WO2021039187A1 - 転写フィルム、転写フィルムの製造方法、積層体の製造方法、積層体、タッチパネルセンサー、タッチパネル - Google Patents

転写フィルム、転写フィルムの製造方法、積層体の製造方法、積層体、タッチパネルセンサー、タッチパネル Download PDF

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WO2021039187A1
WO2021039187A1 PCT/JP2020/027887 JP2020027887W WO2021039187A1 WO 2021039187 A1 WO2021039187 A1 WO 2021039187A1 JP 2020027887 W JP2020027887 W JP 2020027887W WO 2021039187 A1 WO2021039187 A1 WO 2021039187A1
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liquid
transfer film
photosensitive resin
resin layer
mass
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PCT/JP2020/027887
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English (en)
French (fr)
Japanese (ja)
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児玉　邦彦
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富士フイルム株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • 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
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • 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
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • 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
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G—PHYSICS
    • G06—COMPUTING OR CALCULATING; COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G—PHYSICS
    • G06—COMPUTING OR CALCULATING; COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means

Definitions

  • the present invention relates to a transfer film, a method for manufacturing a transfer film, a method for manufacturing a laminate, a laminate, a touch panel sensor, and a touch panel.
  • Liquid crystal display elements or touch panels are used in large electronic devices such as personal computers and televisions, small electronic devices such as car navigation systems, mobile phones and electronic dictionaries, and display devices such as OA devices and FA devices. These liquid crystal display elements or touch panels have transparent electrodes. As a touch panel, various methods have already been put into practical use, and in recent years, the use of a capacitive touch panel has been advancing. Conventionally, as the transparent electrode, an electrode formed by using a material such as ITO (Indium Tin Oxide), indium oxide, and tin oxide is used, but as an alternative electrode, a conductive layer containing conductive fibers is used. It has been proposed to use a conductive pattern formed from a photosensitive conductive film having a texture in a photolithography step.
  • ITO Indium Tin Oxide
  • Patent Document 1 describes a photosensitive conductive film including a temporary support, a conductive layer provided on the temporary support and containing conductive fibers, and a photosensitive resin layer provided on the conductive layer. ing.
  • the present inventor examined the technique disclosed in Patent Document 1, and found that the transfer film described in Patent Document 1 is used when the unexposed portion of the photosensitive resin layer is developed with a developing solution to form a conductive pattern. It was found that there is room for improvement in developability.
  • the means for solving the above problems include the following aspects.
  • the binder polymer has a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylic acid alkyl ester.
  • a method for producing a transfer film which comprises a laminating step.
  • the mass ratio of the content of the non-aromatic hydrocarbon solvent contained in the first liquid and the second liquid to the total amount of the solvent contained in the first liquid and the second liquid is 80% by mass or more [8]. ]
  • a method for producing a laminate having a substrate and a conductive pattern which is the transfer film according to any one of [1] to [7] or the production method according to any one of [8] to [15].
  • a method for producing a laminate which comprises a step of removing a part of the conductive layer of the transfer film together with an unexposed portion of the photosensitive resin layer to form a patterned conductive layer.
  • a laminate produced by the production method according to [16] which comprises a substrate and a patterned conductive layer containing silver nanowires.
  • a transfer film having better developability. Further, according to the present invention, it is possible to provide a method for manufacturing a transfer film, a method for manufacturing a laminate, a laminate, a touch panel sensor, and a touch panel.
  • (meth) acrylic acid is a concept including both acrylic acid and methacrylic acid
  • (meth) acrylate is a concept including both acrylate and methacrylate
  • ( "Meta) acryloyl group” is a concept that includes both acryloyl group and methacrylic acid group.
  • the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition. means.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present specification are TSKgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL and / or TSKgel Super HZM-N (all of which are manufactured by Toso Co., Ltd.).
  • the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight (Mw).
  • the dispersity also referred to as polydispersity
  • Mw / Mn the weight average molecular weight of the weight average molecular weight (Mw) and the number average molecular weight (Mn).
  • the term "process” is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes. ..
  • the term "exposure” as used herein includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams.
  • the light used for exposure is generally the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet light (EUV (Extreme ultraviolet) light), and active light (active energy) such as X-rays. Line).
  • the "main chain” means the relatively longest binding chain in the polymer, and the "constituent unit" of the polymer constitutes the binding chain which is the main chain.
  • the ratio of the constituent units of the polymer is a molar ratio. Further, in the present specification, a combination of two or more preferred embodiments is a more preferred embodiment. Hereinafter, the present invention will be described.
  • the transfer film of the present invention has a temporary support, a conductive layer, and a photosensitive resin layer.
  • the conductive layer contains silver nanowires.
  • the photosensitive resin layer contains a binder polymer having a dispersity (Mw / Mn) of 3.5 or less, a polymerizable compound, and a polymerization initiator.
  • the present inventor exposes the photosensitive resin layer when the transfer film having the above structure transfers the conductive layer and the photosensitive resin layer to the substrate using the transfer film having the above structure. It has been found that the photosensitive resin layer is easily removed by the developing treatment after the process, and the development residue is less likely to remain, so that the photosensitive resin layer after transfer is excellent in developability. Although the details are not clear, this is developed by a component having a relatively high molecular weight and a component having a relatively low molecular weight contained in the photosensitive resin layer because the dispersibility (Mw / Mn) of the binder polymer is small.
  • the transfer film may have a layer other than the temporary support, the conductive layer and the photosensitive resin layer, or may be composed of only the temporary support, the conductive layer and the photosensitive resin layer.
  • layers other than the temporary support, the conductive layer and the photosensitive resin layer include a protective film, an adhesive layer, and a gas barrier layer.
  • FIG. 1 and 2 show a configuration example of the transfer film.
  • the transfer film of the present invention is not limited to those having the configurations shown in FIGS. 1 and 2.
  • FIG. 1 is a schematic view showing an example of the configuration of the transfer film.
  • the temporary support 1, the conductive layer 2, the photosensitive resin layer 3, and the protective film 4 are laminated in this order.
  • FIG. 2 is a schematic view showing another example of the configuration of the transfer film.
  • the temporary support 1, the photosensitive resin layer 3, the conductive layer 2, and the protective film 4 are laminated in this order.
  • Each layer of the transfer film will be described in detail below.
  • the transfer film of the present invention has a temporary support.
  • the temporary support include a glass substrate and a resin film, and a resin film is preferable, and a resin film having heat resistance and solvent resistance is more preferable.
  • a film having flexibility and not causing significant deformation, shrinkage or elongation under pressure, or under pressure and heating is preferable.
  • a resin film include polyethylene terephthalate (PET) film, polyethylene film, polypropylene film and polycarbonate film. Of these, a polyethylene terephthalate film is preferable from the viewpoint of transparency and heat resistance.
  • the surface of the above resin film may be mold-released so that it can be easily peeled off from the photosensitive layer later.
  • a layer having particles is present in order to impart handleability.
  • the thickness of the temporary support is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, still more preferably 15 ⁇ m or more, from the viewpoint of mechanical strength.
  • the thickness of the temporary support is preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less, and 100 ⁇ m or less from the viewpoint of the resolution of the conductive pattern. More preferred. From the above points, the thickness of the temporary support is preferably 5 to 300 ⁇ m, more preferably 10 to 200 ⁇ m, and even more preferably 15 to 100 ⁇ m.
  • the thickness of each layer included in the transfer film is determined by observing a cross section including a direction perpendicular to the main surface of the layer using a scanning electron microscope (SEM) and based on the obtained observation image. It is a value obtained by measuring the thickness of 10 points or more and calculating the average value thereof.
  • SEM scanning electron microscope
  • the haze value of the temporary support is preferably 0.01 to 5.0%, more preferably 0.01 to 3.0%, and more preferably 0.01, from the viewpoint of the exposure sensitivity of the photosensitive resin layer and the resolution of the conductive pattern. -2.0% is more preferable, and 0.01-1.5% is particularly preferable.
  • the haze value is determined by a method based on JIS K 7105 (optical property test method for plastics), for example, using a commercially available turbidity meter such as NDH-1001DP (manufactured by Nippon Denshoku Kogyo Co., Ltd., trade name). Can be measured.
  • the temporary support preferably has a light transmittance of 50% or more at the wavelength of the irradiating active light (more preferably 365 nm). It is more preferably% or more, and even more preferably 70% or more.
  • the transmittance of the layer included in the transfer film is the emission light emitted through the layer with respect to the intensity of the incident light when the light is incident in the direction perpendicular to the main surface of the layer (thickness direction). It is a ratio of intensity and is measured using MCPD Series manufactured by Otsuka Electronics Co., Ltd.
  • the film used as the temporary support has no deformation such as wrinkles or scratches.
  • the number of fine particles, foreign substances, and defects contained in the temporary support is small.
  • the number of the above fine particles and foreign matter and defect diameter 1 ⁇ m is more preferably preferably 50 pieces / 10 mm 2 or less, more preferably 10/10 mm 2 or less, three / 10 mm 2 or less ..
  • the transfer film of the present invention has a conductive layer containing silver nanowires as conductive fibers.
  • the structure of the conductive layer is not particularly limited as long as it can obtain conductivity in the plane direction, but it is preferable that the conductive fibers come into contact with each other to form a network structure.
  • the conductive layer may be arranged on the surface of the photosensitive resin layer facing the temporary support, or may be arranged on the surface of the photosensitive resin layer opposite to the surface facing the temporary support. Further, after the transfer film is produced, a part of the components contained in the photosensitive resin layer (for example, a binder polymer) may be infiltrated into the conductive layer.
  • the silver nanowires contained in the conductive layer are wire-like conductive substances composed of silver or an alloy composed of silver and a metal other than silver. Further, the silver nanowire may have a structure in which a wire-shaped core made of silver is coated with a metal other than silver.
  • the structure coated with a metal other than silver includes not only a structure in which the entire surface of the core silver nanowire is coated, but also a structure in which a part thereof is coated.
  • a metal nobler than silver is preferable, gold, platinum or palladium is more preferable, and gold is further preferable.
  • the shape of the silver nanowire is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a columnar shape, a rectangular parallelepiped shape, and a columnar shape having a polygonal cross section.
  • the fiber diameter of the silver nanowire is preferably 1 to 50 nm, more preferably 2 to 20 nm, and even more preferably 3 to 10 nm.
  • the fiber length of the silver nanowire is preferably 1 to 100 ⁇ m, more preferably 2 to 50 ⁇ m, and even more preferably 3 to 10 ⁇ m.
  • the fiber diameter and fiber length of the silver nanowires are determined by arbitrarily selecting 20 silver nanowires from an observation image including a plurality of silver nanowires obtained by using a scanning electron microscope (SEM). It is a value obtained by arithmetically averaging the lengths of the minor axis and the major axis of silver nanowires.
  • Examples of the method for producing silver nanowires include a method of reducing silver ions with a reducing agent such as NaBH 4 and a method of using a polyol method. Further, a method for producing silver nanowires is described in paragraphs 0019 to 0024 of JP2011-149902A, and the contents of this publication are incorporated in the present specification.
  • the conductive layer may contain conductive fibers other than silver nanowires.
  • conductive fibers other than silver nanowires include metals such as gold, silver, copper and platinum, metal fibers made of alloys of these metals, and carbon fibers such as carbon nanotubes.
  • the shape of the conductive fiber may be the same as the shape of the silver nanowire described above, including its preferred embodiment.
  • the conductive layer may contain an organic conductor as well as conductive fibers.
  • the organic conductor is not particularly limited, and examples thereof include organic conductors such as polymers of thiophene derivatives and aniline derivatives. More specifically, polyethylene dioxythiophene, polyhexylthiophene, and polyaniline can be mentioned.
  • the thickness of the conductive layer varies depending on the use of the conductive pattern produced by using the transfer film and the required conductivity, but is preferably 1 ⁇ m or less, more preferably 1 nm or more and 0.5 ⁇ m or less, and 5 nm or more. It is more preferably 1 ⁇ m or less.
  • the thickness of the conductive layer is 1 ⁇ m or less, the light transmittance in the wavelength range of 450 to 650 nm is high, the pattern forming property is also excellent, and it is particularly suitable for producing a transparent electrode.
  • the method for forming the conductive layer is not particularly limited as long as it is a method capable of forming a layer containing silver nanowires.
  • a method for forming the conductive layer for example, a conductive composition containing silver nanowires is prepared, the conductive composition is applied to the surface of a temporary support or a photosensitive resin layer, and then the conductive composition is applied. Examples thereof include a method of drying the film to form a conductive layer.
  • the content of silver nanowires in the conductive composition is not limited as long as the coating film of the conductive composition can be formed, but is preferably 0.01 to 20% by mass with respect to the total mass of the conductive composition. , 0.1 to 10% by mass is more preferable.
  • the conductive composition preferably contains a solvent.
  • the solvent include water and organic solvents.
  • the conductive composition preferably contains water as a solvent, and more preferably contains water and an organic solvent.
  • an alcohol solvent is preferable.
  • the alcohol-based solvent is not particularly limited, and for example, alcohol having 1 to 5 carbon atoms, ethylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, glycerin, alcandiol propylene glycol having 3 to 6 carbon atoms, dipropylene glycol, 1 -Ethoxy-2-propanol, ethanolamine and diethanolamine can be mentioned.
  • the conductive composition may contain at least one selected from the group consisting of conductive fibers other than the silver nanowires described above, organic conductors, and dispersion stabilizers such as surfactants.
  • the content of water in the conductive composition is preferably 80% by mass or more, more preferably 90% by mass or more, based on the total mass of the conductive composition.
  • the upper limit is not particularly limited, but is preferably 99.99% by mass or less, more preferably 99.9% by mass or less, based on the total mass of the conductive composition.
  • the content of the organic solvent is preferably 0.01 to 20% by mass.
  • Examples of the coating method of the conductive composition include known methods such as a roll coating method, a comma coating method, a gravure coating method, an air knife coating method, a die coating method, a bar coating method, and a spray coating method. , Not limited to these.
  • the method for drying the coating film of the conductive composition is not particularly limited, and examples thereof include a method in which hot air having a temperature of 30 to 150 ° C. is applied to the coating film for 1 to 30 minutes using a hot air convection dryer. ..
  • the transfer film of the present invention has a photosensitive resin layer containing a binder polymer (hereinafter, also referred to as “specific polymer”) having a dispersity (Mw / Mn) of 3.5 or less, a polymerizable compound, and a polymerization initiator.
  • a binder polymer hereinafter, also referred to as “specific polymer” having a dispersity (Mw / Mn) of 3.5 or less
  • Mw / Mn dispersity
  • the photosensitive resin layer is preferably a negative photosensitive resin layer in which the solubility of the exposed portion in the developing solution is reduced by exposure and the non-exposed portion is removed by development.
  • the photosensitive resin layer is not limited to the negative photosensitive resin layer, and even if the photosensitive resin layer is a positive photosensitive resin layer in which the solubility of the exposed portion in the developing solution is improved by exposure and the exposed portion is removed by development. Good.
  • Specific polymers include, for example, (meth) acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenol resin, ester resin, urethane resin, epoxy resin and (meth) acrylic acid.
  • a binder polymer such as an epoxy (meth) acrylate resin obtained and an acid-modified epoxy (meth) acrylate acrylate resin obtained by reacting an epoxy (meth) acrylate resin with an acid anhydride, and having a degree of dispersibility (Mw / Mn). ) Is 3.5 or less.
  • a (meth) acrylic resin is preferable from the viewpoint of excellent alkali developability and film forming property.
  • a (meth) acrylic resin means a resin having a structural unit derived from a (meth) acrylic compound.
  • the content of the structural unit derived from the (meth) acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, based on all the structural units of the (meth) acrylic resin. ..
  • the (meth) acrylic resin may be composed of only a structural unit derived from the (meth) acrylic compound, or may have a structural unit derived from a polymerizable monomer other than the (meth) acrylic compound. .. That is, the upper limit of the content of the structural unit derived from the (meth) acrylic compound is 100% by mass or less with respect to the total mass of the (meth) acrylic resin.
  • Examples of the (meth) acrylic compound include (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylamide and (meth) acrylonitrile.
  • Examples of the (meth) acrylic acid ester include (meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, and (meth) acrylic acid ester.
  • Acrylic acid glycidyl ester (meth) acrylic acid benzyl ester, 2,2,2-trifluoroethyl (meth) acrylate, and 2,2,3,3-tetrafluoropropyl (meth) acrylate.
  • Meta) Acrylic acid alkyl esters are preferred.
  • (meth) acrylamide include acrylamide such as diacetone acrylamide.
  • As the (meth) acrylic compound forming the structural unit constituting the (meth) acrylic resin at least one selected from the group consisting of (meth) acrylic acid and (meth) acrylic acid alkyl ester is preferable.
  • Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, propyl (meth) acrylic acid, butyl (meth) acrylic acid, pentyl (meth) acrylic acid, and (meth).
  • (meth) acrylic acid ester a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms is preferable, and methyl (meth) acrylate or ethyl (meth) acrylate is more preferable.
  • the (meth) acrylic resin may have a structural unit other than the structural unit derived from the (meth) acrylic compound.
  • the polymerizable monomer forming the above-mentioned structural unit is not particularly limited as long as it is a compound other than the (meth) acrylic compound that is copolymerizable with the (meth) acrylic compound, and is, for example, styrene, vinyltoluene and ⁇ -methyl.
  • Styrene compounds which may have a substituent at the ⁇ -position such as styrene or an aromatic ring, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid, maleic acid anhydride, monomethyl maleate, monoethyl maleate and Examples thereof include maleic acid monoesters such as monoisopropyl maleate, fumaric acid, silicic acid, ⁇ -cyanosilicic acid, itaconic acid and crotonic acid. These polymerizable monomers may be used alone or in combination of two or more.
  • the (meth) acrylic resin preferably has a structural unit having an acid group from the viewpoint of improving the alkali developability.
  • the acid group include a carboxy group, a sulfo group, a phosphoric acid group and a phosphonic acid group.
  • the (meth) acrylic resin more preferably has a structural unit having a carboxyl group, and further preferably has a structural unit derived from the above-mentioned (meth) acrylic acid.
  • the content of the constituent unit having an acid group (preferably the constituent unit derived from (meth) acrylic acid) in the (meth) acrylic resin is excellent in developability with respect to the total mass of the (meth) acrylic resin. 10% by mass or more is preferable.
  • the upper limit is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less, in terms of excellent alkali resistance.
  • the (meth) acrylic resin has a structural unit derived from the above-mentioned (meth) acrylic acid alkyl ester.
  • the content of the structural unit derived from the (meth) acrylic acid alkyl ester in the (meth) acrylic resin is preferably 50 to 90% by mass, more preferably 65 to 90% by mass, based on all the structural units of the (meth) acrylic resin. preferable.
  • the (meth) acrylic resin a resin having both a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylic acid alkyl ester is preferable, and the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid are preferable.
  • a resin composed only of structural units derived from (meth) acrylic acid alkyl ester is more preferable.
  • an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate is also preferable.
  • the (meth) acrylic resin may have at least one selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from methacrylic acid alkyl ester in that the protective film is excellent in peelability. It is preferable to have both a structural unit derived from methacrylic acid and a structural unit derived from an alkyl methacrylate ester.
  • the total content of the structural units derived from methacrylic acid and the structural units derived from methacrylic acid alkyl ester in the (meth) acrylic resin is superior to that of all the structural units of the (meth) acrylic resin in that the protective film is excellent in peelability. 40% by mass or more is preferable, and 60% by mass or more is more preferable.
  • the upper limit is not particularly limited and may be 100% by mass or less, and 80% by mass or less is preferable from the viewpoint of excellent developability of the photosensitive resin layer after transfer and laminating property of the photosensitive resin layer.
  • the (meth) acrylic resin preferably has an ester group at the end in that the photosensitive resin layer after transfer is excellent in developability.
  • the terminal portion of the (meth) acrylic resin is composed of a site derived from the polymerization initiator used in the synthesis.
  • a (meth) acrylic resin having an ester group at the terminal can be synthesized by using a polymerization initiator that generates a radical having an ester group.
  • the method for producing a specific polymer is not particularly limited as long as it is a method capable of producing a polymer having a dispersity (Mw / Mn) of 3.5 or less.
  • a specific polymer may be produced by a known method of radically polymerizing a polymerizable monomer in the presence of a polymerization initiator.
  • the polymerization method at this time include a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, and a solution polymerization method.
  • a method for producing a specific polymer by a solution polymerization method will be described in detail.
  • a method for producing a specific polymer by a solution polymerization method for example, (I) A method of adding a second liquid containing a polymerizable monomer, a polymerization initiator and a solvent to a first liquid containing a solvent under heating conditions over 0.5 to 20 hours. (Ii) Under heating conditions, the third liquid containing the polymerizable monomer and the fourth liquid containing the polymerization initiator and the solvent are separately added to the first liquid containing the solvent over 0.5 to 20 hours. Method and (Iii) Examples thereof include a method of adding a fourth liquid containing a polymerization initiator and a solvent to a third liquid containing a polymerizable monomer and a solvent under heating conditions over 0.5 to 20 hours.
  • each of the above methods (i) to (iii) even if the polymerization initiator is decomposed before the polymerization reaction is started, the polymerizable monomer and the radical derived from the polymerization initiator are combined. It is preferable in that the reaction can be suppressed, the amount of high-molecular-weight polymer produced can be reduced, and the degree of dispersion of the polymer can be reduced.
  • the time for adding each of the solutions in the above methods (i) to (iii) is not limited to the above addition time as long as the entire amount of each solution is not added at once and a part thereof is added little by little. ..
  • the second liquid contains a solvent, the reaction between the polymerizable monomer in the second liquid and the radicals derived from the polymerization initiator can be suppressed.
  • the polymerizable monomer and the polymerization initiator are separated, they are derived from the polymerizable monomer and the polymerization initiator until the polymerization by the above method is performed. Does not react with the radicals. Therefore, it is more preferable to produce the specific polymer by the above methods (ii) and (iii).
  • the polymerizable monomer used for solution polymerization is selected depending on the specific polymer to be produced.
  • the polymerizable monomer used for solution polymerization is the above-mentioned (meth) acrylic compound.
  • the amount of the polymerizable monomer used in the solution polymerization is not particularly limited, but 10 mass with respect to the total mass of the reaction system from the viewpoint of reducing the amount of the raw material used, improving the volume efficiency, and reducing the amount of the residual monomer. % Or more is preferable, 15% by mass or more is more preferable, and 20% by mass or more is further preferable.
  • the upper limit is not particularly limited, but is preferably 80% by mass or less, more preferably 60% by mass or less, based on the total mass of the reaction system.
  • the reaction system means all reaction solutions used in solution polymerization.
  • the reaction system is the total amount of the first liquid and the second liquid in the above method (i), and the total amount of the first liquid, the third liquid and the fourth liquid in the above method (ii).
  • the reaction system is the total amount of the third and fourth liquids.
  • the content of the polymerizable monomer in the second liquid of the above method (i) is not particularly limited, and is preferably 10 to 95% by mass, more preferably 20 to 80% by mass, based on the total mass of the second liquid. ..
  • the content of the polymerizable monomer in the third liquid of the above method (ii) is not particularly limited, and is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total mass of the third liquid.
  • the upper limit is not particularly limited, and may be 100% by mass or less, preferably 95% by mass or less, and more preferably 90% by mass or less with respect to the total mass of the third liquid.
  • the content of the polymerizable monomer in the third liquid of the above method (iii) is not particularly limited, and is preferably 10 to 50% by mass, more preferably 15 to 40% by mass, based on the total mass of the third liquid. ..
  • solvents can be used, for example, ether-based solvents, ester-based solvents, ketone-based solvents, amide-based solvents, sulfoxide-based solvents, alcohol-based solvents, hydrocarbon-based solvents, and mixtures thereof.
  • ether-based solvents for example, ether-based solvents, ester-based solvents, ketone-based solvents, amide-based solvents, sulfoxide-based solvents, alcohol-based solvents, hydrocarbon-based solvents, and mixtures thereof.
  • ether solvent and an ether solvent, an ester solvent or a ketone solvent is preferable from the viewpoint of solubility of the polymerizable monomer and the produced polymer.
  • ether solvent examples include chain ethers such as diethyl ether, ethylene glycol dimethyl ether, and propylene glycol monomethyl ether, and cyclic ethers such as tetrahydrofuran and dioxane.
  • ester solvent examples include glycol ether esters such as methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, and methoxyethyl acetate.
  • ketone solvent examples include acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone.
  • Examples of the amide solvent include N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, and N-ethylpyrrolidone.
  • Examples of the sulfoxide solvent include dimethyl sulfoxide.
  • Examples of the alcohol solvent include methanol, ethanol and propanol.
  • Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as benzene, toluene and xylene, aliphatic hydrocarbon solvents such as hexane, and alicyclic hydrocarbon solvents such as cyclohexane.
  • the uniformity of the composition of the polymer to be produced, the solubility of the specific polymer in the photosensitive resin composition used for forming the photosensitive layer, and the ease of forming the photosensitive layer by coating the photosensitive resin composition (hereinafter, "coatability").
  • the content of the non-aromatic hydrocarbon solvent contained in the reaction solution is preferably 60% by mass or more, preferably 80% by mass, based on the total amount of the solvent contained in the reaction system of solution polymerization. The above is more preferable.
  • the upper limit is not particularly limited and may be 100% by mass or less. That is, all the solvents contained in the reaction system of solution polymerization may be non-aromatic hydrocarbon solvents.
  • the mass ratio of the content of the non-aromatic hydrocarbon solvent contained in the first liquid and the second liquid to the total amount of the solvent contained in the first liquid and the second liquid is 80% by mass or more. Is preferable.
  • the ratio is preferably 80% by mass or more.
  • the non-aromatic hydrocarbon solvent means a solvent having no aromatic ring in the molecule.
  • the boiling point of the solvent is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, still more preferably 120 ° C. or higher.
  • the viscosity of the solvent is not particularly limited, but the kinematic viscosity at 20 ° C. is preferably 1 mm 2 / sec or more, and more preferably 1.2 mm 2 / sec or more. These solvents can be used alone or in admixture of two or more.
  • the amount of the solvent used in the solution polymerization is not particularly limited, but is preferably 40 to 90% by mass, more preferably 50 to 80% by mass, based on the total mass of the reaction system. Further, the solvent may be the remainder of the polymerizable monomer and the polymerization initiator in the reaction system.
  • the content of the solvent contained in the second liquid is not particularly limited, and is preferably 5 to 90% by mass, more preferably 20 to 80% by mass, based on the total mass of the second liquid. Further, the content of the solvent contained in the second liquid is more preferably 40% by mass or more with respect to the total mass of the second liquid in that the photosensitive resin layer after transfer is excellent in developability.
  • the content of the solvent contained in the first liquid ((content of the solvent contained in the first liquid) / (contained in the second liquid) with respect to the content of the solvent contained in the second liquid.
  • the mass ratio of (solvent content)) is preferably 1/9 to 9/1, more preferably 2/8 to 8/2, in that the polymer produced is excellent in molecular weight uniformity.
  • the content of the solvent contained in the first liquid ((the content of the solvent contained in the first liquid) is higher than the content of the solvent contained in the second liquid.
  • Amount) / (content of solvent contained in the second liquid)) is more preferably 6/4 or less, further preferably 5/5 or less, and particularly preferably 4/6 or less.
  • the content of the solvent contained in the third liquid may be 0% by mass, that is, the third liquid may not contain the solvent.
  • the content of the solvent contained in the third liquid is preferably 5 to 80% by mass, more preferably 10 to 50% by mass, based on the total mass of the third liquid.
  • the content of the solvent contained in the fourth liquid is preferably 40 to 99% by mass, more preferably 70 to 97% by mass, based on the total mass of the fourth liquid.
  • the content of the solvent contained in the first liquid ((content of the solvent contained in the first liquid)) with respect to the content (total amount) of the solvent contained in the third liquid and the fourth liquid. ) / (Contents of solvent contained in the 3rd and 4th liquids)) is preferably 1/9 to 9/1 in terms of excellent molecular weight uniformity of the produced polymer, 2/8. ⁇ 8/2 is more preferable.
  • the content of the solvent contained in the third liquid is preferably 40 to 90% by mass, more preferably 40 to 80% by mass, based on the total mass of the third liquid.
  • the content of the solvent contained in the fourth liquid is preferably 50 to 99% by mass, more preferably 60 to 97% by mass, based on the total mass of the fourth liquid.
  • the content of the solvent contained in the fourth liquid ((content of the solvent contained in the fourth liquid) / (in the third liquid) with respect to the content of the solvent contained in the third liquid.
  • the mass ratio of the contained solvent)) is preferably 95/5 to 50/50, more preferably 90/10 to 60/40, in that the polymer produced is excellent in molecular weight uniformity.
  • the polymerization initiator (radical polymerization initiator) used for solution polymerization is not particularly limited, and examples thereof include azo compounds, peroxide compounds, and redox compounds.
  • examples of the radical polymerization initiator include dimethyl 2,2'-azobisisobutyrate, azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), t-butylperoxypivalate, and di.
  • the amount of the polymerization initiator used in the solution polymerization is not particularly limited, but is preferably 0.1 to 10% by mass, more preferably 0.5 to 6% by mass, based on the total mass of the polymerizable monomer.
  • the polymerization initiator can be used alone or in combination of two or more.
  • the temperature of the solution (reaction temperature) in the solution polymerization may be, for example, 30 to 150 ° C, preferably 50 to 120 ° C, and 55 to 110. °C is more preferable.
  • the solution polymerization time may be set depending on the type of the polymerizable monomer, the type of the polymerization initiator, and the reaction temperature, but is preferably 0.5 to 20 hours, more preferably 1 to 10 hours, and 1 to 8 hours. Is more preferable.
  • the solution polymerization time is the time for adding the second liquid in the case of the above method (i), and the time for adding the third liquid and the fourth liquid in the case of the above method (ii), respectively. In the case of the above method (iii), it is time to add the fourth solution. In the case of the above method (ii), the time for adding the third liquid and the fourth liquid may be the same or different.
  • the heating time may be set depending on the reaction temperature and the type of the polymerization initiator, but is preferably 1 to 10 hours, more preferably 2 to 8 o'clock.
  • the residual polymerizable monomer may be reduced by adding the polymerization initiator to the mixture again.
  • the polymer produced by solution polymerization may be recovered by precipitation or reprecipitation in contact with the poor solvent of the polymer. Further, a solution containing a polymer may be used for preparing a photosensitive resin composition without precipitation or reprecipitation.
  • the precipitation or reprecipitation solvent include an organic solvent, water, and a mixed solvent thereof.
  • the organic solvent include hydrocarbon solvents, halogenated hydrocarbon solvents, nitro compounds, nitrile solvents, ether solvents, ketone solvents, ester solvents, carbonate solvents, alcohol solvents, and carboxylic acid solvents. , And a mixed solution thereof.
  • the polymer precipitated by precipitation or reprecipitation is separated by filtration and recovered.
  • the filtration method include natural filtration, pressure filtration, vacuum filtration, centrifugal filtration and the like.
  • the acid value of the specific polymer is preferably 50 to 150 mgKOH / g from the viewpoint of developability.
  • the acid value of a particular polymer is measured as follows. First, 1 g of the polymer whose acid value should be measured is precisely weighed. 30 g of acetone is added to the polymer, and this is uniformly dissolved. Next, an appropriate amount of phenolphthalein, which is an indicator, is added to the above solution, and titration is performed using a 0.1 N KOH aqueous solution. The acid value is calculated by the following formula from the titration amount of the KOH aqueous solution.
  • Acid value 10 x Vf x 56.1 / (Wp x I)
  • Vf indicates the titer (mL) of the KOH aqueous solution
  • Wp indicates the measured mass (g) of the resin solution
  • I indicates the ratio of the non-volatile content (mass%) in the measured resin solution.
  • the dispersity (Mw / Mn) of the specific polymer is 3.5 or less.
  • the dispersity (Mw / Mn) of the specific polymer is preferably less than 2.5, more preferably less than 2.0, from the viewpoint of more excellent developability.
  • the lower limit is not particularly limited, but 1.5 or more is preferable, and more than 1.7 is more preferable, from the viewpoint of better laminating property.
  • the weight average molecular weight Mw of the specific polymer is preferably 5,000 to 300,000, more preferably 20,000 to 150,000, and 30,000 from the viewpoint of the balance between mechanical strength, developer resistance and developability. ⁇ 100,000 is more preferable.
  • the photosensitive resin layer may contain only one type of the above-mentioned resin as the specific polymer, or may contain two or more types of the above-mentioned resin.
  • the two or more kinds of resins that the photosensitive resin layer may contain include, for example, two or more kinds of resins having different structural units, two or more kinds of resins having different weight average molecular weights, and two kinds of resins having different dispersities.
  • the above resins can be mentioned.
  • the content of the specific polymer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, based on the total mass of the photosensitive resin layer from the viewpoint of the strength of the cured film and the handleability in the transfer film. , 30-70% by mass is more preferable.
  • the photosensitive resin layer contains a polymerizable compound having a polymerizable group.
  • a photopolymerizable compound having an ethylenically unsaturated group (hereinafter, also referred to as “ethylenically unsaturated compound”) is preferable.
  • An ethylenically unsaturated compound is a compound having one or more ethylenically unsaturated groups in one molecule.
  • an acryloyl group or a methacryloyl group is preferable.
  • the photosensitive resin layer preferably contains a bifunctional or higher functional ethylenically unsaturated compound as an ethylenically unsaturated compound from the viewpoint of curability after curing, and may contain a trifunctional or higher functional ethylenically unsaturated compound. More preferred. From the viewpoint of achieving both curability and developability after curing, it is preferable to use an ethylenically unsaturated compound having trifunctional or higher and hexafunctional or lower in combination with the specific polymer.
  • a bifunctional or higher functional ethylenically unsaturated compound means a compound having two or more ethylenically unsaturated groups in one molecule, and a trifunctional or higher and hexafunctional or lower ethylenically unsaturated compound is defined as a compound.
  • Examples of the ethylenically unsaturated compound include a compound obtained by reacting a polyhydric alcohol with an ⁇ , ⁇ -unsaturated carboxylic acid, and a compound obtained by reacting a glycidyl group-containing compound with an ⁇ , ⁇ -unsaturated carboxylic acid.
  • Urethane monomers such as (meth) acrylate compounds with urethane bonds, ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-(meth) acryloyloxyethyl-o-phthalate, ⁇ -hydroxyethyl- ⁇ '-(meth) acryloyl Examples thereof include phthalic acid compounds such as oxyethyl-o-phthalate and ⁇ -hydroxypropyl- ⁇ '-(meth) acryloyloxyethyl-o-phthalate, and (meth) acrylic acid alkyl esters. These are used alone or in combination of two or more.
  • Examples of the compound obtained by reacting a polyvalent alcohol with ⁇ , ⁇ -unsaturated carboxylic acid include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis.
  • Bisphenol A-based (meth) acrylate compounds such as (4-((meth) acryloxypolypropoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane , Polyethylene glycol di (meth) acrylate having an ethylene oxide group number of 2 to 14, polypropylene glycol di (meth) acrylate having a propylene oxide group number of 2 to 14, and an ethylene oxide group number of 2 to 14.
  • a polymerizable compound having a trimethylolpropane structure is preferable, and trimethylolpropane tri (meth) acrylate or di (trimethylolpropane) tetraacrylate is more preferable.
  • the urethane monomer examples include a (meth) acrylic monomer having a hydroxyl group at the ⁇ -position and a diisocyanate compound such as isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate.
  • a diisocyanate compound such as isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate.
  • Tris [(meth) acryloxytetraethylene glycol isocyanate] hexamethylene isocyanurate, ethylene oxide-modified urethane di (meth) acrylate, and ethylene oxide and propylene oxide-modified urethane di (meth) acrylate examples include Tris [(meth) acryloxytetraethylene glycol is
  • Examples of the ethylene oxide-modified urethane di (meth) acrylate include "UA-11” (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name). Examples of ethylene oxide and propylene oxide-modified urethane di (meth) acrylate include “UA-13” (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name).
  • the photosensitive resin layer may contain only one type of polymerizable compound, or may contain two or more types.
  • the content of the polymerizable compound is preferably 30 to 80 parts by mass, more preferably 40 to 70 parts by mass, based on 100 parts by mass of the total amount of the specific polymer and the polymerizable compound. 30 parts by mass or more is preferable from the viewpoint of excellent photocurability and coatability on the formed conductive layer, and 80 parts by mass or less is preferable from the viewpoint of excellent storage stability when wound as a film.
  • the content of the polymerizable compound in the photosensitive resin layer is preferably 1 to 70% by mass, more preferably 10 to 60% by mass, still more preferably 20 to 50% by mass, based on the total mass of the photosensitive resin layer. ..
  • the weight average molecular weight (Mw) of the polymerizable compound is preferably 200 to 3,000, more preferably 250 to 2,600, further preferably 280 to 2,200, and particularly preferably 300 to 2,200.
  • the photosensitive resin layer contains a polymerization initiator.
  • the polymerization initiator is not particularly limited as long as it is a compound capable of polymerizing a polymerizable compound by irradiation with active light such as ultraviolet rays, visible light and X-rays to cure the photosensitive resin layer.
  • Examples of the polymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferable from the viewpoint of excellent photocurability.
  • Examples of the photoradical polymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter, also referred to as “oxym ester compound”), a photopolymerization initiator having an ⁇ -aminoalkylphenone structure, and an ⁇ -hydroxyalkylphenone structure.
  • Examples thereof include a photopolymerization initiator having an acylphosphine oxide structure, a photopolymerization initiator having an acylphosphine oxide structure (hereinafter, also referred to as “acylphosphine oxide-based compound”), and a photopolymerization initiator having an N-phenylglycine structure.
  • More specific photoradical polymerization initiators include, for example, benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michlerketone), N, N'-tetraethyl-4,4'-diaminobenzophenone, and the like.
  • substituents of the two aryl groups in 2,4,5-triarylimidazole may be the same or different.
  • a thioxanthone-based compound and a tertiary amine compound may be combined, such as a combination of diethylthioxanthone and dimethylaminobenzoic acid.
  • the photoradical polymerization initiator for example, the polymerization initiator described in paragraphs 0031 to 0042 of JP2011-0957116 and paragraphs 0064 to 0081 of JP2015-014783 may be used.
  • an oxime ester compound or an acylphosphine oxide compound is preferable from the viewpoint of excellent transparency and pattern forming ability at 10 ⁇ m or less, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) is preferable.
  • 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) is preferable.
  • -Butanone-1,1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), or 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide preferable.
  • the photosensitive resin layer may contain only one type of polymerization initiator, or may contain two or more types of polymerization initiators.
  • the content of the polymerization initiator is not particularly limited, but is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and 1 to 10% by mass with respect to the total mass of the photosensitive resin layer. Is more preferable.
  • the content of the polymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 1 to 15 parts by mass, and 1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the specific polymer and the polymerizable compound. More preferred. From the viewpoint of excellent light sensitivity, 0.1 part by mass or more is preferable, and from the viewpoint of excellent photocurability inside the photosensitive resin layer, 20 parts by mass or less is preferable.
  • the photosensitive resin layer preferably contains a leveling agent from the viewpoint of improving the coatability of the photosensitive resin composition.
  • the leveling agent include various surfactants such as silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants, and silicone-based surfactants. Activators are preferred.
  • the silicone-based surfactant include a linear polymer composed of a siloxane bond and a modified siloxane polymer having an organic group introduced into a side chain or a terminal.
  • leveling agent examples include DOWNSIL8032 ADDITIVE manufactured by Toray Dow Corning Co., Ltd., and X-22-4952, X-22-2472, X-22-6266, KF-351A, K354L manufactured by Shin-Etsu Chemical Co., Ltd. , KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, and KF-6004. From the viewpoint of achieving both the coatability of the photosensitive resin composition and the developability of the photosensitive resin layer after transfer, it is preferable to use the specific polymer and the silicone-based surfactant in combination.
  • the photosensitive resin layer may contain various additives, if necessary.
  • Additives include plasticizers such as p-toluenesulfonamide, fillers, defoamers, flame retardants, stabilizers, adhesion imparting agents, peeling accelerators, antioxidants, fragrances, imaging agents, thermal cross-linking agents, etc. Can be mentioned.
  • the photosensitive additive can be contained alone or in combination of two or more.
  • the amount of these additives added is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of the specific polymer and the polymerizable compound.
  • the thickness of the photosensitive resin layer is not particularly limited, but the thickness after drying is preferably 1 to 200 ⁇ m, more preferably 2 to 15 ⁇ m, still more preferably 3 to 10 ⁇ m.
  • the thickness of the photosensitive resin layer is 1 ⁇ m or more, the layer formation tends to be facilitated by applying the photosensitive resin composition.
  • the thickness of the photosensitive resin layer is 200 ⁇ m or less, the light transmittance and the sensitivity are improved, and the photocurability of the photosensitive resin layer is more excellent, which is preferable.
  • the thickness of the photosensitive resin layer can be measured by using known means such as a micro gauge and a thickness gauge in addition to the scanning electron microscope.
  • the product of the thickness value ( ⁇ m) of the photosensitive resin layer and the specific polymer (Mw / Mn) contained in the photosensitive resin layer is determined. It is preferably less than 25.0, more preferably less than 22.0, even more preferably less than 17.0, and particularly preferably less than 16.5.
  • the lower limit is not particularly limited, but 4.0 or more is preferable, and 6.0 or more is more preferable.
  • the method for forming the photosensitive resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components.
  • a method for forming the photosensitive resin layer for example, a photosensitive resin composition containing a specific polymer, a polymerizable compound, a polymerization initiator and a solvent is prepared, and the photosensitive resin composition is formed on the surface of a temporary support or a conductive layer. Examples thereof include a method of forming a photosensitive resin layer by drying a coating film of the photosensitive resin composition after applying the material.
  • the photosensitive resin composition preferably contains a solvent in order to adjust the viscosity of the photosensitive resin composition and facilitate the formation of a coating film.
  • the solvent contained in the photosensitive resin composition is not particularly limited as long as it can dissolve or disperse a specific polymer, a polymerizable compound, a polymerization initiator and the above-mentioned additives optionally contained, and a known solvent is used. it can.
  • the content of the solvent contained in the photosensitive resin composition is preferably 30 to 95% by mass, preferably 50 to 90% by mass, based on the total mass of the photosensitive resin composition from the viewpoint of improving the developability of the photosensitive resin layer.
  • the mass% is more preferable, and 65 to 80% by mass is further preferable.
  • an organic solvent is preferable.
  • the organic solvent include methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, and a mixed solvent thereof.
  • the content of the organic solvent in the photosensitive resin layer after drying is such that the diffusion of the organic solvent in a later step is prevented. It is preferably 2% by mass or less based on the total mass of the photosensitive resin layer.
  • Examples of the coating method of the photosensitive resin composition include known methods such as a roll coating method, a comma coating method, a gravure coating method, an air knife coating method, a die coating method, a bar coating method, and a spray coating method. However, it is not limited to these.
  • the method for drying the coating film of the photosensitive resin composition is not particularly limited, and examples thereof include a method in which hot air having a temperature of 70 to 150 ° C. is applied to the coating film for 5 to 30 minutes using a hot air convection dryer. Be done.
  • the minimum light transmittance is preferably 80% or more, and more preferably 85% or more.
  • the transfer film preferably has a protective film that is in contact with a surface that does not face the temporary support.
  • a resin film having heat resistance and solvent resistance can be used, and examples thereof include a polyethylene terephthalate film, a polypropylene film, and a polyolefin film such as a polyethylene film.
  • a resin film made of the same material as the above-mentioned support film may be used. Among them, a polyolefin film is preferable, a polypropylene film or a polyethylene film is more preferable, and a polyethylene film is further preferable.
  • the thickness of the protective film is preferably 1 to 100 ⁇ m, more preferably 5 to 50 ⁇ m, further preferably 5 to 40 ⁇ m, and particularly preferably 15 to 30 ⁇ m.
  • the thickness of the protective film is preferably 1 ⁇ m or more in terms of excellent mechanical strength, and preferably 100 ⁇ m or less in terms of relatively low cost.
  • the adhesive force between the protective film and the photosensitive resin layer is such that the protective film can be easily peeled off from the photosensitive resin layer, so that the adhesive force between the temporary support and the photosensitive layer (conductive layer and photosensitive resin layer) Is preferably smaller than.
  • the protective film preferably contains 5 fish eyes / m 2 or less having a diameter of 80 ⁇ m or more.
  • fisheye means that when a film is produced by heat-melting a material, kneading, extruding, biaxial stretching, casting method, etc., foreign substances, undissolved substances, oxidative deterioration substances, etc. of the material are contained in the film. It was taken in.
  • the transfer film may further have at least one layer selected from the group consisting of an adhesive layer and a gas barrier layer on the surface of the protective film.
  • the method for producing the transfer film of the present invention is not particularly limited, and can be produced, for example, by a method including a laminating step of forming the above-mentioned conductive layer and the above-mentioned photosensitive resin layer on the surface of the temporary support.
  • a method for producing a transfer film will be described with reference to FIGS. 1 and 2.
  • the transfer film having the temporary support 1, the conductive layer 2 and the photosensitive resin layer 3 in this order is, for example, after the conductive composition is applied to the surface of the temporary support 1.
  • the step of forming the conductive layer 2 by drying the coating film of the conductive composition, and after applying the photosensitive resin composition to the surface of the conductive layer 2, the coating film of the photosensitive resin composition is dried. It is produced by a method including the step of forming the photosensitive resin layer 3.
  • the transfer film 10 shown in FIG. 1 is manufactured by adhering a resin film to the surface of the photosensitive resin layer 3 of the laminate manufactured by the above manufacturing method to form the protective film 4.
  • the transfer film having the temporary support 1, the photosensitive resin layer 3 and the conductive layer 2 in this order has, for example, a photosensitive resin composition on the surface of the temporary support 1.
  • the step of drying the coating film of the photosensitive resin composition to form the photosensitive resin layer 3, and after applying the conductive composition to the surface of the conductive layer 2, the coating film of the conductive composition is applied. It is produced by a method including a step of forming a conductive layer 2 by drying.
  • the transfer film 20 shown in FIG. 2 is manufactured by laminating a resin film on the surface of the conductive layer 2 of the laminate manufactured by the above manufacturing method to form the protective film 4.
  • the order of the conductive layer and the photosensitive resin layer in the transfer film is not particularly limited, and the temporary support 1, the conductive layer 2 and the photosensitive resin layer 3 are provided in this order as in the transfer film 10 shown in FIG.
  • the temporary support 1, the photosensitive resin layer 3 and the conductive layer 2 may be provided in this order as in the transfer film 20 shown in FIG.
  • a transfer film having a temporary support, a conductive layer, and a photosensitive resin layer in this order is preferable.
  • the photosensitive resin layer is arranged closer to the substrate, so that the removal of the photosensitive resin layer by the development treatment reduces the development residue derived from the photosensitive resin layer and the conductive layer. Is. Further, since the photosensitive resin layer has higher flexibility than the conductive layer, bubbles or floating between the substrate and the photosensitive resin layer are suppressed during transfer.
  • the transfer film may be stored, for example, in the form of a flat plate as it is, or in the form of a roll wound by using a cylindrical core.
  • the transfer film When the transfer film is wound in a roll form, it is preferable to wind the transfer film so that the temporary support is on the outermost side. Further, when the transfer film does not have a protective film, the transfer film can be stored as it is in a flat plate form.
  • the winding core is not particularly limited as long as it is conventionally used.
  • the material constituting the winding core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer). It is preferable to install an end face separator on the end face of the transfer film wound in a roll shape from the viewpoint of end face protection, and more preferably to install a moisture-proof end face separator from the viewpoint of edge fusion resistance. Further, when packing the transfer film, it is preferable to wrap it in a black sheet having excellent moisture permeability.
  • the use of the transfer film described above is not particularly limited, but since the photosensitive resin layer after transfer is excellent in developability, a transfer film for a laminate having a conductive pattern obtained by patterning a conductive layer having silver nanowires. It is preferable to use it as a transfer film for a touch panel, and it is more preferable to use it as a transfer film for a touch panel.
  • the above-mentioned transfer film and the substrate are bonded to each other by bringing the substrate into contact with the surface opposite to the surface on which the temporary support of the transfer film is arranged (hereinafter, "transfer”).
  • a step of pattern-exposing the photosensitive resin layer of the transfer film hereinafter also referred to as “exposure step”
  • exposure step a step of pattern-exposing the photosensitive resin layer of the transfer film
  • development step a step of forming a patterned conductive layer (conductive pattern)
  • a laminate having a substrate, a cured film formed by curing a patterned photosensitive resin layer, and a patterned conductive layer is manufactured.
  • the substrate contained in the laminate is not particularly limited, and examples thereof include a glass substrate and a plastic substrate such as polycarbonate.
  • the thickness of the substrate can be appropriately selected according to the purpose of use.
  • the substrate may be in the form of a film.
  • the film-like substrate include a polyethylene terephthalate film, a polycarbonate film, and a cycloolefin polymer film.
  • the substrate preferably has a minimum light transmittance of 80% or more in the wavelength range of 450 to 650 nm. When the substrate satisfies such conditions, it becomes easy to increase the brightness of the display panel or the like.
  • FIG. 3 is a schematic view for explaining an example of a method for manufacturing a laminate using a transfer film.
  • the manufacturing method using the transfer film 10 shown in FIG. 1 is described, but the manufacturing method of the laminate is not limited to the method using the transfer film having the configuration shown in FIG.
  • the transfer step it is preferable to press the photosensitive resin layer side of the transfer film onto the substrate while heating the photosensitive resin layer and / or the substrate.
  • the heating temperature and crimping pressure at this time are not particularly limited, but the heating temperature is preferably 70 to 130 ° C., and the crimping pressure is preferably about 0.1 to 1.0 MPa (about 1 to 10 kgf / cm 2 ). Further, from the viewpoint of adhesion and followability, it is preferable to carry out under reduced pressure. Further, instead of the heat treatment of the photosensitive resin layer and / or the substrate in the transfer step, the substrate may be preheat-treated before the transfer step in order to further improve the adhesion.
  • the photosensitive resin layer 3 is pattern-exposed.
  • a part of the photosensitive resin layer 3 is exposed by irradiating the active light L in an image shape through a negative or positive mask pattern 5 called artwork.
  • the photosensitive resin layer 3 is cured to form a cured film 3a.
  • the photosensitive resin layer 3 is not cured in the region (unexposed portion) not irradiated with the active light L.
  • the light source of the active light in the exposure process examples include known light sources.
  • the light source is not particularly limited as long as it is a light source that effectively irradiates the photosensitive resin layer with light having a wavelength that can be exposed (for example, 365 nm or 405 nm), and is, for example, a carbon arc lamp, a mercury vapor arc lamp, or an ultrahigh pressure mercury lamp. , High pressure mercury lamp and xenon lamp.
  • an Ar ion laser or a semiconductor laser may be used, or a photographic flood bulb or a solar lamp may be used.
  • a method of irradiating the active light beam in an image shape without using the mask pattern 5 may be adopted by a direct drawing method using a laser exposure method or the like.
  • Exposure at the exposure step may vary depending on the composition of the device and the photosensitive resin layer to be used is preferably 5 ⁇ 1000mJ / cm 2, more preferably 10 ⁇ 700mJ / cm 2. From the viewpoint of excellent photocurability, 10 mJ / cm 2 or more is preferable, and from the viewpoint of resolution, 1000 mJ / cm 2 or less is preferable.
  • the exposure atmosphere in the exposure process is not particularly limited and can be performed in air, nitrogen or vacuum.
  • a peeling step of peeling the temporary support 1 from the laminated body 30 is performed after the exposure step and before the developing step.
  • the method of peeling is not particularly limited, and a known method can be appropriately adopted.
  • the peeling step is performed after the exposure step of pattern-exposing the photosensitive resin layer 3 via the temporary support 1, but the temporary support is provided from the laminate 30 before the exposure step.
  • a peeling step for peeling the body 1 may be performed.
  • a patterned conductive layer (conductive pattern 2a) is formed by removing a part of the conductive layer 2 together with the unexposed portion of the photosensitive resin layer 3. Specifically, the uncured portion (unexposed portion) of the photosensitive resin layer 3 was removed by bringing the developer into contact with the exposed surface of the laminated body 30 exposed by peeling the temporary support 1. At this time, not only the unexposed portion of the photosensitive resin 3 but also the region of the conductive layer 2 in contact with the unexposed portion is removed.
  • a conductive pattern 2a composed of a patterned conductive layer 2 is formed, and a laminate having a substrate 20, a conductive pattern 2a, and a cured film (cured resin pattern 3a) of the patterned photosensitive resin layer 3 is formed.
  • Manufacture body 30 is
  • Examples of the developing solution include an alkaline aqueous solution, an aqueous developing solution, and an organic solvent-based developing solution.
  • the developing process in the developing step is performed by a known method such as spraying, rocking immersion, brushing and scraping using these developers, for example.
  • an alkaline aqueous solution is preferable because it is safe, stable, and has good operability.
  • As the alkaline aqueous solution 0.1 to 5% by mass sodium carbonate aqueous solution, 0.1 to 5% by mass potassium carbonate aqueous solution, 0.1 to 5% by mass sodium hydroxide aqueous solution, or 0.1 to 5% by mass tetraborax.
  • An aqueous solution of sodium carbonate is preferable.
  • the pH of the alkaline aqueous solution used as the developing solution is preferably in the range of 9 to 11.
  • the temperature of the developing solution is adjusted according to the developability of the photosensitive resin layer.
  • the alkaline aqueous solution may contain a surfactant, a defoaming agent, a small amount of an organic solvent for accelerating development, and the like.
  • an aqueous developing solution composed of water or an alkaline aqueous solution and one or more kinds of organic solvents
  • the base contained in the alkaline aqueous solution in addition to the above-mentioned sodium carbonate, potassium carbonate, sodium hydroxide and sodium tetraborate, for example, borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, etc.
  • borax sodium metasilicate
  • tetramethylammonium hydroxide ethanolamine
  • examples thereof include ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3-propanediol, 1,3-diaminopropanol-2, and morpholin.
  • organic solvent examples include methyl ethyl ketone, acetone, ethyl acetate, alkoxy ethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether. Can be mentioned. These are used alone or in combination of two or more.
  • the content of the organic solvent in the aqueous developer is preferably 2 to 90% by mass with respect to the total mass of the aqueous developer.
  • the temperature of the aqueous developer is adjusted according to the developability of the photosensitive resin layer.
  • the pH of the aqueous developer is not particularly limited as long as the photosensitive resin layer can be developed, but 8 to 12 is more preferable, and 9 to 10 is further preferable.
  • the aqueous developer may contain a small amount of additives such as a surfactant and an antifoaming agent.
  • organic solvent-based developer examples include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and ⁇ -butyrolactone.
  • the organic solvent-based developer preferably contains water in the range of 1 to 20% by mass in order to prevent ignition.
  • the above-mentioned developer may be used in combination of two or more, if necessary.
  • Examples of the development method include a dip method, a battle method, a spray method, brushing, and slapping. Of these, it is preferable to use the high pressure spray method from the viewpoint of improving the resolution.
  • the conductive pattern 2a is formed by heating at 60 to 250 ° C. or exposing with an exposure amount of 0.2 to 10 J / cm 2 as necessary after the developing step. It may be further cured.
  • the laminate having the conductive pattern obtained by the above manufacturing method can be applied to various uses.
  • Applications of the laminate having a conductive pattern include, for example, a touch panel (touch panel sensor), a semiconductor chip, various electric wiring boards, FPC (Flexible printed circuits), COF (Chip on Film), TAB (Tape Automated Bonding), an antenna, and the like. Examples thereof include a multilayer wiring board and a motherboard, which are preferably used for a touch panel sensor.
  • the conductive pattern of the laminated body functions as a detection electrode or a lead-out wiring in the touch panel sensor.
  • the touch panel is not particularly limited as long as it has the above-mentioned touch panel sensor.
  • the above-mentioned touch panel sensor is combined with various display devices (for example, a liquid crystal display device and an organic EL (electro-luminescence) display device).
  • display devices for example, a liquid crystal display device and an organic EL (electro-luminescence) display device.
  • Equipment is mentioned.
  • Examples of the detection method in the touch panel sensor and the touch panel include known methods such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method. Of these, a capacitive touch panel sensor and a touch panel are preferable.
  • the touch panel type includes a so-called in-cell type (for example, those shown in FIGS. 5, 6, 7, and 8 of JP-A-2012-517501), a so-called on-cell type (for example, JP-A-2013-168125).
  • the ones shown in FIG. 19 and those shown in FIGS. 1 and 5 of JP2012-081020A OGS (One Glass Solution) type, and TOR (Touch-on-Lens) type (for example, JP-A-2012).
  • 2013-054727 described in FIG. 2
  • various out-cell types so-called GG, G1 / G2, GFF, GF2, GF1, G1F, etc.
  • other configurations for example, Japanese Patent Application Laid-Open No.
  • the touch panel includes those described in paragraph 0229 of JP2017-120345A.
  • the touch panel manufacturing method is not particularly limited, and a known touch panel manufacturing method may be referred to except that the touch panel sensor having the above-mentioned laminated body is used.
  • Table 1 shows the composition of the monomer mixed solution containing the polymerizable monomer used for the synthesis of the polymer.
  • the polymerizable monomers used in each monomer mixture are as follows. ⁇ Methacrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) ⁇ Methyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) ⁇ Ethyl acrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
  • V-60 Azobisisobutyronitrile
  • V-601 Dimethyl 2,2'-azobis (2-methylpropionate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
  • the polymer synthesized in this example was measured by gel permeation chromatography (GPC) under the following conditions, converted using polystyrene as a standard substance, and had a weight average molecular weight Mw and a degree of dispersion (Mw / Mn). The value of was calculated.
  • the weight average molecular weight Mw of the synthesized polymer A1 was 65,000, and the dispersity (Mw / Mn) was 3.5.
  • the third liquid and the fourth liquid did not come into contact with each other until they were added to the first liquid.
  • the mixture was kept at a temperature of 80 ° C. for another 6 hours under stirring to synthesize polymer A4, and a composition containing polymer A4 was obtained.
  • the weight average molecular weight Mw of the synthesized polymer A4 was 65,000, and the dispersity (Mw / Mn) was 2.4.
  • Polymer A7 was synthesized according to the method described in Synthesis Example 4 to obtain a composition containing polymer A7.
  • the composition containing the obtained polymer A7 was added to a mixture of methanol and water (methanol: water mixture ratio of 70:30 by volume).
  • the precipitate was collected by filtration to obtain polymer A10.
  • the weight average molecular weight Mw of the obtained polymer A10 was 69,000, and the dispersity (Mw / Mn) was 1.7.
  • Example 1 [Preparation of silver nanowire dispersion] 500 mL of ethylene glycol was placed in a three-necked flask having a capacity of 2000 mL. Ethylene glycol was heated to 160 ° C. in an oil bath under a nitrogen atmosphere while stirring with a magnetic stirrer. Then, a solution in which 22 mg of PtCl was dissolved in 50 mL of ethylene glycol was added dropwise to the ethylene glycol in the three-necked flask.
  • reaction solution was left to stand until the temperature of the reaction solution became 30 ° C. or lower, and then the reaction solution was diluted 10-fold with acetone.
  • the diluent was centrifuged at 2000 rpm for 20 minutes with a centrifuge, and the supernatant was decanted.
  • Acetone was added to the obtained precipitate, and the mixture was stirred and then centrifuged under the same conditions as described above to decant the supernatant. Then, it was centrifuged twice using distilled water under the same conditions as above to obtain a silver nanowire-containing liquid.
  • the fiber diameter (diameter) was about 5 nm, and the fiber length was about 5 ⁇ m.
  • the silver nanowires and pentaethylene glycol monododecyl ether obtained above are added to pure water so that their contents are 0.2% by mass and 0.1% by mass, respectively, to obtain a silver nanowire dispersion. Prepared.
  • a photosensitive resin composition was prepared by mixing an amount of methyl ethyl ketone having a content of 28% by mass.
  • a 16 ⁇ m-thick PET film (manufactured by Toyobo Co., Ltd., trade name “A-1517”) was prepared as a temporary support.
  • the silver nanowire dispersion obtained above was uniformly applied to the surface of the temporary support so that the coating amount was 25 g / m 2, and the obtained coating film was coated with hot air at 100 ° C. using a hot air convection dryer. Was dried for 10 minutes.
  • a conductive layer containing silver nanowires as conductive fibers was formed on the surface of the temporary support.
  • the film thickness of the conductive layer after drying was 0.01 ⁇ m.
  • the solution of the photosensitive resin composition obtained above was stirred and then uniformly applied to the surface of the formed conductive layer.
  • the obtained coating film was dried with hot air at 100 ° C. using a hot air convection dryer for 10 minutes to form a photosensitive resin layer.
  • the film thickness of the formed photosensitive resin layer after drying was 7.0 ⁇ m.
  • a polyethylene film manufactured by Tamapoli Co., Ltd., trade name "NF-13" was attached to the surface of the formed photosensitive resin layer to form a protective film, and the transfer film of Example 1-1 was prepared.
  • Examples 1-2 to 1-17 according to the above method, except that polymers A2 to A10, B1 to B7, X1 and Y1 were used in place of the polymer A1 in the above method for preparing the photosensitive resin composition. And the transfer films of Comparative Examples 1-1 to 1-2 were prepared, respectively.
  • a laminate is produced by laminating the transfer film of Example 1-1 from which the protective film has been peeled off and a transparent film substrate (cycloolefin polymer film, thickness: 38 ⁇ m, refractive index: 1.53) (transfer step). did.
  • the above transfer step uses a vacuum laminator manufactured by MCK Co., Ltd. under the conditions of substrate temperature: 40 ° C., rubber roller temperature: 100 ° C., linear pressure: 3 N / cm, and transfer speed: 2 m / min. went. Further, in the above transfer step, the surface of the photosensitive resin layer exposed by peeling the protective film from the transfer film is brought into contact with the surface of the transparent film substrate.
  • a transparent electrode pattern film was produced according to the following procedure.
  • An exposure mask having a mask pattern (a quartz exposure mask having a transparent electrode forming pattern) and a temporary support, which will be described later, are brought into close contact with each other, and then a proximity type exposure machine having an ultra-high pressure mercury lamp (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.).
  • the photosensitive resin layer was pattern-exposed via an exposure mask and a temporary support using an exposure main wavelength: 365 nm (i-line) (exposure step).
  • the exposure amount was 100 mJ / cm 2 .
  • the temporary support was peeled from the laminated body (peeling step).
  • peeling step a 1% by mass aqueous solution of sodium carbonate having a liquid temperature of 32 ° C. was used as a developing solution for 60 seconds of development treatment (development step).
  • development step a 1% by mass aqueous solution of sodium carbonate having a liquid temperature of 32 ° C. was used as a developing solution for 60 seconds of development treatment (development step).
  • development treatment the unexposed photosensitive resin layer and the conductive layer laminated on the unexposed photosensitive resin layer were removed from the laminate.
  • the residue of the photosensitive resin layer is removed from the surface of the transparent film substrate by injecting ultrapure water from the ultrapure water cleaning nozzle onto the surface of the laminate on which the photosensitive resin layer and the conductive layer are formed. Removed.
  • a transparent electrode pattern film (laminated body having a conductive pattern) of 1-1 was obtained.
  • the transparent electrode pattern film having the patterned silver nanowire layer is a so-called circuit board.
  • Example 1-2 according to the above method, except that the transfer films of Examples 1-2 to 1-17 and Comparative Examples 1-1 to 1-2 were used instead of the transfer film of Example 1-1.
  • the transparent electrode pattern films of 1-17 and Comparative Examples 1-1 to 1-2 were prepared, respectively.
  • a transparent electrode pattern film for evaluation of developability was produced according to the above method for producing a transparent electrode pattern film, except that an exposure mask having the mask patterns shown in the following patterns 1 to 3 was used.
  • -Pattern 1 Line-and-space pattern with line width 50 ⁇ m and space width 50 ⁇ m
  • -Pattern 2 Line-and-space pattern with line width 75 ⁇ m and space width 25
  • ⁇ m-Pattern 3 Line-and-space pattern with line width 90 ⁇ m and space width 10 ⁇ m
  • the development residue in the space portion (unexposed portion) of the photosensitive resin layer is observed using an optical microscope and a scanning electron microscope (SEM). did. From the observation results, the developability of each transfer film was evaluated based on the following criteria. A: Development residue was not observed at the bottom of the space of the photosensitive resin layer B: Development residue was slightly observed at the bottom of the space of the photosensitive resin layer C: Development residue was not observed at the bottom of the space of the photosensitive resin layer Observed at the bottom of the part D: Development residue remained in the space part of the photosensitive resin layer, and the unexposed part of the photosensitive resin layer could not be removed until the transparent film substrate was exposed. The developability of each transparent electrode pattern film. The evaluation results of are shown in Table 3.
  • the laminate for evaluating the laminateability of Example 1-1 was prepared using the transfer film of Example 1-1.
  • the laminate for evaluation of laminateability of Example 1-1 has a PET substrate with a copper layer, a photosensitive resin layer, and a conductive layer.
  • Example 1 was carried out according to the above method. Laminates for evaluation of laminateability of -2-1-17 and Comparative Examples 1-1 to 1-2 were prepared, respectively.
  • a cycloolefin polymer film (thickness: 38 ⁇ m, refractive index: 1.53) having a copper electrode as a take-out wiring on the surface is used, and the surface of the photosensitive resin layer is used in the transfer process.
  • a transparent electrode pattern film was produced according to the method for producing a transparent electrode pattern film, except that the film was brought into contact with the surface of the cycloolefin polymer film on the side where the copper electrode was formed.
  • a capacitance type touch panel sensor was produced according to the method described in Japanese Patent No. 6173831. When we confirmed the operation of the manufactured touch panel sensors, they all operated normally.
  • Example 2 In the method for preparing the photosensitive resin composition of Example 1, the photosensitive resin composition was prepared by using an amount of methyl ethyl ketone having a solid content of 17% by mass, but the process was carried out according to the method described in Example 1. Transfer films of Examples 2-1 to 2-17 and Comparative Examples 2-1 to 2-2 were prepared. The film thickness of the photosensitive resin layer of each of the obtained transfer films after drying was 5.0 ⁇ m.
  • Example 3 The photosensitive resin composition of Example 3 was prepared according to the method for preparing the photosensitive resin composition of Example 1, except that the polymer A7 was used instead of the polymer A1.
  • a 16 ⁇ m-thick PET film (manufactured by Toyobo Co., Ltd., trade name “A-1517”) was prepared as a temporary support.
  • the solution of the photosensitive resin composition obtained above was stirred and then uniformly applied to the surface of the temporary support.
  • the obtained coating film was dried with hot air at 100 ° C. using a hot air convection dryer for 10 minutes to form a photosensitive resin layer.
  • the film thickness of the formed photosensitive resin layer after drying was 7.0 ⁇ m.
  • the silver nanowire dispersion liquid obtained above was uniformly applied to the surface of the formed photosensitive resin layer so that the coating amount was 25 g / m 2, and the obtained coating film was dried by hot air convection. It was dried for 10 minutes by hot air at 100 ° C. by a machine. As a result, a conductive layer containing silver nanowires as conductive fibers was formed on the surface of the photosensitive resin layer. The film thickness of the conductive layer after drying was 0.01 ⁇ m.
  • a polyethylene film manufactured by Tamapoli Co., Ltd., trade name "NF-13" was attached to the surface of the formed conductive layer to form a protective film, and a transfer film of Example 3-1 was prepared.
  • the transparent electrode pattern film of Example 3-1 was prepared according to the method described in Example 1, and the developability of the obtained transparent electrode pattern film was evaluated. Further, using the obtained transfer film, a laminate for evaluating the laminate property of Example 3-1 was prepared according to the method described in Example 1, and the laminate property of the obtained laminate was evaluated. Table 5 shows the evaluation results of the developability of the transparent electrode pattern film of Example 3-1 and the evaluation results of the laminate for evaluating the laminateability of Example 3-1.
  • the transfer film of the present invention is excellent in the developability of the photosensitive resin layer after transfer.
  • the dispersity (Mw / Mn) of the specific polymer is more preferably less than 2.5 from the viewpoint of being more excellent in the developability of the photosensitive resin layer after transfer (comparison between Examples 1-2 and 1-3, Comparison between Example 1-12 and Example 1-13, Comparison between Example 2-2 and Example 2-3, Comparison between Example 2-12 and Example 2-13), less than 2.0 Was further preferred (comparison between Example 1-6 and Example 1-7, comparison between Example 1-16 and Example 1-17). Further, it was confirmed that the dispersity (Mw / Mn) of the specific polymer was more preferably more than 1.7 from the viewpoint of more excellent laminating property of the photosensitive resin layer (Examples 2-7 and 2-7). Comparison with 10).
  • Parameter A (product of the thickness value ( ⁇ m) of the photosensitive resin layer and (Mw / Mn) of the specific polymer contained in the photosensitive resin layer) from the viewpoint of being more excellent in the developability of the photosensitive resin layer after transfer) Is more preferably less than 22.0 (comparison between Example 1-1 and Example 1-2, comparison between Example 1-11 and Example 1-12), further less than 17.0.
  • Preferably (comparison between Example 1-2 and Example 1-3, comparison between Example 1-12 and Example 1-13, comparison between Example 2-1 and Example 2-2, Example 2 -11 and Example 2-12), less than 16.5 is particularly preferred (Comparison of Examples 1-3 and 1-4 with Example 1-5, Examples 1-13 and 1-14 Comparison with Example 1-15) was confirmed.
  • the total of the structural units derived from methacrylic acid and the structural units derived from methacrylic acid in the (meth) acrylic resin because the developability of the photosensitive resin layer after transfer and the laminateability of the photosensitive resin layer are more excellent. It was confirmed that the content is preferably 80% by mass or less based on all the constituent units of the (meth) acrylic resin (comparison between Examples 1-6 and 1-9, Examples 2-6 and Implementation). Comparison with Example 2-9).
  • the (meth) acrylic resin preferably has an ester group at the terminal from the viewpoint of being more excellent in the developability of the photosensitive resin layer after transfer (Examples 1-6 and 1-7). Comparison, comparison between Example 1-16 and Example 1-17).
  • the content of the solvent contained in the second liquid is preferably 40% by mass or more with respect to the total mass of the second liquid from the viewpoint of being more excellent in the developability of the photosensitive resin layer after transfer (Example). Comparison between 1-3 and Example 1-8). Further, from the viewpoint that the developability of the photosensitive resin layer after transfer is more excellent, the content of the solvent contained in the first liquid ((of the solvent contained in the first liquid) is higher than the content of the solvent contained in the second liquid. It was confirmed that the content) / (content of the solvent contained in the second liquid)) was preferably 4/6 or less (comparison between Examples 1-3 and Examples 1-8).
  • the transfer film preferably has a temporary support, a conductive layer, and a photosensitive resin layer in this order from the viewpoint of being more excellent in the developability of the photosensitive resin layer after transfer (Examples 1-7 and 2). Comparison of -7 with Example 3-1).
  • Temporary support Conductive layer 2a Conductive pattern 3 Photosensitive resin layer 3a Cured resin pattern 4 Protective film 5 Mask pattern 10 Transfer film 20 Substrate 30 Laminated body L Active light beam

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JP2014085643A (ja) * 2012-10-26 2014-05-12 Fujifilm Corp 感光性転写材料、パターン形成方法およびエッチング方法
WO2017130427A1 (ja) * 2016-01-28 2017-08-03 日立化成株式会社 感光性樹脂組成物、感光性エレメント、レジストパターンの形成方法及びタッチパネルの製造方法
JP2018169543A (ja) * 2017-03-30 2018-11-01 富士フイルム株式会社 感光性転写材料、及び回路配線の製造方法
JP2018183878A (ja) * 2015-09-24 2018-11-22 日立化成株式会社 積層体及びその製造方法、フィルムセット、並びに、感光性導電フィルム
JP2019067818A (ja) * 2017-09-28 2019-04-25 日立化成株式会社 転写形導電フィルム及び積層体

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014085643A (ja) * 2012-10-26 2014-05-12 Fujifilm Corp 感光性転写材料、パターン形成方法およびエッチング方法
JP2018183878A (ja) * 2015-09-24 2018-11-22 日立化成株式会社 積層体及びその製造方法、フィルムセット、並びに、感光性導電フィルム
WO2017130427A1 (ja) * 2016-01-28 2017-08-03 日立化成株式会社 感光性樹脂組成物、感光性エレメント、レジストパターンの形成方法及びタッチパネルの製造方法
JP2018169543A (ja) * 2017-03-30 2018-11-01 富士フイルム株式会社 感光性転写材料、及び回路配線の製造方法
JP2019067818A (ja) * 2017-09-28 2019-04-25 日立化成株式会社 転写形導電フィルム及び積層体

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