resin composition, a recess can be formed on the structure without performing a development step in the following step (ii) or the like.
- the resin composition will be specifically described below.
- the structure having the non-flat surface is not particularly limited.
- the structure is a structure in which a conductive film or the like is to be formed and has a non-flat surface.
- the structure has a curved surface and an uneven surface.
- Examples include structures having at least one surface selected from the group. Examples of such a structure include a tile-shaped structure, a structure having a convex part and / or a concave part, a cylindrical structure, and a spherical structure.
- the surface to be applied is a non-planar surface.
- the structure has a non-flat surface in step (i).
- Structures including non-flat surfaces include electrical and electronic equipment, information terminal equipment, home appliances, OA equipment, and parts of these equipment; housing parts, parts or members of mechanical parts, vehicle parts, building members, and lighting equipment Is mentioned.
- Electrical and electronic devices, information terminal devices, home appliances, OA devices, and parts of these devices include, for example, display devices such as personal computers, game machines, watches, liquid crystal televisions, organic EL televisions, and electronic papers; printers; Scanner; Fax; Electronic notebook; PDA (Personal Digital Assistant), mobile phone, tablet terminal and other portable terminals; Electronic desk calculator; Electronic dictionary; Digital camera, video camera and its lens; Battery pack; And a reading device; a mouse; a numeric keypad; a portable music player; and the like.
- Machine parts and vehicle parts include instrument panel, console box, glove box, meter panel, door ornament, switch panel, center cluster panel, dashboard, door trim, roof trim, rear side trim, trunk room trim, handle, etc .;
- building materials various building materials (eg, building materials for smart houses such as inner walls of houses);
- lighting devices LED lighting, organic EL lighting, and the like can be given.
- examples of the structure including a non-flat surface include various sensors, wearable devices, and toys. According to the present invention, it is possible to easily form a concave pattern in these three-dimensional structures, and further, by forming a conductive film on the concave pattern, the space-saving size, slimming, and weight reduction are achieved. A structure with a conductive film can be obtained, and the resulting structure with a conductive film is expected to have high functionality.
- the material of the structure may be appropriately selected depending on the desired application and is not particularly limited.
- glass such as alkali-free glass; polyester (eg, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate), Fluorene ring-modified polyester, polyolefin (eg, polyethylene, polypropylene), alicyclic polyolefin, polystyrene, triacetyl cellulose, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, polyarylate, polyethersulfone, polysulfone, poly Ether ether ketone, polycarbonate, fluorene ring modified polycarbonate, alicyclic modified polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyurethane, poly (meta Acryloyl compounds, ring-opening polymers of cyclic olefins (ROMP polymers) and hydrogenated products thereof, acryl
- the surface of the structure may be pretreated as necessary, such as cleaning, roughening, or providing a minute uneven surface.
- the surface of a structure that is a cube or a rectangular parallelepiped
- the surface is roughened, or the surface on which minute irregularities are formed is referred to as the “non-flat surface”. It is not determined whether the surface is a non-flat surface by macroscopically viewing the surface.
- the method for providing the resin composition is not particularly limited. Wiping, dipping, spraying, spin coating (spin coating), slit die coating, bar coating using a brush, brush, cloth or the like. Appropriate methods such as ink jet printing, dispensing method, various curved surface printing methods and the like can be adopted. Among these, a spray method, a dipping method, or a wipe method is particularly preferable.
- the thickness of the coating film formed in step (i) may be appropriately adjusted according to the desired use, but is preferably 0.1 to 20 ⁇ m, more preferably 0.2 to 10 ⁇ m.
- the pre-baking conditions vary depending on the composition of the resin composition used, but are preferably 60 to 120 ° C. for about 1 to 10 minutes.
- Step (ii) is a step of forming recesses by irradiating a predetermined portion of the coating film formed in step (i) with radiation.
- a part of the coating film on the structure is irradiated with radiation to form a coating film having a radiation irradiated part and a radiation non-irradiated part.
- the acid dissociable group is eliminated and volatilized by the effect of the acid generator in step (ii).
- the film thickness of the radiation irradiated part becomes thinner than the film thickness of the non-radiated part, and a recess is formed.
- the film thickness of a radiation non-irradiation part does not change fundamentally from the time of coating film formation.
- the coating film obtained in step (i) and the radiation-unirradiated part exhibit liquid repellency, but the radiation-irradiated part (concave part) is an acid-dissociable group. With the disappearance of, it becomes more lyophilic than the non-irradiated part.
- the liquid repellent property is formed on the structure by the step (ii).
- a coating film having a radiation non-irradiated portion (convex portion) and a radiation irradiated portion that is a lyophilic concave portion (concave pattern) is formed from the portion.
- a conductive film forming composition such as a conductive film forming ink is provided on such a coating film by dropping, dipping, spray coating, or various printing, the composition is formed on the recesses by the unevenness of the coating film surface.
- the group which has a fluorine atom will detach
- this leaving group is relatively easy to volatilize, in step (ii), it is possible to more easily form a coating film having a large film thickness difference between the unirradiated portion and the concave portion.
- a predetermined pattern is formed through a photomask or mask seal having a predetermined pattern or using a direct drawing exposure apparatus so that a concave part having the same shape as the concave pattern to be formed is formed.
- the pattern is preferably drawn and exposed.
- wire width etc. can be formed.
- visible rays, ultraviolet rays, far ultraviolet rays, charged particle beams, X-rays and the like can be used as radiation used for exposure.
- radiation having a wavelength in the range of 190 nm to 450 nm is preferable, and radiation including ultraviolet light having a wavelength of 365 nm is particularly preferable.
- the exposure amount in the step (ii) is preferably such that the radiation is exposed so that the film thickness of the formed concave pattern (concave portion) with respect to the unirradiated portion falls within the above range.
- the radiation wavelength is 365 nm. as a value measured by the intensity of the luminometer (OAI model356, OAI Optical Associates Ltd. Inc.) at, preferably 10mJ / cm 2 ⁇ 1000mJ / cm 2, more preferably at 20mJ / cm 2 ⁇ 700mJ / cm 2.
- the recess formed in the step (ii) may be a recess pattern formed on the structure, but the recess of the recess is further deepened (the film thickness of the recess is further reduced).
- the production method of the present invention preferably includes a step (iii) of heating the coating film after the radiation irradiation obtained in the step (ii). When this step (iii) is performed, a structure having a concave pattern is manufactured by this step.
- the component generated in the radiation irradiation part of the step (ii) in which the acid dissociable group is eliminated due to the effect of the acid generator is further volatilized by the step (iii). be able to.
- the dents in the recesses are further deepened (the film thickness of the recesses is further reduced), and a coating film having a thickness that is 5% or more and less than 90% thinner than the film thickness of the protrusions is easily formed. can do.
- disconnected by irradiation as a resin composition used in process (i)
- the chemical bond of the compound in a coating film by the irradiation of the said process (ii) is carried out.
- the cleaved compound can be efficiently removed by the step (iii), and a concave pattern is formed.
- the compound capable of cleaving a chemical bond by irradiation with radiation include irradiation with radiation having a wavelength of 150 to 450 nm, preferably radiation having a short wavelength of 150 to 365 nm, of 10 to 1000 mJ / cm 2.
- disconnected by is mentioned.
- the resin composition used in the step (i) is a composition containing a component that undergoes photo-crosslinking by irradiation with radiation and further causes shrinkage due to the cross-linking
- the resin composition is obtained in the step (ii).
- the concave portion obtained in step (ii) can be further deepened, and a desired concave pattern can be formed.
- liquid repellent radiation is not irradiated on the substrate in step (iii).
- a coating film having a portion (convex portion) and a lyophilic concave pattern from the portion is formed.
- a conductive film forming composition such as a conductive film forming ink is provided on such a coating film by dropping, dipping, spray coating, or various printing, the film thickness difference between the convex part and the concave pattern is large.
- the composition tends to gather on the concave pattern due to unevenness on the surface of the coating film, but not only the effect of the surface shape of the coating film but also the lyophilic / liquid repellency of the surface makes the composition on the concave pattern It becomes easy to gather (assist patterning of the composition for forming a conductive film), and it becomes easy to form a more desired shape, specifically, a fine and elaborate conductive film on the structure.
- the group which has a fluorine atom will detach
- a method of heating the coating film in the step (iii) for example, a method of heating the structure with a coating film obtained in the step (ii) using a hot plate, a batch type oven or a conveyor type oven, a dryer or the like A method of drying with hot air using a method and a method of vacuum baking are used.
- the heating conditions vary depending on the composition of the resin composition used in step (i), the thickness of the coating film obtained in step (ii), etc., but the radiation of the concave pattern formed in step (iii) has not been confirmed. Heating is preferably performed so that the film thickness with respect to the irradiated portion falls within the above range, and preferably 60 to 150 ° C. for about 3 to 60 minutes.
- the film thickness of the concave pattern obtained in the step (iii) may be adjusted as appropriate according to the desired application, but the film thickness should be within the above range with respect to the film thickness of the radiation non-irradiated part. Is preferably 0.01 to 18 ⁇ m, more preferably 0.05 to 15 ⁇ m.
- the method for forming a conductive film of the present invention includes a step of forming a conductive film using a conductive film forming composition on a concave pattern formed by the method for producing a structure having a concave pattern. To do.
- a high-definition conductive film (wiring) can be easily formed on a structure having a non-flat surface, and cannot be easily formed by a conventional method.
- a conductive film (wiring) having a width of 10 ⁇ m or less, for example, about 1 ⁇ m can be easily formed on a structure having a non-flat surface.
- the method for forming a conductive film of the present invention includes a display device such as a personal computer, a game machine, a clock, a liquid crystal television, an organic EL television, an electronic paper, a printer, a copier, a scanner, a fax machine, an electronic notebook;
- a display device such as a personal computer, a game machine, a clock, a liquid crystal television, an organic EL television, an electronic paper, a printer, a copier, a scanner, a fax machine, an electronic notebook
- Various portable terminals such as mobile phones and tablet terminals; electronic desk calculators, electronic dictionaries; digital cameras, video cameras and their lenses; battery packs, recording media drives and reading devices, mice, numeric keys, portable music players; instruments
- Vehicle parts such as panels, console boxes, glove boxes, meter panels, door ornaments, switch panels, center cluster panels, dashboards, door trims, roof trims, rear side trims, trunk room trims, and handles; various building materials (eg, interior walls of houses
- Tohausu building materials can be suitably applied as a method for forming the conductive film on the LED lighting and organic EL illumination, and the like. Moreover, it can apply suitably as a method at the time of forming an electrically conductive film in various sensors, wearable devices, toys, etc.
- the method for forming the conductive film preferably includes a step (iv) of providing a composition for forming a conductive film on the concave pattern and then heating the composition and / or irradiating with radiation.
- the composition for forming a conductive film will be specifically described below.
- the method for providing the composition for forming a conductive film is not particularly limited.
- a coating method using a brush or a brush a dropping method, a dipping method, a spray method, a spin coating method (spin coating method), a slit die.
- Appropriate methods such as a coating method, a bar coating method, a squeegee method, inkjet printing, a dispensing method, and various curved surface printing methods can be employed.
- the dropping method, dipping method, and spraying method are particularly preferable.
- the liquid-repellent non-irradiated part and the parent In the case of using a composition containing a compound containing an acid-dissociable group having a fluorine atom as the resin composition used in the step (i), in the production method, the liquid-repellent non-irradiated part and the parent
- the composition is repelled in the radiation non-irradiated part, and a concave pattern is formed. Since it tends to gather in the part, it tends to be in a state where the composition is provided along the concave pattern.
- the temperature of the heating in the said process (iv) 190 degrees C or less is preferable.
- the temperature is preferably equal to or lower than the heat resistant temperature of the structure, specifically 150 ° C. or lower.
- the heating time is not particularly limited, but is preferably 1 to 120 minutes, more preferably 3 to 60 minutes.
- Examples of the heating method include a method of heating using a hot plate, a batch type oven or a conveyor type oven, a method of drying with hot air using a dryer or the like, and a method of vacuum baking.
- the step is not particularly limited on the condition of irradiating radiation in the (iv), using a flash lamp, irradiation amount is preferably 500 ⁇ 6000mJ / cm 2, more preferably 1000 ⁇ 5000mJ / cm 2.
- the said process after passing through the process of forming an electrically conductive film as needed, Preferably after passing through a process (iv), the said process (by the radiation irradiation or heating from the obtained structure with an electrically conductive film) You may perform the process (v) of removing the radiation non-irradiation part of i).
- step (v) (a) the step of heating at a temperature exceeding the heating temperature in step (iv), or (b) the convex portion of the structure with conductive film obtained in step (iv) (said step (i) It is preferable that the radiation-irradiated part) is irradiated with radiation under the same conditions as in the step (ii) and then heated under the same conditions as in the step (iii).
- the step (v) is preferably a step of removing the convex portion so that the film thickness of the convex portion existing after the step (iv) is equivalent to the film thickness of the concave pattern.
- Examples of the heating method in step (v) include a method of heating using a hot plate, a batch type oven or a conveyor type oven, a method of drying with hot air using a dryer, and a method of vacuum baking.
- the atmosphere during heating in any of the above steps may be appropriately set according to the type of the conductive film forming composition to be used, and is not particularly limited, but may be performed in the air or under reduced pressure. It may be performed in a non-oxidizing atmosphere or in a reducing atmosphere.
- the non-oxidizing atmosphere include a nitrogen atmosphere, a helium atmosphere, and an argon atmosphere. Among these, a nitrogen atmosphere in which inexpensive nitrogen gas can be used is preferable.
- reducing atmosphere such as hydrogen gas, is mentioned.
- the heating condition in (a) is preferably a temperature at which the convex portion decomposes or volatilizes, preferably 120 to 300 ° C., more preferably in consideration of the conductive film forming composition and structure to be used. Is 150-250 ° C.
- the heating time in (a) is not particularly limited as long as it is a temperature at which the convex portion decomposes or volatilizes.
- the heating temperature is set to about 250 ° C., about 3 to 15 minutes is preferable, and when the heating temperature is set to about 200 ° C., about 5 to 30 minutes is preferable, and about 150 ° C.
- the heating temperature is set, it is preferably about 10 to 60 minutes.
- the electronic circuit of the present invention includes a conductive film formed by the method for forming a conductive film, and preferably includes a stacked body of the conductive film formed by the method for forming a conductive film and the structure.
- the electronic circuit of the present invention is formed on a structure body in which a coating film having a portion (concave pattern portion) having a thin film thickness of 5% or more and less than 90% is formed on a non-flat surface, and the concave pattern portion.
- a conductive film is formed on a structure body in which a coating film having a portion (concave pattern portion) having a thin film thickness of 5% or more and less than 90% is formed on a non-flat surface, and the concave pattern portion.
- a conventionally known layer for example, a protective film or an insulating film for protecting the conductive film is further stacked on the stacked body of the conductive film and the structure formed by the conductive film forming method. It may be what you did.
- the electronic device of the present invention includes the electronic circuit. For this reason, it becomes an electronic device miniaturized, thinned, and highly functionalized.
- Examples of the electronic device include portable information devices such as a touch panel, a liquid crystal display, and a mobile phone, a digital camera, an organic display, organic EL lighting, various sensors, and a wearable device.
- the resin composition contains a polymer having an acid dissociable group (hereinafter also referred to as “[A] polymer”) and an acid generator (hereinafter also referred to as “[C] acid generator”). It is. According to such a composition, since the coating film formed from this composition volatilizes and decomposes
- Such a resin composition suppresses bleeding of the composition for forming a conductive film on the structure and serves as a composition for forming an underlayer for forming a high-definition pattern. It can be suitably used as a composition for forming an underlayer that improves the adhesion to the structure.
- the resin composition may further contain a solvent (hereinafter also referred to as “[B] solvent”).
- the composition exhibits a liquid state by containing the [B] solvent, and can easily form a coating film by a coating or dipping process.
- the resin composition may further contain a sensitizer (hereinafter also referred to as “[D] sensitizer”) as an auxiliary material for the [C] acid generator, and the acid from the [C] acid generator.
- a quencher hereinafter also referred to as “[E] quencher” may be included as a diffusion suppressing material.
- the resin composition may contain a polymerizable compound having an ethylenically unsaturated bond other than the [A] polymer (hereinafter also referred to as “[F] polymerizable compound”), and is a radiation-sensitive polymerization initiator. (Hereinafter also referred to as “[G] radiation-sensitive polymerization initiator”). Furthermore, other arbitrary components can be mix
- the viscosity (temperature: 20 ° C., shear rate: 10 sec ⁇ 1 ) of the resin composition may be adjusted by the method of providing the desired resin composition, the film thickness of the coating film to be formed, and the like.
- a spin coating method as a method for providing a resin composition
- it is preferably 5 cP (0.005 Pa ⁇ s) to 20 cP (0.02 Pa ⁇ s).
- the spray coating method is used as a method for providing the resin composition, it is preferably 1 cP (0.001 Pa ⁇ s) to 10 cP (0.01 Pa ⁇ s).
- the acid dissociable group is preferably a group containing a fluorine atom. Since the polymer [A] has such a group, a liquid repellent coating film can be formed in the step (i), and the liquid repellent can be obtained through the subsequent step (ii). High-definition conductive film that can be easily formed with a non-irradiated radiation-irradiated portion and a lyophilic concave portion (concave pattern) from the portion, and through subsequent steps (iv) and (v) Is preferable.
- the acid-dissociable group is a group having a group containing at least one bond selected from the group consisting of an acetal bond and a hemiacetal ester bond from the viewpoint that a high-definition conductive film can be formed. More preferably, such a group is at least one group selected from the group consisting of a group represented by the following formula (1-1) and a group represented by the following formula (1-2). Particularly preferred.
- R 1 and R 2 each independently represents a hydrogen atom or a methyl group, and Rf independently represents an organic group having a fluorine atom. Indicates a binding site.
- a polymer containing an acetal bond can be obtained by reacting an alcohol with a compound having a group CH 2 ⁇ C (R 1 ) —O—, and a polymer containing a hemiacetal ester bond can be obtained by reacting with a carboxylic acid It can be obtained by reacting with a compound having the group CH 2 ⁇ C (R 1 ) —O—.
- Rf groups represented by the following formulas (1-1) to (1-33), 2,2,2-trifluoroethyl group and 1,2,2-trifluorovinyl group are preferable.
- a protecting group derived from a vinyl ether compound represented by the following formula (1) (hereinafter also referred to as “compound (1)”) is introduced into the hydroxyl group of the precursor compound having a hydroxyl group. It is preferable that it is a compound which has the structure which becomes.
- the polymer may be a compound having a structure in which a protective group derived from the compound (1) is introduced into a carboxyl group of a compound having a carboxyl group as a precursor.
- compound (a) in particular, compounds in which a protecting group is introduced into the hydroxyl group of a compound having a hydroxyl group, have the property that the protecting group is not easily removed by heat, Since it has the property that the elimination of the protecting group by irradiation can be controlled, it can be suitably used as the [A] polymer. Furthermore, the compound (a) is preferable because it can control the removal of the protecting group with higher accuracy by irradiation with a combination with the [C] acid generator described later.
- R 0 represents a hydrogen atom or a methyl group.
- R A independently represents a methylene group, an alkylene group having 2 to 12 carbon atoms, an alkenylene group having 2 to 12 carbon atoms, a part of the alkylene group or alkenylene group, —O—, — A group substituted by (C ⁇ O) O— or —O (C ⁇ O) —, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 13 carbon atoms, a substituted or unsubstituted group having 4 to 12 carbon atoms An alicyclic hydrocarbon group or a group in which one or more hydrogen atoms of these groups are substituted with a fluorine atom.
- alkylene group having 2 to 12 carbon atoms in R A examples include ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group and dodecylene group.
- alkenylene group having 2 to 12 carbon atoms in R A examples include vinylene group, ethene-1,2-diyl group, 2-butene-1,4-diyl and the like.
- Examples of the substituted or unsubstituted aromatic hydrocarbon group having 6 to 13 carbon atoms in R A include a phenylene group, a tolylene group, a mesitylene group, a naphthylene group, and a biphenylene group.
- Examples of the substituted or unsubstituted alicyclic hydrocarbon group having 4 to 12 carbon atoms in R A include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a bicyclohexyl group, and the like.
- R A a methylene group, an alkylene group having 2 to 12 carbon atoms, an alkenylene group having 2 to 12 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 13 carbon atoms, or a group having 4 to 12 carbon atoms
- Examples of the group in which one or more hydrogen atoms of a substituted or unsubstituted alicyclic hydrocarbon group are substituted with fluorine atoms include groups in which one or more hydrogen atoms of the groups exemplified above are substituted with fluorine atoms, etc. Is mentioned.
- R A is preferably a methylene group, an ethylene group, a propylene group, a butylene group, a pentamethylene group, a hexamethylene group, a phenylene group, or a vinylene group.
- R B represents a group in which one or more hydrogen atoms of the hydrocarbon group are substituted with fluorine atoms.
- R B represents, for example, groups represented by the above formulas (1-1) to (1-33), 2,2,2-trifluoroethyl group, 1,2,2-trifluorovinyl 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group of the above formula (1-1), 4,4,4-trifluoro group of the formula (1-2) Butyl group, 3,3,4,4,4-pentafluorobutyl group of formula (1-4), 4,4,5,5,6,6,6-heptafluorohexyl of formula (1-16) Group, 3,3,4,4,5,5,6,6-6-nonafluorohexyl group of formula (1-7), 3,3,4,4,5,5 of formula (1-8) , 6,6,7,7,8,8,8-tridecafluorooctyl group, 3,3,4,4,5,5,6,6,7,7,8 of formula (1-9) 8, 9, 9, 10, 10 10 heptadecafluorodecyl group, 1,2,2-trifluor
- x represents an integer of 0 to 12, an integer of 0 to 9 is preferable, and 0 is more preferable.
- the coating film formed in the step (i) exhibits characteristics based on the [A] polymer, and the [A] polymer
- the characteristic derived from the protective group of this compound (a) is shown. Specifically, when a coating film is formed from the resin composition containing the compound (a), first, in the step (i), a liquid-repellent coating film is formed. In the portion, elimination of the protective group occurs, and in the portion from which the protective group is eliminated, a vinyloxy group or a hydroxyl group remains, and liquid repellency due to the protective group is lost.
- a method for obtaining the [A] polymer will be described.
- a method for obtaining the [A] polymer two methods are possible: a method using a polymer as a compound serving as a precursor and a method using a monomer as a compound serving as a precursor.
- the precursor polymer contains a hydroxyl group or a carboxyl group in the molecule, and the compound (1) is reacted with the hydroxyl group or carboxyl group of the precursor polymer.
- the [A] polymer can be obtained.
- the precursor monomer contains a hydroxyl group or carboxyl group in the molecule, and the compound (1) is reacted with the hydroxyl group or carboxyl group of the precursor monomer.
- the [A] polymer can be obtained by polymerizing the obtained monomer.
- the two methods for obtaining the [A] polymer will be described more specifically.
- a monomer having a hydroxyl group or a carboxyl group is polymerized to obtain a polymer having a hydroxyl group or a carboxyl group (precursor), and then the precursor and The [A] polymer can be obtained by reacting the compound (1) with a hydroxyl group or a carboxyl group of the resulting polymer.
- a polymer (precursor) having a hydroxyl group or a carboxyl group is obtained by a conventionally known method, for example, a method of reacting phenol and formaldehyde, and then the compound is added to the hydroxyl group or carboxyl group of the polymer to be the precursor. (1) can be reacted to obtain the [A] polymer.
- the monomer having a hydroxyl group is preferably a (meth) acrylic acid ester, for example, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl methacrylate, 2 -Hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxylethylphthalic acid, dipropylene glycol methacrylate, dipropylene glycol acrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate , Cyclohexanedimethanol monoacrylate, cyclohexanedimethanol monomethacrylate, ethyl ⁇ - (hydroxy Chill) acrylate, polypropylene glycol monomethacrylate, polypropylene glycol monoacrylate, glycerin monomethacrylate, glycerin monoacrylate
- Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl phthalic acid, and 2-acryloyl.
- Oxyethyltetrahydrophthalic acid 2-methacryloyloxyethyltetrahydrophthalic acid, 2-acryloyloxyethylhexahydrophthalic acid, 2-methacryloyloxyethylhexahydrophthalic acid, 2-acryloyloxypropylphthalic acid, 2-methacryloyloxypropylphthalic acid 2-acryloyloxypropyltetrahydrophthalic acid, 2-methacryloyloxypropyltetrahydrophthalic acid, 2-acryloyloxypropylhexahydrophthalate Acid, and 2-methacryloyloxy propyl hexahydrophthalic acid.
- a polymer having a hydroxyl group or a carboxyl group, which is a precursor of the polymer, can be obtained using only the monomer having a hydroxyl group or a carboxyl group, and the monomer having a hydroxyl group or a carboxyl group; Or it can obtain by copolymerizing monomers other than the monomer which has a carboxyl group.
- (meth) acrylic acid chain alkyl ester As monomers other than the monomer having a hydroxyl group or a carboxyl group, (meth) acrylic acid chain alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated aromatic compound, conjugated diene, tetrahydrofuran Mention may be made of unsaturated compounds containing skeletons, maleimides and monomers other than these.
- examples of the (meth) acrylic acid chain alkyl ester include, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, methacrylic acid.
- 2-ethylhexyl isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, Examples include 2-ethylhexyl acrylate, isodecyl acrylate, n-lauryl acrylate, tridecyl acrylate, and n-stearyl acrylate.
- Examples of the (meth) acrylic acid cyclic alkyl ester include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 2,6 ] decan-8-yl methacrylate, isobornyl methacrylate, Examples thereof include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 2,6 ] decan-8-yl acrylate, and isobornyl acrylate.
- Examples of the (meth) acrylic acid aryl ester include phenyl methacrylate, benzyl methacrylate, phenyl acrylate, and benzyl acrylate.
- Examples of the unsaturated aromatic compound include styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and p-methoxystyrene.
- conjugated diene examples include 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.
- Examples of the unsaturated compound containing a tetrahydrofuran skeleton include tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, and 3- (meth) acryloyloxytetrahydrofuran-2-one.
- maleimide examples include N-phenylmaleimide, N-cyclohexylmaleimide, N-tolylmaleimide, N-naphthylmaleimide, N-ethylmaleimide, N-hexylmaleimide, and N-benzylmaleimide.
- Examples of monomers other than the aforementioned monomers include glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- ( Acryloyloxymethyl) -3-ethyloxetane, tricyclo [5.2.1.0 2,6 ] decan-8-yloxyethyl methacrylate, tricyclo [5.2.1.0 2,6 ] decane-8- Iloxyethyl acrylate is mentioned.
- a solvent When synthesizing a polymer having a hydroxyl group or a carboxyl group, which is a precursor of the polymer, a solvent may be used.
- the solvent include alcohols, glycol ethers, ethylene glycol alkyl ether acetates, Examples include diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol monoalkyl ether propionate, ketone and ester.
- a molecular weight modifier can be used to adjust the molecular weight.
- the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and thioglycolic acid;
- xanthogens such as dimethylxanthogen sulfide and diisopropylxanthogen disulfide; terpinolene and ⁇ -methylstyrene dimer.
- the polystyrene-reduced weight average molecular weight (Mw) of the polymer having a hydroxyl group or a carboxyl group by gel permeation chromatography (GPC) is preferably from 1000 to 40000, more preferably from 5000 to 30000.
- the method of reacting the compound (1) with the hydroxyl group or carboxyl group of a polymer having a hydroxyl group or a carboxyl group to obtain the [A] polymer is represented by the following formula: hydroxyl group or carboxyl group and vinyl ether This can be done by reacting with a group.
- a method for obtaining a polymer can be referred to a known method, for example, a method described in JP-A-2005-187609.
- an acetal bond is formed by the hydroxyl group of the polymer having a hydroxyl group and the vinyl ether group of the compound (1), or by the carboxyl group of the polymer having a carboxyl group and the vinyl ether group of the compound (1).
- a hemiacetal ester bond is formed to form an adduct.
- an equimolar or excess amount of the compound (1) is added to the hydroxyl group or carboxyl group of the polymer, and the resulting reaction is obtained. After cooling the mixture to a temperature of about 0 ° C.
- an adduct is obtained by reacting the compound (1) with a hydroxyl group or a carboxyl group of a monomer having a hydroxyl group or a carboxyl group, and the adduct is polymerized.
- a known method can be referred to for obtaining such a polymer [A].
- an acetal bond is formed by a hydroxyl group of a monomer having a hydroxyl group and a vinyl ether group of the compound (1), or a carboxyl group of a monomer having a carboxyl group
- a hemiacetal ester bond is formed by the vinyl ether group of the compound (1) to form an adduct.
- the [A] polymer can be obtained in the same manner as in the method for producing a polymer having a hydroxyl group or a carboxyl group.
- Preferred examples of the [A] polymer obtained as described above include polymers having at least one selected from the group consisting of structural units represented by the following formulas (2) to (5). .
- R 3 independently represents a hydrogen atom or a methyl group.
- R 4 independently represents a methylene group, an alkylene group having 2 to 12 carbon atoms, or 2 to 12 carbon atoms. A group in which a part of the alkenylene group, the alkylene group or the alkenylene group is substituted with —O—, — (C ⁇ O) O— or —O (C ⁇ O) —, a substitution of 6 to 13 carbon atoms, or An unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted alicyclic hydrocarbon group having 4 to 12 carbon atoms, or a group in which one or more hydrogen atoms of these groups are substituted with a fluorine atom.
- R 5 independently represents a group in which one or more hydrogen atoms of a hydrocarbon group are substituted with a fluorine atom, m represents 0 or 1, and n represents an integer of 0 to 12 independently.
- R 4 examples include the same groups as those exemplified for R A.
- R 5 examples include the same groups as those exemplified for R B.
- N is preferably an integer of 0 to 9.
- the polymer include a polymer having at least one selected from the group consisting of structural units represented by the following formula. Further, the side chain terminal of the structural unit represented by the following formula is a group represented by the above (1-1) to (1-33), a 2,2,2-trifluoroethyl group, or a 1,2,2-trimethyl group.
- the structural unit which is a fluorovinyl group is also mentioned as a preferable example.
- a polymer may be used individually by 1 type, and may use 2 or more types.
- Suitable [B] solvents include alcohol solvents, ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates, aliphatic hydrocarbons. , Aromatic hydrocarbons, ketones and esters.
- alcohol solvents examples include long-chain alkyl alcohols such as 1-hexanol, 1-octanol, 1-nonanol, 1-dodecanol, 1,6-hexanediol, 1,8-octanediol; Aromatic alcohols such as benzyl alcohol; Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; Examples include dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl
- benzyl alcohol ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether are particularly preferable from the viewpoint of improving coating properties.
- ethers examples include tetrahydrofuran, hexyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, and 1,4-dioxane.
- diethylene glycol alkyl ethers examples include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether.
- ethylene glycol alkyl ether acetates examples include methyl cellosolve acetate, ethyl cellosolve acetate, and ethylene glycol monobutyl ether acetate.
- propylene glycol monoalkyl ether acetates examples include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate.
- propylene glycol monoalkyl ether propionates examples include propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, and propylene glycol monobutyl ether propionate. be able to.
- Examples of the aliphatic hydrocarbons include n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, cyclohexane and decalin. it can.
- aromatic hydrocarbons examples include benzene, toluene, xylene, ethylbenzene, n-propylbenzene, i-propylbenzene, n-butylbenzene, mesitylene, chlorobenzene, and dichlorobenzene.
- ketones examples include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, and 4-hydroxy-4-methyl-2-pentanone.
- esters examples include methyl acetate, ethyl acetate, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, and 2-hydroxy-2-methyl.
- Ethyl propionate methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, 3 -Butyl hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate Butyl ethoxy acetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butylbutoxyacetate,
- the amount of the solvent used is preferably 200 to 1600 parts by mass, more preferably 400 to 1000 parts by mass with respect to 100 parts by mass of the component excluding the solvent of the resin composition.
- the acid generator is a compound that generates an acid at least upon irradiation with radiation.
- the resin composition contains the [C] acid generator, the acid dissociable group can be eliminated from the [A] polymer.
- Examples of the acid generator include oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and carboxylic acid ester compounds.
- the acid generator may be used alone or in combination of two or more.
- oxime sulfonate compound As said oxime sulfonate compound, the compound containing the oxime sulfonate group represented by following formula (5) is preferable.
- R 11 is an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 4 to 12 carbon atoms, or an aryl having 6 to 20 carbon atoms. Group or a group in which some or all of the hydrogen atoms of the alkyl group, alicyclic hydrocarbon group and aryl group are substituted with a substituent.
- the alkyl group represented by R 11 is preferably a linear or branched alkyl group having 1 to 12 carbon atoms.
- the linear or branched alkyl group having 1 to 12 carbon atoms may be substituted with a substituent.
- the substituent include an alkoxy group having 1 to 10 carbon atoms and 7,7-dimethyl-2.
- -An alicyclic group containing a bridged cyclic alicyclic group such as an oxonorbornyl group.
- the fluoroalkyl group having 1 to 12 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, and a heptylfluoropropyl group.
- the alicyclic hydrocarbon group having 4 to 12 carbon atoms represented by R 11 may be substituted with a substituent.
- substituents include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a halogen atom, and the like. Atom.
- the aryl group having 6 to 20 carbon atoms represented by R 11 is preferably a phenyl group, a naphthyl group, a tolyl group, or a xylyl group.
- the aryl group may be substituted with a substituent, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.
- Examples of the compound containing an oxime sulfonate group represented by the formula (5) include oxime sulfonate represented by the following formula (5-1), the following formula (5-2), and the following formula (5-3). Compounds.
- R 11 has the same meaning as the formula (5).
- R 15 is an alkyl group having 1 to 12 carbon atoms or a fluoroalkyl group having 1 to 12 carbon atoms.
- X represents an alkyl group, an alkoxy group or a halogen atom.
- m is an integer of 0 to 3. However, when there are a plurality of Xs, the plurality of Xs may be the same or different.
- the alkyl group represented by X in the formula (5-3) is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
- the alkoxy group represented by X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
- the halogen atom represented by X is preferably a chlorine atom or a fluorine atom.
- m 0 or 1 is preferable.
- a compound in which m is 1, X is a methyl group, and the substitution position of X is an ortho position is particularly preferable.
- Examples of the oxime sulfonate compound represented by (5-3) include compounds represented by the following formulas (5-3-1) to (5-3-5).
- the compounds represented by the formulas (5-3-1) to (5-3-5) are respectively (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) Acetonitrile, (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-octylsulfonyloxyimino)-(4-methoxyphenyl) acetonitrile, commercially available it can.
- onium salt examples include diphenyliodonium salt, triphenylsulfonium salt, alkylsulfonium salt, benzylsulfonium salt, dibenzylsulfonium salt, substituted benzylsulfonium salt, benzothiazonium salt, and tetrahydrothiophenium salt.
- diphenyliodonium salt examples include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, Diphenyliodonium butyltris (2,6-difluorophenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluoro Arsenate, bis (4-tert-butylphenyl) iodonium trif Oromethan
- triphenylsulfonium salt examples include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, triphenylsulfonium salt, and the like.
- An example is phenylsulfonium butyl tris (2,6-difluorophenyl) borate.
- alkylsulfonium salt examples include 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-
- Examples include 4- (benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, and dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate.
- benzylsulfonium salt examples include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4- Methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4- Examples include hydroxyphenylmethylsulfonium hexafluorophosphate.
- dibenzylsulfonium salt examples include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium hexafluoroantimonate, and dibenzyl-4-methoxy.
- Phenylsulfonium hexafluoroantimonate dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-t-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxy Benzyl-4-hydroxyphenylsulfonium hexafluorophosphate.
- Examples of the substituted benzylsulfonium salt include p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-chlorobenzyl-4-hydroxy Phenylmethylsulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl- Examples include 3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate.
- benzothiazonium salt examples include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- (p- Methoxybenzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate.
- tetrahydrothiophenium salt examples include 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate and 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium.
- Trifluoromethanesulfonate 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-1 , 1,2,2-Tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (5-t-butoxycarbonyl) Oxybicyclo [2.2.1] heptan-2-yl)- , 1,2,2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (6-tert-butoxycarbonyloxybicyclo [2.2.1] heptane -2-yl) -1,1,2,2-t
- Preferred sulfonimide compounds as acid generators include, for example, N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N— (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-tri Fluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) succinimi
- Halogen-containing compounds [Halogen-containing compounds] [C] Preferred halogen-containing compounds as acid generators include, for example, haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds.
- Preferred diazomethane compounds as acid generators include, for example, bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, bis (2 , 4-Xylylsulfonyl) diazomethane, bis (p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) Examples include diazomethane and phenylsulfonyl
- Preferred sulfone compounds as acid generators include, for example, ⁇ -ketosulfone compounds, ⁇ -sulfonylsulfone compounds, and diaryldisulfone compounds.
- Preferred sulfonic acid ester compounds as acid generators include, for example, alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates.
- Carboxylic ester compounds include, for example, carboxylic acid o-nitrobenzyl ester.
- the acid generator is preferably an oxime sulfonate compound, an onium salt, or a sulfonate compound, more preferably an oxime sulfonate compound.
- the oxime sulfonate compound is preferably a compound containing an oxime sulfonate group represented by the formulas (5-3-1) to (5-3-5), and is represented by the formula (5-3-5). Compounds are more preferred.
- the onium salt is preferably a tetrahydrothiophenium salt or a benzylsulfonium salt, and is 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, benzyl-4-hydroxyphenylmethylsulfonium hexanium. Fluorophosphate is more preferable, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate is more preferable.
- the sulfonic acid ester compound is preferably a haloalkylsulfonic acid ester, more preferably N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester.
- the content of the [C] acid generator is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the [A] polymer. [C] By setting the content of the acid generator within the above range, the sensitivity of the resin composition can be optimized. Therefore, a high-resolution concave pattern can be formed through the steps (i) to (ii).
- the resin composition may contain a [D] sensitizer.
- the radiation sensitivity of the composition can be further improved.
- the sensitizer is preferably a compound that absorbs actinic rays or radiation to be in an electronically excited state.
- the [D] sensitizer in an electronically excited state comes into contact with the [C] acid generator, electron transfer, energy transfer, heat generation, and the like occur, thereby causing the [C] acid generator to undergo a chemical change. To produce acid.
- Sensitizers include compounds belonging to the following compounds and having an absorption wavelength in the region of 350 nm to 450 nm.
- sensitizer examples include pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene and the like.
- Xanthenes such as fluorescein, eosin, erythrosine, rhodamine B, rose bengal;
- Xanthones such as xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthen-9-one;
- Cyanines such as thiacarbocyanine, oxacarbocyanine; Merocyanines such as merocyanine and carbomerocyanine; Rhodocyanines; Oxonols; Thiazines such as thionine, methylene blue and toluidine blue;
- Acridines such as acridine orange, chloroflavin, acriflavine;
- Acridones such as acridone, 10-butyl-2-chloroacridone;
- Anthraquinones such as an
- [D] sensitizers polynuclear aromatics, acridones, styryls, base styryls, coumarins, and xanthones are preferred, and xanthones are more preferred.
- xanthones diethylthioxanthone, 2,4-diethylthioxanthen-9-one and isopropylthioxanthone are particularly preferred
- a sensitizer may be used alone or in combination of two or more.
- the amount thereof to be used is preferably 0.05 to 8 parts by mass, more preferably 0.1 to 4 parts by mass with respect to 100 parts by mass of the [A] polymer.
- the sensitivity of the resin composition can be optimized by setting the amount of the sensitizer used in the above range, a high-resolution concave pattern can be formed by performing the steps (i) to (ii).
- the resin composition may contain an [E] quencher.
- [E] quencher functions as an acid diffusion inhibitor that prevents diffusion of acid from the [C] acid generator.
- the quencher includes cyclic amines such as alkylamines and imidazoles, specifically, for example, compounds having an imidazole structure (such as 2-phenylbenzimidazole and 2,4,5-triphenylimidazole) ), Compounds having a piperidine structure (such as N-hydroxyethylpiperidine and bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate), compounds having a pyridine structure (such as 4-dimethylaminopyridine), And compounds having an antipyrine structure (such as antipyrine and hydroxyantipyrine), 1,5-diazabicyclo [4.3.0] non-5-ene and 1,8-diazabicyclo [5.4.0] -undec-7-ene Is mentioned.
- cyclic amines such as alkylamines and imidazoles, specifically, for example, compounds having
- [E] quenchers include photodegradable bases that are exposed to light upon exposure to generate weak acids.
- the photodegradable base generates an acid in the exposed area, while the non-exposed area exhibits a high acid scavenging function by an anion to supplement the acid from the [C] acid generator, and from the exposed area to the unexposed area. Deactivates the acid that diffuses into the surface. That is, since the acid is deactivated only in the unexposed area, the contrast of the protecting group elimination reaction is improved, and as a result, the resolution can be further improved.
- an onium salt compound that is decomposed by exposure and loses acid diffusion controllability can be mentioned.
- a quencher may be used individually by 1 type, and may use 2 or more types.
- the content of the quencher is preferably 0.001 to 5 parts by mass and more preferably 0.005 to 3 parts by mass with respect to 100 parts by mass of the [A] polymer.
- [D] By setting the content of the sensitizer in the above range, the reactivity of the resin composition can be optimized, so that a high-resolution concave pattern can be formed through the steps (i) to (ii). .
- the resin composition can cure the composition by containing the [F] polymerizable compound.
- the polymerizable compound is preferably a polymerizable compound having an ethylenically unsaturated bond.
- [A] is a compound other than a polymer.
- monofunctional, bifunctional or trifunctional or more (meth) acrylic acid Esters are preferred.
- the monofunctional compound refers to a compound having one (meth) acryloyl group
- the bifunctional or trifunctional or higher functional compound is a compound having two or three (meth) acryloyl groups, respectively. I mean.
- Examples of the monofunctional (meth) acrylic acid ester include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, (2-acryloyloxyethyl) (2-hydroxypropyl) ) Phthalate, (2-methacryloyloxyethyl) (2-hydroxypropyl) phthalate, and ⁇ -carboxypolycaprolactone monoacrylate.
- bifunctional (meth) acrylic acid ester examples include ethylene glycol diacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, and tetraethylene.
- examples include glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, and 1,9-nonanediol dimethacrylate.
- tri- or higher functional (meth) acrylic acid ester examples include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipenta Erythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethylene oxide modified dipentaerythritol hexaacrylate, tri (2- Acryloyloxyethylene ) Phosphate, tri (2-methacryloyloxyeth
- Examples of commercially available products include Aronix (registered trademark) M-309, M-315, M-400, M-405, M-450, M-7100, M-8030, M-8060.
- TO-1450 above, Toagosei Co., Ltd.
- KAYARAD registered trademark
- TMPTA DPHA
- DPCA-20 DPCA-30
- DPCA-60 DPCA-120
- DPEA-12 above
- Biscoat 295, 300, 360, GPT, 3PA, 400 Osaka Organic Chemical Co., Ltd.
- commercial products containing polyfunctional urethane acrylate compounds include New Frontier ( Registered trademark) R-1150 (Daiichi Kogyo Seiyaku Co., Ltd.), KAYARAD (registered trademark) DPHA-40H (Nippon Kayaku Co., Ltd.) and the like.
- Commercial products containing acrylate compounds are preferred. Among them, a tri- or higher functional (meth) acrylic acid ester is preferable, and a mixture of dipenta
- the polymerizable compound may be used alone or in combination of two or more.
- the amount of the polymerizable compound used is preferably 1 to 300 parts by weight, more preferably 3 to 200 parts by weight, and still more preferably 4 to 100 parts by weight with respect to 100 parts by weight of the [A] polymer.
- the usage-amount of a polymeric compound By making the usage-amount of a polymeric compound into the said range, the height of the coating film obtained from a resin composition can be raised and heat resistance can be made more favorable.
- the radiation-sensitive polymerization initiator is a compound that accelerates the polymerization of the [F] polymerizable compound when irradiated with radiation. Therefore, when the resin composition contains a [F] polymerizable compound, it is preferable to use a [G] radiation sensitive polymerization initiator.
- radiation-sensitive polymerization initiators examples include O-acyloxime compounds, acetophenone compounds, biimidazole compounds, and the like.
- O-acyloxime compound examples include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H.
- O-acyloxime compounds include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), Ethanone-1- [9-ethyl-6- ⁇ 2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl ⁇ -9. H. -Carbazol-3-yl] -1- (O-acetyloxime).
- acetophenone compound examples include an ⁇ -aminoketone compound and an ⁇ -hydroxyketone compound.
- ⁇ -aminoketone compound examples include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl)- Mention may be made of 1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one.
- ⁇ -hydroxyketone compound examples include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropane-1 Examples include -one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, and 1-hydroxycyclohexyl phenylketone.
- the above acetophenone compounds can be used alone or in combination of two or more.
- acetophenone compounds ⁇ -aminoketone compounds are preferred, and 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2- Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one is particularly preferred.
- biimidazole compound examples include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, , 2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′ , 5,5′-Tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 Mention may be made of '-biimidazole. These biimidazole compounds can be used alone or in combination of two or more.
- an aliphatic or aromatic compound having a dialkylamino group (hereinafter referred to as “amino-based sensitization”) is used to sensitize the compound.
- An agent can be added.
- amino sensitizers examples include 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone. Of these amino sensitizers, 4,4'-bis (diethylamino) benzophenone is particularly preferred. These amino sensitizers can be used alone or in combination of two or more.
- a thiol compound can be added as a hydrogen radical donor.
- a biimidazole compound is sensitized by an amino sensitizer and cleaved to generate an imidazole radical, but may not exhibit high polymerization initiation ability as it is.
- a hydrogen radical is donated from the thiol compound to the imidazole radical.
- the imidazole radical is converted into neutral imidazole, and a component having a sulfur radical having a high polymerization initiating ability is generated.
- a biimidazole compound, an amino sensitizer, and a thiol compound are added to the resin composition, a film having high hardness can be formed even at a low radiation dose.
- thiol compounds include aromatic thiol compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole; Aliphatic monothiol compounds such as 3-mercaptopropionic acid and methyl 3-mercaptopropionate; Bifunctional or higher functional aliphatic thiol compounds such as pentaerythritol tetra (mercaptoacetate) and pentaerythritol tetra (3-mercaptopropionate) can be exemplified. These thiol compounds can be used alone or in combination of two or more. Of these thiol compounds, 2-mercaptobenzothiazole is particularly preferable.
- the amount of the amino sensitizer used is preferably 0.1 to 50 parts by mass, more preferably 100 parts by mass of the biimidazole compound. Is 1 to 20 parts by mass.
- the reactivity at the time of exposure can be improved by making the usage-amount of an amino sensitizer into the said range.
- the amount of the thiol compound used is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the biimidazole compound.
- the amount is preferably 1 to 20 parts by mass.
- the resin composition contains a [G] radiation-sensitive polymerization initiator, it preferably contains at least one selected from the group consisting of an O-acyloxime compound and an acetophenone compound, and further contains a biimidazole compound. May be.
- a radiation sensitive polymerization initiator may be used alone or in combination of two or more.
- the amount of the radiation-sensitive polymerization initiator used is preferably 0.05 to 50 parts by mass, more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the [A] polymer.
- a coating film can be hardened
- the resin composition may further contain other optional components as long as the effects of the present invention are not impaired.
- other optional components include a surfactant, a storage stabilizer, an adhesion aid, and a heat resistance improver.
- Other optional components may be used alone or in combination of two or more.
- composition for forming a conductive film is not particularly limited as long as it is a composition capable of forming a conductive film, and is preferably a liquid ink or paste having fluidity.
- conductive film forming ink and conductive film forming paste are preferable.
- ink or paste in which metal particles are dispersed, ink or paste containing a metal salt and a reducing agent, and metallization by heating in a reducing atmosphere Preferred is an ink or paste in which metal oxide particles are dispersed, a dispersion or solution of a conductive polymer, and an ink or paste in which nanocarbons such as carbon nanotubes and graphene are dispersed, particularly from the viewpoint of conductivity and coating properties.
- Ink or paste in which metal particles are dispersed, or ink or paste containing a metal salt and a reducing agent is preferable.
- These inks or pastes can be formed into a coating film by various printing methods, coating methods, dipping methods, and the like, and the coating film is heated to become a conductive conductive film (conductive film).
- Such an ink or paste has a viscosity (temperature: 20 ° C., shear rate: 10 sec ⁇ 1 ), preferably in the range of 0.001 to 100 Pa ⁇ s, more preferably 0.001 to 1 Pa ⁇ s. Is desirable.
- a conductive film When forming a conductive film, it has a low viscosity of 0.001 to 100 Pa ⁇ s, preferably 0.001 to 1 Pa ⁇ s (temperature: 20 ° C., shearing) from the viewpoints of applicability, handling, and storage. Conventionally, it has been required to use a composition for forming a conductive film at a speed of 10 sec ⁇ 1 ). However, in the conventional method for manufacturing a conductive film, the composition for forming a conductive film is wetted and spread. In order to produce a high-definition conductive film, such a low viscosity composition could not be used.
- the conductive film is formed on the concave pattern, even if the low-viscosity conductive film forming composition is used, wetting spread and bleeding of the composition are suppressed, and a high-definition conductive film Can be manufactured. For this reason, it is preferable to use the said composition for low conductive film formation from the point that the effect of this invention is exhibited more.
- Metal salt In the metal salt, metal ions contained in the metal salt are reduced by the reducing agent to form a single metal. And in the electrically conductive film formed, it plays the role which expresses electroconductivity. For example, when the metal salt is a copper salt, copper ions contained in the copper salt are reduced by a reducing agent to form copper alone, thereby forming a conductive film.
- the metal salt is preferably a copper salt or a silver salt.
- the said metal salt may be used individually by 1 type, and may use 2 or more types.
- the copper salt is not particularly limited as long as it is a compound containing copper ions, and examples thereof include copper salts composed of copper ions and at least one of inorganic anion species and organic anion species. Among these, from the viewpoint of solubility, it is preferable to use one or more selected from the group consisting of a copper carboxylate, a copper hydroxide, and a complex salt of copper and an acetylacetone derivative.
- copper carboxylates examples include copper salts with dicarboxylic acids such as copper malonate, copper succinate and copper maleate, copper salts with aromatic carboxylic acids such as copper benzoate and copper salicylate, copper acetate, Copper trifluoroacetate, copper propionate, copper butyrate, copper isobutyrate, copper 2-methylbutyrate, copper 2-ethylbutyrate, copper valerate, copper isovalerate, copper pivalate, copper hexanoate, copper heptanoate, octane
- Organic compounds having monocarboxy groups such as copper oxide, copper 2-ethylhexanoate, copper nonanoate, copper formate, copper hydroxyacetate, copper glyoxylate, copper lactate, copper oxalate, copper tartrate, copper malate, copper citrate
- a suitable salt is a copper salt with an acid.
- copper formate may be anhydrous or hydrated.
- Examples of the hydrate of copper formate include tetra
- Examples of the complex salt of copper and an acetylacetone derivative include acetylacetonato copper, 1,1,1-trimethylacetylacetonato copper, 1,1,1,5,5,5-hexamethylacetylacetonato copper. 1,1,1-trifluoroacetylacetonatocopper, and 1,1,1,5,5,5-hexafluoroacetylacetonatocopper are suitable compounds.
- Copper carboxylates such as copper, copper formate tetrahydrate and copper glyoxylate are preferred.
- the silver salt is not particularly limited as long as it is a silver salt.
- a copper salt is preferably used from the viewpoint of suppressing migration of metal atoms in the formed conductive film.
- copper formate is particularly preferable because of its excellent reducibility. Copper formate may be anhydrous or copper formate tetrahydrate.
- the content of the metal salt in the conductive film forming composition is preferably in the range of 0.01 to 50% by mass and more preferably in the range of 0.1 to 30% by mass with respect to the total amount of the composition.
- a conductive film having stable and excellent conductivity can be formed.
- the content of the metal salt is preferably 0.01% by mass or more.
- the content of the metal salt is preferably 50% by mass or less.
- the conductive film-forming composition preferably contains a reducing agent together with the metal salt for the purpose of reducing metal ions contained in the metal salt to form a simple metal.
- the reducing agent is not particularly limited as long as it has reducibility to the metal ion contained in the metal salt used.
- Examples of the reducing agent include monomolecular compounds having one or more functional groups selected from the group consisting of thiol groups, nitrile groups, amino groups, hydroxy groups, and hydroxycarbonyl groups, nitrogen atoms, oxygen atoms And a polymer having in its molecular structure one or more heteroatoms selected from the group consisting of sulfur atoms.
- Examples of the monomolecular compound include alkanethiols, amines, hydrazines, monoalcohols, diols, hydroxyamines, ⁇ -hydroxyketones, and carboxylic acids.
- polymer examples include polyvinylpyrrolidone, polyethyleneimine, polyaniline, polypyrrole, polythiophene, polyacrylamide, polyacrylic acid, carboxymethylcellulose, polyvinyl alcohol, and polyethylene oxide.
- At least one selected from the group consisting of alkanethiols and amines is preferable.
- alkanethiols examples include ethanethiol, n-propanethiol, i-propanethiol, n-butanethiol, i-butanethiol, t-butanethiol, n-pentanethiol, n-hexanethiol, n-heptane.
- alkanethiols examples include ethanethiol, n-propanethiol, i-propanethiol, n-butanethiol, i-butanethiol, t-butanethiol, n-pentanethiol, n-hexanethiol, n-heptane.
- amines examples include amine compounds such as 3- (2-ethylhexyloxy) propylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, i-butylamine, t- Butylamine, n-pentylamine, n-hexylamine, cyclohexylamine, n-heptylamine, n-octylamine, 2-ethylhexylamine, 2-ethylhexylpropylamine, 3-ethoxypropylamine, n-nonylamine, n-decylamine, monoamine compounds such as n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, benzylamine, aminoacetal
- hydrazines examples include 1,1-di-n-butylhydrazine, 1,1-di-t-butylhydrazine, 1,1-di-n-pentyldrazine, 1,1-di-n- Hexylhydrazine, 1,1-dicyclohexylhydrazine, 1,1-di-n-heptylhydrazine, 1,1-di-n-octylhydrazine, 1,1-di- (2-ethylhexyl) hydrazine, 1,1-diphenyl Hydrazine, 1,1-dibenzylhydrazine, 1,2-di-n-butylhydrazine, 1,2-di-t-butylhydrazine, 1,2-di-n-pentylhydrazine, 1,2-di-n -Hexylhydrazine, 1,2-dicyclohexylhydrazine, 1,2-di-n-
- Examples of the monoalcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, sec-butyl alcohol, pentanol, hexanol, heptanol, octanol, cyclohexanol, Examples include benzyl alcohol and terpineol.
- diols examples include ethylene glycol, propylene glycol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 2,3-butanediol, 2,3-pentanediol, , 3-hexanediol, 2,3-heptanediol, 3,4-hexanediol, 3,4-heptanediol, 3,4-octanediol, 3,4-nonanediol, 3,4-decanediol, 4, 5-octanediol, 4,5-nonanediol, 4,5-decanediol, 5,6-decanediol, 3-N, N-dimethylamino-1,2-propanediol, 3-N, N-diethylamino- 1,2-propanediol, 3-N, N-dio
- hydroxyamines examples include N, N-diethylhydroxylamine, N, N-di-n-propylhydroxylamine, N, N-di-n-butylhydroxylamine, N, N-di-n-pentyl. And hydroxylamine and N, N-di-n-hexylhydroxylamine.
- Examples of the ⁇ -hydroxy ketones include hydroxyacetone, 1-hydroxy-2-butanone, 3-hydroxy-2-butanone, 1-hydroxy-2-pentanone, 3-hydroxy-2-pentanone, 2-hydroxy- 3-pentanone, 3-hydroxy-2-hexanone, 2-hydroxy-3-hexanone, 4-hydroxy-3-hexanone, 4-hydroxy-3-heptanone, 3-hydroxy-4-heptanone and 5-hydroxy-4- Octanone is mentioned.
- the carboxylic acids are not particularly limited as long as they are reducible to metal salts, and examples thereof include formic acid, hydroxyacetic acid, glyoxylic acid, lactic acid, oxalic acid, tartaric acid, malic acid and citric acid. It is done.
- the reducing agent is preferably an amine compound, more preferably 2-ethylhexylpropylamine and 3-ethoxypropylamine.
- the content of the reducing agent in the conductive film forming composition is preferably in the range of 1 to 99% by mass and more preferably in the range of 10 to 90% by mass with respect to the total amount of the composition.
- a conductive film having excellent conductivity can be formed.
- a conductive film having a low resistance value and excellent adhesion to the electrode can be formed.
- the composition for forming a conductive film can contain fine metal particles for the purpose of improving the reduction precipitation rate of a metal salt or adjusting the viscosity of the composition.
- the metal fine particles are not particularly limited, but from the viewpoint of the conductivity and stability of the particles, for example, one or more selected from the group consisting of gold, silver, copper, platinum and palladium It is preferable that the particles contain the above metal species. These metal species may be simple substances or alloys with other metals. When these metal species are a simple substance, preferable metal fine particles include at least one kind or a combination of two or more kinds selected from the group consisting of gold fine particles, silver fine particles, copper fine particles, platinum fine particles and palladium fine particles.
- metal fine particles containing one or more metal species selected from the group consisting of silver, copper and palladium from the viewpoint of cost, availability, and catalytic ability when forming a conductive film.
- Metal fine particles other than these may be used.
- the metal fine particles are oxidized by copper ions, or the catalytic ability is reduced to reduce the copper salt to metal copper. It is more preferable to use the metal fine particles because the deposition rate may decrease.
- the average particle size of the metal fine particles is preferably in the range of 0.05 to 5 ⁇ m.
- the particle diameter of the metal fine particles is preferably 0.05 ⁇ m or more.
- the average particle diameter of the metal fine particles is preferably 5 ⁇ m or less.
- the method for measuring the average particle size is as follows. Select any three locations from the field of view observed using a transmission electron microscope (TEM), field emission transmission electron microscope (FE-TEM), field emission scanning electron microscope (FE-SEM), etc. Then, shoot at the most suitable magnification for particle size measurement. From each of the obtained photographs, arbitrarily select 100 particles, measure the long axis of the particles with TEM, FE-TEM, FE-SEM, etc., and calculate the particle size by dividing the measurement magnification. It can be obtained by arithmetically averaging the values. The standard deviation can be obtained from the particle size and number of individual metal fine particles during the observation.
- TEM transmission electron microscope
- FE-TEM field emission transmission electron microscope
- FE-SEM field emission scanning electron microscope
- the metal fine particles may be commercially available or may be synthesized by a known method, and is not particularly limited.
- a known synthesis method for example, a gas phase method (dry method) such as a sputtering method or an in-gas deposition method, or a liquid phase in which a metal compound solution is reduced in the presence of a surface protective agent to precipitate metal fine particles.
- dry method a gas phase method
- wet method a liquid phase in which a metal compound solution is reduced in the presence of a surface protective agent to precipitate metal fine particles.
- the metal purity in the metal fine particles is not particularly limited, 95% or more is preferable and 99% or more is more preferable because there is a possibility of adversely affecting the conductivity of the conductive film obtained when the purity is low.
- the content of the metal fine particles in the conductive film forming composition is preferably in the range of 0 to 60% by mass, more preferably 1 to 40% by mass, and more preferably 1 to 20% by mass with respect to the total amount of the composition. A range is particularly preferred.
- composition for forming a conductive film preferably contains a solvent from the viewpoint of adjusting the viscosity of the composition to improve the productivity of the conductive film and obtaining a uniform conductive film with low resistance.
- the solvent examples include organic solvents that can dissolve or disperse each component in the composition for forming a conductive film and do not participate in the reduction reaction of the metal salt.
- organic solvents include one kind selected from the group consisting of ethers, esters, aliphatic hydrocarbons, and aromatic hydrocarbons, or a mixture of two or more compatible.
- ethers examples include the compounds exemplified as the [B] solvent.
- esters examples include methyl formate, ethyl formate, butyl formate, ⁇ -butyrolactone, and other compounds exemplified as [B] solvent.
- ethers are particularly preferable from the viewpoint of easy adjustment of viscosity, and hexyl methyl ether, diethylene glycol dimethyl ether, and the like are particularly preferable.
- the content of the solvent contained in the composition for forming a conductive film is preferably in the range of 0 to 95% by mass, more preferably in the range of 1 to 70% by mass with respect to the total amount of the composition. A range of 10 to 50% by mass is particularly preferable.
- the composition for forming a conductive film can be produced by mixing the components described above.
- this mixing method For example, the stirring by a stirring blade, the stirring by a stirrer and a stirring bar, the stirring by a boiling machine, the stirring by an ultrasonic wave (homogenizer) is mentioned.
- the rotation speed of the stirring blades is usually in the range of 1 to 4000 rpm, preferably in the range of 100 to 2000 rpm.
- solid content concentration means the ratio of the copolymer mass which occupies for the total mass of a copolymer solution.
- Reprecipitation purification is carried out by dropping the obtained reaction solution into a large excess of methanol, and then the precipitate is dissolved in 10 parts by mass of diethylene glycol dimethyl ether and then dripped into a large excess of hexane for reprecipitation purification. Then, the precipitate was dried to obtain 6.8 parts by mass of [A] polymer (P-1) as a white solid copolymer.
- the obtained [A] polymer (P-1) was analyzed using 1 H-NMR to confirm that acetalization had progressed (chemical shift: 4.80 ppm, acetal group C—H). .
- Reprecipitation purification is performed by dropping the obtained reaction solution into an excessive amount of methanol, and then the precipitate is dissolved again in 15 parts by mass of diethylene glycol dimethyl ether, and then reprecipitation purification is performed by dropwise addition to hexane.
- the precipitate was dried to obtain 11.0 parts by mass of [A] polymer (P-2) as a white solid copolymer.
- the obtained [A] polymer (P-2) was analyzed using 1 H-NMR to confirm that acetalization had progressed (chemical shift: 4.80 ppm, acetal group C—H). .
- Reprecipitation purification is performed by dropping the obtained reaction solution into an excessive amount of methanol, and then the precipitate is dissolved again in 15 parts by mass of diethylene glycol dimethyl ether, and then reprecipitation purification is performed by dropwise addition to hexane.
- the precipitate was dried to obtain 10.9 parts by mass of [A] polymer (P-3) as a white solid copolymer.
- the obtained [A] polymer (P-3) was analyzed using 1 H-NMR to confirm that acetalization had progressed (chemical shift: 5.74 ppm, acetal group C—H). .
- Reprecipitation purification is performed by dropping the obtained reaction solution into an excessive amount of methanol, and then the precipitate is dissolved again in 15 parts by mass of tetrahydrofuran, and then reprecipitation purification is performed by dropwise addition to hexane.
- the precipitate was dried to obtain 6.0 parts by mass of [A] polymer (P-4) as a white solid copolymer.
- the obtained [A] polymer (P-4) was analyzed using 1 H-NMR to confirm that acetalization had progressed (chemical shift: 5.74 ppm, acetal group C—H). .
- Reprecipitation purification is carried out by dropping the obtained reaction solution into an excessive amount of methanol, and then the precipitate is dissolved again in 30 parts by mass of tetrahydrofuran, and then reprecipitation purification is carried out by dropwise addition to hexane, The precipitate was dried to obtain [A] polymer (P-5) as a white solid copolymer.
- the obtained [A] polymer (P-5) was analyzed using 1 H-NMR to confirm that acetalization had progressed (chemical shift: 5.48 ppm, acetal group C—H). .
- C-1 N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester
- C-2 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate
- C-3 CGI725 (manufactured by BASF)
- E-1 2-phenylbenzimidazole
- E-2 4- (dimethylamino) pyridine
- G-1 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Irgacure (registered trademark) 907, manufactured by BASF)
- G-2 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (Irgacure (registered trademark) 379, manufactured by BASF)
- G-3 Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure (registered trademark) OXE02, manufactured by BASF AG )
- Examples 1 to 9 and Comparative Examples 1 and 2 Each component of the type and content shown in Table 1 is mixed, and after adding propylene glycol monomethyl ether as a solvent [B] so that the solid content concentration is 10% by mass, a membrane filter having a pore size of 0.5 ⁇ m Each resin composition was prepared by filtering with (made by Merck Millipore). In Table 1, “-” indicates that the corresponding component was not used.
- the coating film was formed by baking for 10 minutes at 100 degreeC using clean oven.
- the exposed part (concave part) became a lyophilic part
- the part other than the exposed part (convex part) became a lyophobic part.
- a film patterned in accordance with the portion (hereinafter, sometimes referred to as a “hydrophobic patterning film”) was obtained.
- the contact angle meter (CA-X, manufactured by Kyowa Interface Science Co., Ltd.), measure the contact angles of water and tetradecane on the exposed surface and unexposed surface, respectively. The repellency was confirmed.
- Table 2 the contact angle of water on the exposed portion surface is indicated as “lyophilic portion water”, and the contact angle of water on the unexposed portion surface is indicated as “liquid repellent portion water”. The same applies to the contact angle of tetradecane.
- a high-pressure mercury lamp (exposure machine: MA-1400, manufactured by Dainippon Kagaku Co., Ltd.) on the three-dimensional structure with the film seal attached, irradiation was performed so that the exposure amount of the coating film was 500 mJ / cm 2. It was. Thereafter, the film seal was peeled off and baked at 100 ° C. for 10 minutes using a clean oven to form a coating film.
- the three-dimensional structure a is curved glass, and the resin composition was spray coated on the entire upper surface of the curved glass in FIG.
- the three-dimensional structure b is a three-dimensional structure made of polycarbonate / AES resin (“CW50”: manufactured by Techno Polymer Co., Ltd.), and the resin composition was spray coated on the entire upper surface of FIG. 1B of this three-dimensional structure.
- the three-dimensional structure c is a three-dimensional structure made of polycarbonate / ABS (acrylonitrile butadiene styrene) resin (“CK50”: manufactured by Techno Polymer Co., Ltd.), and the resin composition was spray coated on the entire surface of the three-dimensional structure. .
- a three-dimensional structure with a coating film was prepared in the same manner as in the evaluation of [Forming concave pattern on three-dimensional structure]. For this three-dimensional structure with a coating film, if the three-dimensional structure has not deteriorated and a concave pattern that can be visually confirmed is formed ( ⁇ ), a concave pattern that can be visually confirmed cannot be formed. If the film was visually roughened or whitened or the like was visually observed on the three-dimensional structure, the appearance was visually evaluated as defective (x).
- a three-dimensional structure with a coating film was prepared in the same manner as in the evaluation of [Forming concave pattern on three-dimensional structure].
- a 1 cm square rectangular coating film portion including a concave pattern was cut using a cutter knife, and a tape peeling test (CT-18 cello tape, manufactured by Nichiban Co., Ltd.) was made at this portion.
- CT-18 cello tape manufactured by Nichiban Co., Ltd.
- the adhesion between the coating film and the three-dimensional structure was evaluated. If peeling did not occur, it was evaluated as good ( ⁇ ), and the case where peeling occurred was evaluated as defective ( ⁇ ).
- a linear silver wiring with a width of 500 ⁇ m is obtained, and the resistance using a 2000 type digital multimeter (manufactured by Keithley) is measured at two points with an interval of 10 cm in length of the silver wiring portion. If no continuity was confirmed ( ⁇ ), a straight silver wiring having a width of 500 ⁇ m could not be obtained. In addition, it was confirmed using the optical microscope (Eclipse L200D, Nikon Corporation) whether the linear silver wiring was obtained.
- a three-dimensional structure with silver wiring was prepared in the same manner as in the evaluation of [Metal wiring formation: dropping method] and [Metal wiring formation: Dip method].
- This three-dimensional structure with silver wiring was cut with a cutter knife so that the silver wiring was 1 cm long isolated, and a tape peeling test (CT-18 cello tape, manufactured by Nichiban Co., Ltd.) was carried out on this part.
- the adhesion between the film and the coating film was evaluated. If peeling did not occur, it was evaluated as good ( ⁇ ), and the case where peeling occurred was evaluated as defective ( ⁇ ).
- a structure having a hydrophilic / repellent patterning film was obtained. From the results shown in Table 2, the hydrophilic / repellent patterning films formed by using the resin compositions prepared in Examples 1 to 9 for structures having a non-flat coated surface were prepared in Comparative Examples 1 and 2. Compared with the coating film formed using the made resin composition, it turned out that it has favorable repellency performance, an external appearance, and adhesiveness, and has a desired concave pattern.
- the resin compositions prepared in Examples 1 to 9 can be suitably used for manufacturing a three-dimensional structure having a concave pattern.
- the film thickness and contact angle of the concave pattern portion and the non-irradiated portion of the coating film formed on the three-dimensional structures a to c are considered to be the same as those of the coating film formed on the substrate on the flat plate. .
- the present invention it is possible to easily form a coating film having a concave pattern on a three-dimensional structure having a non-flat surface, and a composition comprising a polymer containing an acid-dissociable group having a fluorine atom Can be formed from the coating film by irradiation with radiation.
- This repellent patterning film assists the patterning of these inks by repellent performance when various inks such as conductive film forming inks are applied using the dropping method, dipping method, spray coating method and various printing methods. Can do.
- a fine and elaborate pattern can be formed, and the pattern obtained is excellent also in the adhesiveness with respect to the three-dimensional structure which has a non-flat surface. From the above, the structure having a concave pattern formed by the present invention can be suitably used as a base material in printed electronics.
- a fine and fine conductive film (wiring) is formed on a three-dimensional structure having a non-flat surface by a simple method such as a dropping method, a dipping method, a spray coating method, or various printing methods. Can be formed. And since conductive films, such as obtained metal wiring, are excellent in electroconductivity and the adhesiveness with respect to a three-dimensional structure, the formation method of the electrically conductive film of this invention becomes suitable for formation of an electronic circuit.
- the structure having a concave pattern manufactured by the manufacturing method according to the present invention becomes a base material on which a semiconductor chip or the like is mounted, and is used for automobile parts, liquid crystal displays, portable information devices such as mobile phones, digital cameras, and organic displays. It is effective for downsizing, thinning, weight reduction, and high functionality in electronic devices such as organic EL lighting, various sensors, and wearable devices.
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Abstract
Description
本発明の構成例は以下のとおりである。
(i)酸解離性基を有する重合体及び酸発生剤を含む樹脂組成物を用いて、構造体の非平坦面に塗膜を形成する工程
(ii)前記塗膜の一部の所定部分に放射線照射を行うことにより凹部を形成する工程
[7] 前記酸解離性基が、下記式(1-1)及び(1-2)で示される基からなる群より選ばれる少なくとも1つの基を有する、[1]~[6]のいずれかに記載の製造方法。
[9] 前記樹脂組成物が、下記式(2)~(5)で示される構成単位の群から選ばれる少なくとも1つを有する、[1]~[8]のいずれかに記載の製造方法。
[11] フッ素原子を含む酸解離性基を有する重合体、及び酸発生剤を含有する樹脂組成物。
[12] アセタール結合及びヘミアセタールエステル結合からなる群より選ばれる少なくとも1つの結合を含む酸解離性基を有する重合体、並びに、酸発生剤を含有する樹脂組成物。
[15] [14]に記載の電子回路を有する、電子デバイス。
本発明に係る凹パターンを有する構造体の製造方法は、下記工程(i)及び(ii)を含み、該凹パターンが、下記工程(i)で得られる塗膜の膜厚に対して、5%以上90%未満薄い膜厚であることを特徴とする。
(i)酸解離性基を有する重合体及び酸発生剤を含む樹脂組成物を用いて、構造体の非平坦面に塗膜を形成する工程
(ii)前記塗膜の一部の所定部分に放射線照射を行うことにより凹部を形成する工程
従って、本発明の製造方法は、所望の凹パターンを有する構造体を、容易に、安価に、大幅な工程の簡略化及びプロセス上の負荷を低減しながら製造できる等の点から、現像工程を含まないことが好ましい。
本発明によれば、放射線照射を経て凹パターンを形成するため、現像工程を行わず、放射線の当たりにくい箇所に集中的に放射線照射したり、過剰に放射線を照射することで、それほどバラツキがなく均一な凹パターンを形成することができる。
得られる凹パターンがこのような形状を有していると、該塗膜に導電膜形成用組成物を塗布等する際に、塗膜表面の凹凸の段差により、凹パターンから該組成物が溢れ出にくく、また、凹パターン以外の箇所に該組成物が残りにくくなるため、多量の導電膜形成用組成物を塗布等することができ、多量の導電膜形成用組成物を用いても高精細な導電膜(膜幅50μm以下の導電膜(パターン))を得ることができる。
放射線未照射部及び凹パターンの膜厚は、具体的には、下記実施例に記載の方法で測定することができる。
前記接触角差は、具体的には、下記実施例に記載の方法で測定することができる。
また、接触角を測定する際に、テトラデカンを用いたのは、テトラデカンが導電膜形成用組成物に一般的に使用され、かつ揮発しにくく、接触角を測定することに適しているためである。
工程(i)は、酸解離性基を有する重合体及び酸発生剤を含む樹脂組成物を用いて、構造体の非平坦面に塗膜を形成する工程であり、好ましくは樹脂組成物を構造体の非平坦面に設け、次いで、該組成物を加熱(プレベーク)することにより、塗膜を形成する工程である。
工程(i)において、前記樹脂組成物を用いることにより下記工程(ii)等において現像工程を行うことなく、構造体上に凹部を形成することができる。
尚、前記樹脂組成物については、以下で具体的に説明する。
このような構造体としては、例えば、瓦状の構造体、凸部及び/又は凹部を有する構造体、筒状の構造体、球状の構造体が挙げられる。
尚、本発明では、立方体や直方体などの角柱体の少なくとも2面に前記樹脂組成物を塗布等する場合、該塗布等する面は非平坦面であるため、本発明では、このような角柱体も、その少なくとも2面に前記樹脂組成物が塗布等される場合には、工程(i)における、非平坦面を有する構造体とする。
本発明によれば、これら立体構造物に簡便に凹パターンを形成することができ、更に、該凹パターン上に導電膜を形成することで、省スペースによる小型化、スリム化及び軽量化された導電膜付構造体を得ることができ、また、得られる導電膜付構造体は、高機能化が期待される。
尚、本発明において、例えば、立方体や直方体である構造体表面にこのような前処理をすることにより、表面が粗面化されたり、微小な凹凸が形成された表面は、前記「非平坦面」ではなく、非平坦面か否かは、表面を巨視的にみて判断する。
工程(ii)は、工程(i)で形成した塗膜の一部の所定部分に放射線照射を行うことにより凹部を形成する工程である。
工程(ii)では、構造体上の塗膜の一部に放射線が照射され、放射線照射部と放射線未照射部とを有する塗膜が形成される。
この時、酸解離性基がフッ素原子を含んでいれば、工程(i)で得られた塗膜及び放射線未照射部は撥液性を示すが、放射線照射部(凹部)は酸解離性基の消失に伴い、放射線未照射部に比べ親液性となる。
また、放射線照射は、線幅の狭い凹部を形成できる等の点から、工程(i)で形成した塗膜側から放射線を照射することが好ましい。
本発明では、前記工程(ii)で形成された凹部が、構造体上に形成された凹パターンであってもよいが、前記凹部のくぼみを更に深化させる(凹部の膜厚を更に薄くする)等の点から、本発明の製造方法は、工程(ii)で得られた放射線照射後の塗膜を加熱する工程(iii)を含むことが好ましい。
この工程(iii)を行う場合には、この工程により、凹パターンを有する構造体が製造される。
本発明の導電膜の形成方法は、前記凹パターンを有する構造体の製造方法で形成された凹パターン上に、導電膜形成用組成物を用いて導電膜を形成する工程を含むことを特徴とする。
この導電膜の形成方法によれば、高精細な導電膜(配線)を容易に、非平坦面を有する構造体上に形成することができ、従来の方法では容易に形成することができなかった、幅10μm以下、例えば、1μm程度の導電膜(配線)も非平坦面を有する構造体上に容易に形成することができる。
尚、導電膜形成用組成物については、以下で具体的に説明する。
また、加熱時間も特に制限されないが、1~120分間が好ましく、3~60分間がより好ましい。
本発明の電子回路は、前記導電膜の形成方法で形成された導電膜を有し、好ましくは、前記導電膜の形成方法で形成された導電膜と前記構造体との積層体を有する。つまり、本発明の電子回路は、非平坦面に、5%以上90%未満薄い膜厚の部分(凹パターン部)を有する塗膜が形成された構造体と、該凹パターン部上に形成された導電膜とを有する。
また、本発明の電子回路は、前記導電膜の形成方法で形成された導電膜と構造体との積層体に、従来公知の層、例えば、導電膜を保護する保護膜や絶縁膜をさらに積層したものであってもよい。
前記電子デバイスとしては、例えば、タッチパネル、液晶ディスプレイ、携帯電話等の携帯情報機器、デジタルカメラ、有機ディスプレイ、有機EL照明、各種センサーやウェアラブルデバイスが挙げられる。
前記樹脂組成物は、酸解離性基を有する重合体(以下「[A]重合体」ともいう。)及び酸発生剤(以下「[C]酸発生剤」ともいう。)を含有する組成物である。
このような組成物によれば、該組成物から形成される塗膜が、放射線の照射及び必要により行われる加熱により、揮発、分解するため好ましい。
このような樹脂組成物は、前記構造体上で導電膜形成用組成物の滲みを抑え、高精細なパターンを形成するための下地層形成用組成物として、また、導電膜(配線)と前記構造体との密着性を向上させる下地層形成用組成物として、好適に使用することができる。
前記樹脂組成物は、[C]酸発生剤の補助材料として、更に、増感剤(以下「[D]増感剤」ともいう。)を含んでもよく、[C]酸発生剤からの酸の拡散抑制材料としてクエンチャー(以下「[E]クエンチャー」ともいう。)を含んでもよい。
また、前記樹脂組成物は、[A]重合体以外のエチレン性不飽和結合を有する重合性化合物(以下「[F]重合性化合物」ともいう。)を含んでもよく、感放射線性重合開始剤(以下「[G]感放射線性重合開始剤」ともいう。)を含んでもよい。
さらに、前記樹脂組成物には、本発明の効果を損なわない限り、その他の任意成分を配合することができる。
前記[A]重合体は、酸により、解離する性質を有する基を含有する重合体であれば特に制限されない。
これらの化合物(以下「化合物(a)」ともいう。)、特に水酸基を有する化合物の水酸基に保護基が導入された化合物は、熱による保護基の脱離が生じ難いという性質を備え、一方で、放射線照射による保護基の脱離の制御ができるという性質を備えるため、[A]重合体として好適に使用できる。さらに、化合物(a)は、後述する[C]酸発生剤との組み合わせによって、放射線照射による、より高精度の保護基の脱離の制御が可能となるため好ましい。
また、前駆体となる化合物としてモノマーを用いる方法では、前駆体となるモノマーが分子内に水酸基又はカルボキシル基を含有し、前駆体となるモノマーの水酸基又はカルボキシル基に前記化合物(1)を反応させた後、得られたモノマーを重合させることで[A]重合体を得ることができる。
以下、[A]重合体を得るための2つの方法について、より具体的に説明する。
この方法では、水酸基又はカルボキシル基を有するモノマーを重合して水酸基又はカルボキシル基を有する重合体(前駆体)を得て、その後、前駆体となる重合体の水酸基又はカルボキシル基に前記化合物(1)を反応させて、[A]重合体を得ることができる。また、従来公知の方法、例えば、フェノールとホルムアルデヒドとを反応させる方法で水酸基又はカルボキシル基を有する重合体(前駆体)を得て、その後、前駆体となる重合体の水酸基又はカルボキシル基に前記化合物(1)を反応させて、[A]重合体を得ることができる。
例えば、水酸基又はカルボキシル基を有する重合体を適宜の有機溶媒中に溶解した後、重合体の有する水酸基又はカルボキシル基に対して等モル又は過剰量の前記化合物(1)を加え、得られた反応混合物を0℃から室温(25℃)程度の温度に冷却した後、前記有機溶媒と同じ溶媒に溶解させた酸(例えば、シュウ酸溶液)を触媒として滴下し、滴下終了後、室温下で1時間~24時間攪拌し、反応させる。反応終了後、有機溶剤を除去することにより、目的の[A]重合体を得ることができる。
この方法では、水酸基又はカルボキシル基を有するモノマーの水酸基又はカルボキシル基に前記化合物(1)を反応させて付加物を得て、該付加物を重合させることで、[A]重合体を得る。このような[A]重合体を得る方法は、公知の方法を参考にすることができる。例えば、特開2005-187609号公報に記載されているように、水酸基を有するモノマーの水酸基と化合物(1)のビニルエーテル基によってアセタール結合を生成して、又は、カルボキシル基を有するモノマーのカルボキシル基と前記化合物(1)のビニルエーテル基によってヘミアセタールエステル結合を生成して、付加物を形成する。次いで、得られた付加物を用いて、前記水酸基又はカルボキシル基を有する重合体の製造方法と同様にして、[A]重合体を得ることができる。
前記R5としては、前記RBで例示した基と同様の基等が挙げられる。
前記nとしては、0~9の整数が好ましい。
[B]溶剤としては特に限定されないが、[A]重合体の他、後述する[C]酸発生剤及び[F]重合性化合物等の各成分を均一に溶解又は分散することができる溶剤が好ましい。
ベンジルアルコール等の芳香族アルコール類;
エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル等のエチレングリコールモノアルキルエーテル類;
プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル等のプロピレングリコールモノアルキルエーテル類;
ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノブチルエーテル等のジプロピレングリコールモノアルキルエーテル類などを挙げることができる。
これらのアルコール系溶剤は、単独で又は2種以上を使用することができる。
[C]酸発生剤は、少なくとも放射線の照射によって酸を発生する化合物である。樹脂組成物が、[C]酸発生剤を含有することで、[A]重合体から酸解離性基を脱離させることができる。
[C]酸発生剤は、単独で用いてもよく、2種類以上を用いてもよい。
前記オキシムスルホネート化合物としては、下記式(5)で表されるオキシムスルホネート基を含む化合物が好ましい。
式(5-3)中、Xは、アルキル基、アルコキシ基又はハロゲン原子である。mは、0~3の整数である。但し、Xが複数の場合、複数のXは同一であっても異なっていてもよい。
オニウム塩としては、例えば、ジフェニルヨードニウム塩、トリフェニルスルホニウム塩、アルキルスルホニウム塩、ベンジルスルホニウム塩、ジベンジルスルホニウム塩、置換ベンジルスルホニウム塩、ベンゾチアゾニウム塩、テトラヒドロチオフェニウム塩が挙げられる。
[C]酸発生剤として好ましいスルホンイミド化合物としては、例えば、N-(トリフルオロメチルスルホニルオキシ)スクシンイミド、N-(カンファスルホニルオキシ)スクシンイミド、N-(4-メチルフェニルスルホニルオキシ)スクシンイミド、N-(2-トリフルオロメチルフェニルスルホニルオキシ)スクシンイミド、N-(4-フルオロフェニルスルホニルオキシ)スクシンイミド、N-(トリフルオロメチルスルホニルオキシ)フタルイミド、N-(カンファスルホニルオキシ)フタルイミド、N-(2-トリフルオロメチルフェニルスルホニルオキシ)フタルイミド、N-(2-フルオロフェニルスルホニルオキシ)フタルイミド、N-(トリフルオロメチルスルホニルオキシ)ジフェニルマレイミド、N-(カンファスルホニルオキシ)ジフェニルマレイミド、4-メチルフェニルスルホニルオキシ)ジフェニルマレイミド、N-(2-トリフルオロメチルフェニルスルホニルオキシ)ジフェニルマレイミド、N-(4-フルオロフェニルスルホニルオキシ)ジフェニルマレイミド、N-(4-フルオロフェニルスルホニルオキシ)ジフェニルマレイミド、N-(フェニルスルホニルオキシ)ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシイミド、N-(4-メチルフェニルスルホニルオキシ)ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシイミド、N-(トリフルオロメタンスルホニルオキシ)ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシイミド、N-(ノナフルオロブタンスルホニルオキシ)ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシイミド、N-(カンファスルホニルオキシ)ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシイミド、N-(カンファスルホニルオキシ)-7-オキサビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシイミド、N-(トリフルオロメチルスルホニルオキシ)-7-オキサビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシイミド、N-(4-メチルフェニルスルホニルオキシ)ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシイミド、N-(4-メチルフェニルスルホニルオキシ)-7-オキサビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシイミド、N-(2-トリフルオロメチルフェニルスルホニルオキシ)ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシイミド、N-(2-トリフルオロメチルフェニルスルホニルオキシ)-7-オキサビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシイミド、N-(4-フルオロフェニルスルホニルオキシ)ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシイミド、N-(4-フルオロフェニルスルホニルオキシ)-7-オキサビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシイミド、N-(トリフルオロメチルスルホニルオキシ)ビシクロ[2.2.1]ヘプタン-5,6-オキシ-2,3-ジカルボキシイミド、N-(カンファスルホニルオキシ)ビシクロ[2.2.1]ヘプタン-5,6-オキシ-2,3-ジカルボキシイミド、N-(4-メチルフェニルスルホニルオキシ)ビシクロ[2.2.1]ヘプタン-5,6-オキシ-2,3-ジカルボキシイミド、N-(2-トリフルオロメチルフェニルスルホニルオキシ)ビシクロ[2.2.1]ヘプタン-5,6-オキシ-2,3-ジカルボキシイミド、N-(4-フルオロフェニルスルホニルオキシ)ビシクロ[2.2.1]ヘプタン-5,6-オキシ-2,3-ジカルボキシイミド、N-(トリフルオロメチルスルホニルオキシ)ナフチルジカルボキシイミド、N-(カンファスルホニルオキシ)ナフチルジカルボキシイミド、N-(4-メチルフェニルスルホニルオキシ)ナフチルジカルボキシイミド、N-(フェニルスルホニルオキシ)ナフチルジカルボキシイミド、N-(2-トリフルオロメチルフェニルスルホニルオキシ)ナフチルジカルボキシイミド、N-(4-フルオロフェニルスルホニルオキシ)ナフチルジカルボキシイミド、N-(ペンタフルオロエチルスルホニルオキシ)ナフチルジカルボキシイミド、N-(ヘプタフルオロプロピルスルホニルオキシ)ナフチルジカルボキシイミド、N-(ノナフルオロブチルスルホニルオキシ)ナフチルジカルボキシイミド、N-(エチルスルホニルオキシ)ナフチルジカルボキシイミド、N-(プロピルスルホニルオキシ)ナフチルジカルボキシイミド、N-(ブチルスルホニルオキシ)ナフチルジカルボキシイミド、N-(ペンチルスルホニルオキシ)ナフチルジカルボキシイミド、N-(ヘキシルスルホニルオキシ)ナフチルジカルボキシイミド、N-(ヘプチルスルホニルオキシ)ナフチルジカルボキシイミド、N-(オクチルスルホニルオキシ)ナフチルジカルボキシイミド、N-(ノニルスルホニルオキシ)ナフチルジカルボキシイミド等が挙げられる
[C]酸発生剤として好ましいハロゲン含有化合物としては、例えば、ハロアルキル基含有炭化水素化合物、ハロアルキル基含有ヘテロ環状化合物が挙げられる。
[C]酸発生剤として好ましいジアゾメタン化合物としては、例えば、ビス(トリフルオロメチルスルホニル)ジアゾメタン、ビス(シクロヘキシルスルホニル)ジアゾメタン、ビス(フェニルスルホニル)ジアゾメタン、ビス(p-トリルスルホニル)ジアゾメタン、ビス(2,4-キシリルスルホニル)ジアゾメタン、ビス(p-クロロフェニルスルホニル)ジアゾメタン、メチルスルホニル-p-トルエンスルホニルジアゾメタン、シクロヘキシルスルホニル(1,1-ジメチルエチルスルホニル)ジアゾメタン、ビス(1,1-ジメチルエチルスルホニル)ジアゾメタン、フェニルスルホニル(ベンゾイル)ジアゾメタン等が挙げられる。
[C]酸発生剤として好ましいスルホン化合物としては、例えば、β-ケトスルホン化合物、β-スルホニルスルホン化合物、ジアリールジスルホン化合物が挙げられる。
[C]酸発生剤として好ましいスルホン酸エステル化合物としては、例えば、アルキルスルホン酸エステル、ハロアルキルスルホン酸エステル、アリールスルホン酸エステル、イミノスルホネートが挙げられる。
[C]酸発生剤として好ましいカルボン酸エステル化合物としては、例えば、カルボン酸o-ニトロベンジルエステルが挙げられる。
前記樹脂組成物は、[D]増感剤を含有することができる。
フルオレセイン、エオシン、エリスロシン、ローダミンB、ローズベンガル等のキサンテン類;
キサントン、チオキサントン、ジメチルチオキサントン、ジエチルチオキサントン、イソプロピルチオキサントン、2,4-ジエチルチオキサンテン-9-オン等のキサントン類;
チアカルボシアニン、オキサカルボシアニン等のシアニン類;
メロシアニン、カルボメロシアニン等のメロシアニン類;
ローダシアニン類;
オキソノール類;
チオニン、メチレンブルー、トルイジンブルー等のチアジン類;
アクリジンオレンジ、クロロフラビン、アクリフラビン等のアクリジン類;
アクリドン、10-ブチル-2-クロロアクリドン等のアクリドン類;
アントラキノン等のアントラキノン類;
スクアリリウム等のスクアリリウム類;
スチリル類;
2-[2-[4-(ジメチルアミノ)フェニル]エテニル]ベンゾオキサゾール等のベーススチリル類;
7-ジエチルアミノ4-メチルクマリン、7-ヒドロキシ4-メチルクマリン、2,3,6,7-テトラヒドロ-9-メチル-1H,5H,11H[1]ベンゾピラノ[6,7,8-ij]キノリジン-11-オン等のクマリン類等が挙げられる。
前記樹脂組成物は、[E]クエンチャーを含有することができる。
[E]クエンチャーの含有量としては、[A]重合体100質量部に対して、0.001~5質量部が好ましく、0.005~3質量部がより好ましい。[D]増感剤の含有量を前記範囲にすることで、樹脂組成物の反応性を最適化できるため、前記工程(i)~(ii)を経ることで高解像度な凹パターンを形成できる。
樹脂組成物は、[F]重合性化合物を含有することで、該組成物を硬化させることができる。
このような[F]重合性化合物としては、重合性が良好であり、樹脂組成物から得られる膜の強度が向上するという観点から、単官能、2官能又は3官能以上の(メタ)アクリル酸エステルが好ましい。
尚、単官能化合物とは、(メタ)アクリロイル基を1つ有する化合物のことをいい、2官能又は3官能以上の化合物とは、それぞれ、(メタ)アクリロイル基を2つ又は3つ以上有する化合物のことをいう。
[G]感放射線性重合開始剤は、放射線の照射を受けて、[F]重合性化合物の重合を促進する化合物である。したがって、樹脂組成物が[F]重合性化合物を含有する場合、[G]感放射線性重合開始剤を用いることが好ましい。
以上のアセトフェノン化合物は、単独で又は2種以上を使用することができる。
3-メルカプトプロピオン酸、3-メルカプトプロピオン酸メチル等の脂肪族モノチオール化合物;
ペンタエリストールテトラ(メルカプトアセテート)、ペンタエリストールテトラ(3-メルカプトプロピオネート)等の2官能以上の脂肪族チオール化合物を挙げることができる。
これらのチオール化合物は、単独で又は2種以上を使用することができる。
これらのチオール化合物の中でも、2-メルカプトベンゾチアゾールが特に好ましい。
[G]感放射線性重合開始剤の使用量は、[A]重合体100質量部に対して、好ましくは0.05~50質量部、より好ましくは0.1~20質量部である。[G]感放射線性重合開始剤の使用量を前記範囲内とすることによって、低露光量でも、高い放射線感度で塗膜の硬化を行うことができる。
前記樹脂組成物は、さらに、本発明の効果を損なわない限りその他の任意成分を含有することができる。
その他の任意成分としては、界面活性剤、保存安定剤、接着助剤、耐熱性向上剤等を挙げることができる。
その他の任意成分は、1種を単独で使用してもよいし、2種以上を使用してもよい。
前記導電膜形成用組成物は特に限定されるものではなく、導電膜を形成できるような組成物であればよく、流動性を持った液状のインク、ペーストであることが好ましい。
例えば、導電膜形成インク、導電膜形成ペースト、顔料や染料を含む着色性インク、着色性ペースト、有機半導体溶液や酸化物半導体分散体、有機EL発光体溶液や量子ドット、カーボンナノチューブ、グラフェン、カーボンブラック等のナノカーボンを含むインクが挙げられる。
これらのインク又はペーストは各種の印刷法、塗布法、浸漬法などにより塗膜の形成が可能であり、またその塗膜は、加熱されて導電性の導通性膜(導電膜)となる。
一方、本発明では、前記凹パターン上に導電膜を形成するため、前記低粘度の導電膜形成用組成物を用いても、該組成物の濡れ広がりや滲みが抑制され、高精細な導電膜を製造できる。
このため、本発明の効果がより発揮されるという点からは、前記低粘度の導電膜形成用組成物を用いることが好ましい。
前記金属塩は、その金属塩に含まれる金属イオンが前記還元剤により還元されて金属単体となる。そして、形成される導電膜において、導電性を発現させる役割を果たす。例えば、金属塩が銅塩である場合、銅塩に含まれる銅イオンは還元剤により還元され、銅単体となり、導電膜が形成される。
前記金属塩としては銅塩、銀塩が好ましい。
前記金属塩は、1種を単独で使用してもよいし、2種以上を使用してもよい。
例えば、硝酸銀、酢酸銀、酸化銀、アセチルアセトン銀、安息香酸銀、臭素酸銀、臭化銀、炭酸銀、塩化銀、クエン酸銀、フッ化銀、ヨウ素酸銀、ヨウ化銀、乳酸銀、亜硝酸銀、過塩素酸銀、リン酸銀、硫酸銀、硫化銀、及びトリフルオロ酢酸銀を挙げることができる。
前記導電膜形成用組成物は、金属塩に含まれる金属イオンを還元して金属単体とすることを目的として、前記金属塩とともに、還元剤を含有することが好ましい。還元剤は、用いられる金属塩に含まれる金属イオンに対し還元性を有していれば特に限定するものではない。
前記導電膜形成用組成物は、金属塩の還元析出速度を向上させる目的、又は、該組成物の粘度を調節する目的で、金属微粒子を含有することができる。
透過型電子顕微鏡(TEM)、電界放射型透過電子顕微鏡(FE-TEM)、電界放射型走査電子顕微鏡(FE-SEM)等の顕微鏡を用いて観測された視野の中から、任意の3箇所選択し、粒径測定に最も適した倍率で撮影する。得られた各々の写真から、任意に粒子を100個選択し、粒子の長軸をTEM、FE-TEM、FE-SEM等で測定し、測定倍率を除して粒子径を算出し、これらの値を算術平均することにより求めることができる。また、標準偏差については、前記観察時に個々の金属微粒子の粒子径と数により求めることができる。
前記導電膜形成用組成物は、該組成物の粘度を調節して導電膜の生産性を向上させる観点や、低抵抗で均一な導電膜を得る観点から、溶剤を含有することが好ましい。
以下の合成例で得られた重合体のポリスチレン換算の重量平均分子量(Mw)及び分子量分布(Mw/Mn)は、以下の条件で測定した。
・測定方法:ゲルパーミエーションクロマトグラフィー(GPC)法
・標準物質:ポリスチレン換算
・装置 :東ソー(株)製、商品名:HLC-8220
・カラム :東ソー(株)製ガードカラムHXL-H、TSK gel G7000HXL、TSK gel GMHXL 2本、TSK gel G2000HXLを順次連結したもの
・溶媒 :テトラヒドロフラン
・サンプル濃度:0.7質量%
・注入量 :70μL
・流速 :1mL/min
1H-NMRは、溶媒としてCDCl3を用い、核磁気共鳴装置(Bruker製、AVANCEIII AV400N)を用い、温度25℃の条件下で測定した。
[合成例1]
冷却管及び撹拌機を備えたフラスコに、ジメチル2,2’-アゾビス(2-メチルプロピオネート)8質量部、2,4-ジフェニル-4-メチル-1-ペンテン2質量部、及び、ジエチレングリコールジメチルエーテル200質量部を仕込んだ。引き続きメタクリル酸2-ヒドロキシエチル42質量部及びメタクリル酸ベンジル58質量部を仕込み、窒素雰囲気下で緩やかに攪拌しつつ、溶液の温度を80℃に上昇させ、この温度を4時間保持して重合することにより、共重合体である重合体(A-1)を含む溶液を得た(固形分濃度=34.6質量%、Mw=26000、Mw/Mn=2.2)。尚、固形分濃度は共重合体溶液の全質量に占める共重合体質量の割合を意味する。
冷却管及び撹拌機を備えたフラスコに、ジメチル2,2’-アゾビス(2-メチルプロピオネート)8質量部、ペンタエリスリトールテトラキス(3-メルカプトプロピオネート)2質量部、及び、プロピレングリコールモノメチルエーテル200質量部を仕込んだ。引き続きメタクリル酸2-ヒドロキシエチル75質量部及びメタクリル酸ベンジル25質量部を仕込み、窒素置換した後、緩やかに攪拌しつつ、溶液の温度を80℃に上昇させ、この温度を4時間保持して重合することにより、共重合体である重合体(A-2)を含有する溶液を得た。得られた溶液を大過剰のヘキサンに滴下し、沈殿物を乾燥させることで白色固体状の重合体(A-2)を得た(Mw=28000、Mw/Mn=2.3)。
冷却管及び撹拌機を備えたフラスコに、ジメチル2,2’-アゾビス(2-メチルプロピオネート)8質量部、2,4-ジフェニル-4-メチル-1-ペンテン2質量部、及び、プロピレングリコールモノメチルエーテル200質量部を仕込んだ。引き続きメタクリル酸30質量部及びメタクリル酸ベンジル70質量部を仕込み、窒素置換した後、緩やかに攪拌しつつ、溶液の温度を80℃に上昇させ、この温度を4時間保持して重合することにより、共重合体である重合体(A-3)を含有する溶液を得た。得られた溶液を大過剰のヘキサンに滴下し、沈殿物を乾燥させることで白色固体状の重合体(A-3)を得た(Mw=24000、Mw/Mn=2.2)。
冷却管及び撹拌機を備えたフラスコに、ジメチル2,2’-アゾビス(2-メチルプロピオネート)8質量部、2,4-ジフェニル-4-メチル-1-ペンテン2質量部、及び、プロピレングリコールモノメチルエーテル200質量部を仕込んだ。引き続き2-メタクリロイルオキシエチルコハク酸60質量部及びメタクリル酸ベンジル40質量部を仕込み、窒素置換した後、緩やかに攪拌しつつ、溶液の温度を80℃に上昇させ、この温度を4時間保持して重合することにより、共重合体である重合体(A-4)を含有する溶液を得た。得られた溶液を大過剰のヘキサンに滴下し、沈殿物を乾燥させることで白色固体状の重合体(A-4)を得た(Mw=23400、Mw/Mn=2.2)。
冷却管及び撹拌機を備えたフラスコに、ポリビニルフェノール(マルカリンカーS-4P 丸善石油化学(株))5質量部を加え、テトラヒドロフラン50質量部で溶かし、3,3,4,4,5,5,6,6,7,7,8,8,8-トリデカフルオロ-1-ビニルオキシオクタン16質量部を加え、十分に攪拌した後にトリフルオロ酢酸0.50質量部を加え、窒素雰囲気下、60℃で9時間反応させた。続いて反応溶液を室温まで冷却し、ピリジン0.5質量部を加え、反応をクエンチした。得られた反応溶液を過剰量のメタノールに滴下することにより再沈殿精製を行い、続いて沈殿物を再度30質量部のテトラヒドロフランに溶解させた後、ヘキサンに滴下することにより再沈殿精製を行い、沈殿物を乾燥させることで白色固形状の共重合体として[A]重合体(P-5)を得た。得られた[A]重合体(P-5)について1H-NMRを用いて分析を行い、アセタール化が進行していることを確認した(化学シフト:5.48ppm、アセタール基C-H)。
冷却管及び撹拌機を備えたフラスコに、下記式で表されるフェノールノボラック樹脂P-200(荒川化学工業(株)製)5質量部を加え、テトラヒドロフラン60質量部で溶かし、3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-ヘプタデカフルオロ-1-ビニルオキシデカン20質量部を加え、十分に攪拌した後にトリフルオロ酢酸0.50質量部を加え、窒素雰囲気下、60℃で9時間反応させた。続いて反応溶液を室温まで冷却し、ピリジン0.5質量部を加え、反応をクエンチした。得られた反応溶液を過剰量のメタノールに滴下することにより再沈殿精製を行い、続いて沈殿物を再度30質量部のテトラヒドロフランに溶解させた後、ヘキサンに滴下することにより再沈殿精製を行い、沈殿物を乾燥させることで白色固形状の共重合体として[A]重合体(P-6)12.1質量部を得た。得られた[A]重合体(P-6)について1H-NMRを用いて分析を行い、アセタール化が進行していることを確認した(化学シフト:5.49ppm、アセタール基C-H)。
冷却管及び撹拌機を備えたフラスコに、メタクリル酸2-ヒドロキシエチル25質量部、3,3,4,4,5,5,6,6,7,7,8,8,8-トリデカフルオロ-1-ビニルオキシオクタン101質量部、トリフルオロ酢酸(TFA)2.0質量部及びテトラヒドロフラン(THF)200質量部を仕込み、窒素雰囲気下、60℃で9時間保持して反応させた。冷却後、反応液にピリジン2.1質量部を加え、クエンチした。得られた反応液を水洗、分液し、ロータリーエバポレーターで溶剤を除去し、減圧蒸留により未反応成分を除去することによりアセタール化生成物(M-1)を得た。
冷却管及び撹拌機を備えたフラスコに、ヒドロキシフェニルメタクリレート25質量部、3,3,4,4,5,5,6,6,7,7,8,8,8-トリデカフルオロ-1-ビニルオキシオクタン82質量部、トリフルオロ酢酸(TFA)1.6質量部及びテトラヒドロフラン(THF)200質量部を仕込み、窒素雰囲気下、60℃で9時間保持して反応させた。冷却後、反応液にピリジン1.7質量部を加え、反応をクエンチした。得られた反応液を水洗、分液し、ロータリーエバポレーターで溶剤を除去し、減圧蒸留により未反応成分を除去することによりアセタール化生成物(M-2)を得た。
冷却管及び撹拌機を備えたフラスコに、メタクリル酸2-(2-ビニロキシエトキシ)エチル(VEEM、(株)日本触媒製)25質量部、3,3,4,4,5,5,6,6,7,7,8,8,8-トリデカフルオロオクタノール45質量部、パラトルエンスルホン酸ピリジニウム(PPTSA)1.6質量部及びテトラヒドロフラン(THF)200質量部を仕込み、窒素雰囲気下、室温で8時間保持して反応させた。反応終了後、反応液にピリジン0.7質量部を加え、反応をクエンチした。得られた反応液を水洗、分液し、ロータリーエバポレーターで溶剤を除去し、減圧蒸留により未反応成分を除去することによりアセタール化生成物(M-3)を得た。
実施例及び比較例で用いた各成分の詳細を以下に示す。
C-1:N-ヒドロキシナフタルイミド-トリフルオロメタンスルホン酸エステル
C-2:4,7-ジ-n-ブトキシ-1-ナフチルテトラヒドロチオフェニウム トリフルオロメタンスルホネート
C-3:CGI725 (BASF社製)
D-1:2-イソプロピルチオキサントン
D-2:2,4-ジエチルチオキサンテン-9-オン
E-1:2-フェニルベンゾイミダゾール
E-2:4-(ジメチルアミノ)ピリジン
F-1:ジペンタエリスリトールヘキサアクリレート
F-2:1,9-ノナンジオールジアクリレート
G-1:2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノプロパン-1-オン(イルガキュア(登録商標)907、BASF社製)
G-2:2-ジメチルアミノ-2-(4-メチルベンジル)-1-(4-モルフォリン-4-イル-フェニル)-ブタン-1-オン(イルガキュア(登録商標)379、BASF社製)
G-3:エタノン-1-〔9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル〕-1-(O-アセチルオキシム)(イルガキュア(登録商標)OXE02、BASF社製)
表1に示す種類、含有量の各成分を混合し、固形分濃度が10質量%となるように、それぞれ[B]溶剤として、プロピレングリコールモノメチルエーテルを加えた後、孔径0.5μmのメンブレンフィルター(メルクミリポア社製)でろ過することにより、各樹脂組成物を調製した。尚、表1中の「-」は該当する成分を使用しなかったことを表す。
実施例1~9及び比較例1~2で調製した各樹脂組成物を用いて膜形成を行い、以下の評価を実施した。結果を表2又は3に示す。
ポリカーボネート/AES(アクリロニトリル・エチレン-プロピレン-ジエン・スチレン)樹脂(CW50:テクノポリマー社製)からなる平板上に、実施例1~9又は比較例1~2で調製した樹脂組成物をそれぞれスピンナーで塗布した後、90℃のクリーンオーブン上で5分間プレベークすることにより0.5μm厚の塗膜を形成した。次いで、得られた塗膜に石英マスク(コンタクト)を介して高圧水銀ランプを用い(露光機:大日本科研社製MA-1400)、露光量を500mJ/cm2として放射線照射を行った。その後、クリーンオーブンを用い100℃で10分ベークすることにより、塗膜を形成した。
実施例1~9で調製した樹脂組成物を用いた場合には、露光部(凹部)が親液部となり、露光部分以外(凸部)が撥液部となった、親液部と撥液部とによりパターニングされた膜(以下、「親撥パターニング膜」と称することがある。)が得られた。
前記[接触角]と同様の方法で得られた膜に関して、露光部(凹部)と未露光部(凸部)の膜厚を接触式膜厚計((株)キーエンス製:アルファステップIQ)で測定した。そして、未露光部(撥液部)の膜厚と露光部(親液部)の膜厚との差を算出し、下記式からの膜厚減少率(%)を算出することにより凹パターニング形成性を確認した。
膜厚減少率(%)=(撥液部の膜厚-親液部の膜厚)×100/撥液部の膜厚
実施例1~9及び比較例1~2で調製した樹脂組成物を用いて、立体構造物上での膜形成を行い、以下の評価を実施した。結果を表2に示す。
図1(A)~(C)に示す形状の立体構造物a~c上に、実施例1~9又は比較例1~2で調製した樹脂組成物をそれぞれスプレーコートした後、90℃のクリーンオーブン上で5分間ベークして溶剤を乾燥させ0.5μm厚の塗膜を形成した。次いで、得られた塗膜に、図2(A)~(C)に示す形状の凹パターンを有する構造体が形成されるように、所望の遮光部と500μm幅の直線状の透過部を有するフィルムシールを貼った。該フィルムシールを貼った立体構造物に高圧水銀ランプ(露光機:(株)大日本科研製、MA-1400)を用い、塗膜の露光量が500mJ/cm2になるように放射線照射を行った。その後、フィルムシールを剥離し、クリーンオーブンを用い100℃で10分ベークすることにより、塗膜を形成した。
立体構造物bは、ポリカーボネート/AES樹脂(「CW50」:テクノポリマー社製)からなる立体構造物であり、この立体構造物の図1(B)における上面全体に樹脂組成物をスプレーコートした。
立体構造物cは、ポリカーボネート/ABS(アクリロニトリル・ブタジエン・スチレン)樹脂(「CK50」:テクノポリマー社製)からなる立体構造物であり、この立体構造物の表面全体に樹脂組成物をスプレーコートした。
[立体構造物への凹パターン形成]の評価と同様の方法で塗膜付立体構造物を作成した。この塗膜付立体構造物について、立体構造物が劣化しておらず、目視で確認可能な凹パターンが形成されていれば良好(○)、目視で確認可能な凹パターンが形成できていない場合や立体構造物に目視で膜荒れ、白化等が起こっていれば不良(×)として目視での外観の評価を行った。
[立体構造物への凹パターン形成]の評価と同様の方法で塗膜付立体構造物を作成した。この塗膜付立体構造物について、凹パターンを含む1cm角の四角状の塗膜部分にカッターナイフを用いて切り込みを入れ、該部分でテープ剥離試験(CT-18セロテープ、ニチバン(株)製)を実施し、塗膜と立体構造物との密着性を評価した。
剥離が生じなければ良好(○)と評価し、剥離が生じた場合を不良(×)として評価を行った。
前記[立体構造物への凹パターン形成]で得られた直線状の凹パターンを有する塗膜の凹パターン上に、銀ナノインクNPS-JL(ハリマ化成(株)製)を滴下し、該インクが流動し終わった後にクリーンオーブンで100℃で60分焼成することで銀配線を形成した。形成された銀配線について、500μm幅の直線状の銀配線が得られ、銀配線部の長さ10cm間隔の2点で2000型デジタルマルチメーター(ケースレー社製)を用いた抵抗を測定し、断線無く導通が確認できれば(○)、500μm幅の直線状の銀配線が得られなければ(×)として評価した。
尚、直線状の銀配線が得られているか否かは、光学顕微鏡(エクリプスL200D、(株)ニコン製)を用いて確認した。
前記[立体構造物への凹パターン形成]で得られた直線状の凹パターンを有する立体構造物を、銀ナノインクNPS-JL(ハリマ化成(株)製)中に3秒浸漬し、その後立体構造物を引き上げ、立体構造体a及びbを用いた場合には傾斜をつけて静置し(例えば、図2の(A)及び(B)において上面が床面に対し60°以上となるような角度で静置し)、立体構造体cを用いた場合には図2の(C)の向きで静置した。その後クリーンオーブンで100℃で60分焼成することで銀配線を形成した。形成された銀配線について、500μm幅の直線状の銀配線が得られ、銀配線部の長さ10cm間隔の2点で2000型デジタルマルチメーター(ケースレー社製)を用いた抵抗を測定し、断線無く導通が確認できれば(○)、500μm幅の直線状の銀配線が得られなければ(×)として評価した。
尚、直線状の銀配線が得られているか否かは、光学顕微鏡(エクリプスL200D、(株)ニコン製)を用いて確認した。
[金属配線形成:滴下法]及び[金属配線形成:ディップ法]の評価と同様の方法で銀配線付立体構造物を作成した。この銀配線付立体構造物について、銀配線が孤立した1cm長になるようカッターナイフで切り込みを入れ、該部分でテープ剥離試験(CT-18セロテープ、ニチバン(株)製)を実施し、銀配線と塗膜との密着性を評価した。
剥離が生じなければ良好(○)と評価し、剥離が生じた場合を不良(×)として評価を行った。
表2の結果から、塗布面が非平坦面である構造体に対し、実施例1~9で調製された樹脂組成物を用いて形成された親撥パターニング膜は、比較例1~2で調製された樹脂組成物を用いて形成された塗膜と比べ、良好な親撥性能、外観及び密着性を有し、所望の凹パターンを有することがわかった。すなわち、実施例1~9で調製された樹脂組成物は、凹パターンを有する立体構造物の製造に好適に使用できることがわかった。
尚、立体構造物a~c上に形成された塗膜の凹パターン部と放射線未照射部の膜厚及び接触角は、前記平板上の基板に形成した塗膜と同程度であると考えられる。
すなわち、実施例1~9で調製された樹脂組成物は、凹パターンを有する立体構造物の凹パターン上に導電膜を形成するのに好適に使用できることがわかった。
20:立体構造物b
30:立体構造物c
12:塗膜付立体構造物a
14:凹パターン又は銀配線
22:塗膜付立体構造物b
24:凹パターン又は銀配線
32:塗膜付立体構造物c
34:凹パターン又は銀配線
Claims (15)
- 下記工程(i)及び(ii)を含み、下記工程(i)で得られる塗膜の膜厚に対して、5%以上90%未満薄い膜厚の凹パターンを有する、構造体の製造方法。
(i)酸解離性基を有する重合体及び酸発生剤を含む樹脂組成物を用いて、構造体の非平坦面に塗膜を形成する工程
(ii)前記塗膜の一部の所定部分に放射線照射を行うことにより凹部を形成する工程 - さらに、(iii)放射線照射後の塗膜を加熱する工程を含む、請求項1に記載の製造方法。
- 前記非平坦面が、曲面及び凹凸面からなる群より選ばれる少なくとも1種の面を含む、請求項1又は2に記載の製造方法。
- 前記酸解離性基がフッ素原子を含む、請求項1~3のいずれか一項に記載の製造方法。
- 凹パターン部と放射線未照射部とのテトラデカンに対する接触角差が30°以上である、請求項1~4のいずれか一項に記載の製造方法。
- 前記酸解離性基が、アセタール結合及びヘミアセタールエステル結合からなる群より選ばれる少なくとも1つの結合を含む基である、請求項1~5のいずれか一項に記載の製造方法。
- 前記樹脂組成物が、エチレン性不飽和結合を有する重合性化合物を含む、請求項1~7のいずれか一項に記載の製造方法。
- 前記樹脂組成物が、下記式(2)~(5)で示される構成単位の群から選ばれる少なくとも1つを有する、請求項1~8のいずれか一項に記載の製造方法。
(式(2)~(5)中、R3は独立して、水素原子又はメチル基を示す。R4は独立して、メチレン基、炭素数2~12のアルキレン基、炭素数2~12のアルケニレン基、該アルキレン基又はアルケニレン基の一部が、-O-、-(C=O)O-又は-O(C=O)-で置換された基、炭素数6~13の置換若しくは非置換の芳香族炭化水素基、炭素数4~12の置換若しくは非置換の脂環式炭化水素基、又は、これらの基の1つ以上の水素原子がフッ素原子で置換された基を示す。R5は独立して、炭化水素基の1つ以上の水素原子がフッ素原子で置換された基を示す。mは0又は1を示す。nは独立して0~12の整数を示す。) - 請求項1~9のいずれか一項に記載の製造方法に用いる、樹脂組成物。
- フッ素原子を含む酸解離性基を有する重合体、及び酸発生剤を含有する樹脂組成物。
- アセタール結合及びヘミアセタールエステル結合からなる群より選ばれる少なくとも1つの結合を含む酸解離性基を有する重合体、並びに、酸発生剤を含有する樹脂組成物。
- 請求項1~9のいずれか一項に記載の製造方法で形成された凹パターン上に、導電膜形成用組成物を用いて導電膜を形成する工程を含む、導電膜の形成方法。
- 請求項13に記載の導電膜の形成方法で形成された導電膜を有する、電子回路。
- 請求項14に記載の電子回路を有する、電子デバイス。
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| CN201580048538.2A CN107073516B (zh) | 2014-09-12 | 2015-09-08 | 具有凹图案的构造体的制造方法、树脂组合物、导电膜的形成方法、电子电路及电子器件 |
| US15/509,662 US10392699B2 (en) | 2014-09-12 | 2015-09-08 | Method for manufacturing structure having recessed pattern, resin composition, method for forming electroconductive film, electronic circuit, and electronic device |
| KR1020177005886A KR20170053620A (ko) | 2014-09-12 | 2015-09-08 | 오목 패턴을 갖는 구조체의 제조 방법, 수지 조성물, 도전막의 형성 방법, 전자 회로 및 전자 디바이스 |
| JP2016547445A JP6528776B2 (ja) | 2014-09-12 | 2015-09-08 | 凹パターンを有する構造体の製造方法、樹脂組成物、導電膜の形成方法、電子回路及び電子デバイス |
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| US (1) | US10392699B2 (ja) |
| JP (1) | JP6528776B2 (ja) |
| KR (1) | KR20170053620A (ja) |
| CN (1) | CN107073516B (ja) |
| WO (1) | WO2016039327A1 (ja) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019001913A (ja) * | 2017-06-15 | 2019-01-10 | Jsr株式会社 | 硬化性樹脂組成物、感放射線性脂組成物 |
| JPWO2021166619A1 (ja) * | 2020-02-20 | 2021-08-26 |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020218062A1 (ja) * | 2019-04-24 | 2020-10-29 | Jsr株式会社 | 感光性樹脂組成物、レジストパターン膜の製造方法、およびメッキ造形物の製造方法 |
| CN112321875B (zh) * | 2020-11-01 | 2023-02-03 | 浙江世窗光学薄膜制造有限公司 | 带有花纹的自修复弹性体保护膜及其制备方法 |
| KR102645392B1 (ko) * | 2021-07-28 | 2024-03-11 | 한국다이요잉크 주식회사 | 전자기기의 제조를 위한 곡면 커버 부재의 제조방법 |
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| JP2012232434A (ja) | 2011-04-28 | 2012-11-29 | Dic Corp | 導電性インク受容層形成用樹脂組成物、導電性インク受容基材及び回路形成用基板ならびに印刷物、導電性パターン及び回路基板 |
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- 2015-09-08 WO PCT/JP2015/075441 patent/WO2016039327A1/ja not_active Ceased
- 2015-09-08 CN CN201580048538.2A patent/CN107073516B/zh active Active
- 2015-09-08 KR KR1020177005886A patent/KR20170053620A/ko not_active Ceased
- 2015-09-08 JP JP2016547445A patent/JP6528776B2/ja active Active
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Also Published As
| Publication number | Publication date |
|---|---|
| US20170306481A1 (en) | 2017-10-26 |
| KR20170053620A (ko) | 2017-05-16 |
| US10392699B2 (en) | 2019-08-27 |
| CN107073516B (zh) | 2020-09-15 |
| JPWO2016039327A1 (ja) | 2017-06-22 |
| JP6528776B2 (ja) | 2019-06-12 |
| CN107073516A (zh) | 2017-08-18 |
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