WO2017209193A1 - 転写フィルム、加飾パターン及びタッチパネル - Google Patents

転写フィルム、加飾パターン及びタッチパネル Download PDF

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Publication number
WO2017209193A1
WO2017209193A1 PCT/JP2017/020305 JP2017020305W WO2017209193A1 WO 2017209193 A1 WO2017209193 A1 WO 2017209193A1 JP 2017020305 W JP2017020305 W JP 2017020305W WO 2017209193 A1 WO2017209193 A1 WO 2017209193A1
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Prior art keywords
resin layer
photosensitive resin
transfer film
mass
polymerizable monomer
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PCT/JP2017/020305
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English (en)
French (fr)
Japanese (ja)
Inventor
一真 両角
壮二 石坂
隆志 有冨
漢那　慎一
克己 篠田
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富士フイルム株式会社
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Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to CN201780025062.XA priority Critical patent/CN109073970B/zh
Priority to JP2018520963A priority patent/JP6703104B2/ja
Publication of WO2017209193A1 publication Critical patent/WO2017209193A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR 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
    • G06F3/0446—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a grid-like structure of electrodes in at least two directions, e.g. using row and column electrodes
    • 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
    • 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
    • G06—COMPUTING; CALCULATING OR 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; CALCULATING OR 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
    • G06F3/0445—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using two or more layers of sensing electrodes, e.g. using two layers of electrodes separated by a dielectric layer
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR 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
    • G06F3/045—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means using resistive elements, e.g. a single continuous surface or two parallel surfaces put in contact

Definitions

  • This disclosure relates to a transfer film, a decorative pattern, and a touch panel.
  • Various image display devices such as cathode ray tube display devices, plasma displays, electroluminescence displays, fluorescent display displays, field emission displays and liquid crystal display devices (LCDs), or smartphones or tablet terminals equipped with touch panels.
  • a decorative material having a decorative layer on the substrate is provided on the surface of the display for the purpose of applying various designs such as concealing the wiring arranged in the main body.
  • a decorative material provided with a decorative layer which is a black resin cured layer containing a black pigment, is widely used on the periphery of the surface of an image display device for the purpose of concealing wiring.
  • the decorative layer used for applications such as a touch panel may be formed using a transfer film having a photosensitive resin layer.
  • a step of transferring the photosensitive resin layer of the transfer film to a substrate a step of exposing the photosensitive resin layer with a desired pattern, and developing the photosensitive resin layer
  • the process passes through the process of heat-treating (baking) the photosensitive resin layer to form a tapered shape.
  • the photosensitive resin layer is softened by heat treatment, and the pattern is tapered, thereby preventing the pattern of the decorative layer from being chipped after the lapse of time and improving the concealment of the wiring, which is the purpose of the decorative layer. be able to.
  • a composition capable of forming a stable black resin cured layer for example, at least one of metal particles and metal-containing particles, and a high-boiling solvent having a boiling point of 120 ° C. or higher
  • a photosensitive resin composition containing at least one kind and at least one kind of a resin and a precursor thereof and having a content of 70% or more of the high boiling point solvent with respect to the total amount of the solvent is proposed (for example, JP 2008-256735 publication).
  • a photosensitive resin composition containing a resin having a glass transition temperature of 70 ° C. or lower, metal particles, a polymerizable monomer, and a polymerization initiator, and a light-shielding film for a display device using the photosensitive resin composition has been proposed (see, for example, Japanese Patent Application Laid-Open No. 2008-249868).
  • the photosensitive resin composition described in JP-A-2008-256735 and the photosensitive resin composition described in JP-A-2008-249868 are both compositions that form a black resin cured layer for color resist applications.
  • a baking process at a high temperature of 200 ° C. or higher is necessary after the pattern formation.
  • the high-temperature baking process is performed for the purpose of forming a hard film having excellent light shielding properties. It is not considered to soften the pattern and form a tapered shape by the baking process.
  • a resin base material may be used as the base material.
  • the heating temperature is 140 in the step of baking to form a tapered shape. It is required to perform a low-temperature baking process in which baking is performed at a relatively low temperature of about 150 ° C. to 150 ° C., and softening is required by the low-temperature baking process.
  • a taper shape cannot be formed by a low temperature baking process. It cannot be used for applications such as pattern formation.
  • the photosensitive resin layer before being subjected to the baking process becomes soft to some extent, and there is a problem that the protective film is difficult to peel off. It became clear by examination of inventors.
  • the protective film is roughened as a release treatment, the surface of the obtained photosensitive resin layer may be affected.
  • An object of one embodiment of the present invention is that a taper shape can be formed by a low-temperature baking process, preferably a low-temperature baking process at a heating temperature of about 140 ° C. to 150 ° C., and the transfer film has good peelability. Is to provide a film.
  • the subject of another embodiment of the present invention is to provide a touch panel having a tapered shape and a decorative pattern having a good appearance, and a decorative pattern having a tapered shape and a good appearance.
  • Means for solving the problem includes the following embodiments. ⁇ 1> a temporary support, a photosensitive resin layer provided on the temporary support, containing a binder, a polymerizable monomer, and a pigment; and a protective film provided in contact with the photosensitive resin layer;
  • the ratio of the content of the polymerizable monomer to the content of the binder in the photosensitive resin layer is 0.32 to 0.50 on a mass basis, and the surface roughness Rz of the surface of the protective film on the side in contact with the photosensitive resin layer Transfer film having a thickness of less than 0.12 ⁇ m.
  • ⁇ 2> The transfer film according to ⁇ 1>, wherein the protective film is a polyester film.
  • the pigment is a black pigment.
  • ⁇ 4> The transfer film according to any one of ⁇ 1> to ⁇ 3>, wherein the polymerizable monomer includes a bifunctional polymerizable monomer.
  • ⁇ 5> The transfer film according to any one of ⁇ 1> to ⁇ 4>, wherein the polymerizable monomer includes a polymerizable monomer having a molecular weight of 500 or less.
  • ⁇ 6> The transfer film according to any one of ⁇ 1> to ⁇ 5>, wherein the binder includes a binder having a weight average molecular weight of 5000 to 10,000.
  • ⁇ 7> The transfer film according to any one of ⁇ 1> to ⁇ 6>, further including a functional layer between the temporary support and the photosensitive resin layer.
  • ⁇ 8> The transfer film according to any one of ⁇ 1> to ⁇ 7>, wherein the surface roughness Rz is 0.01 ⁇ m or more and less than 0.12 ⁇ m.
  • ⁇ 9> The transfer film according to any one of ⁇ 1> to ⁇ 8>, wherein the ratio of the content of the polymerizable monomer to the content of the binder is 0.35 or more and less than 0.40 on a mass basis.
  • a decorative pattern which is a patterned cured product of the photosensitive resin layer in the transfer film according to any one of ⁇ 1> to ⁇ 9>.
  • ⁇ 11> A touch panel provided with the decoration pattern according to ⁇ 10>.
  • a taper shape can be formed by a low-temperature baking process, preferably a low-temperature baking process at a heating temperature of about 140 ° C. to 150 ° C., and a transfer film with good protective film peelability.
  • a film is provided.
  • a patterned cured product of the photosensitive resin layer in the transfer film of the above-described embodiment has a tapered shape, a decorative pattern with a good appearance, and a tapered shape. None, a touch panel having a decorative pattern with a good appearance is provided.
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • an upper limit value or a lower limit value described in a numerical range may be replaced with an upper limit value or a lower limit value in another numerical range.
  • the upper limit value or the lower limit value described in a certain numerical range may be replaced with the values shown in the examples.
  • the amount of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. .
  • the term “process” is not only an independent process, but is included in this term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes.
  • “(meth) acrylic acid” is a concept including both acrylic acid and methacrylic acid
  • “(meth) acrylate” is a concept including both acrylate and methacrylate
  • the “(meth) acryloyl group” is a concept including both an acryloyl group and a methacryloyl group.
  • total solid content means the total mass of nonvolatile components excluding the solvent contained in the composition.
  • the transfer film of the present disclosure includes a temporary support, a photosensitive resin layer that is provided on the temporary support, and contains a binder, a polymerizable monomer, and a pigment, and a protective film that is provided in contact with the photosensitive resin layer.
  • the ratio of the content of the polymerizable monomer to the content of the binder in the photosensitive resin layer is 0.32 to 0.50 on a mass basis, and the surface of the protective film on the side in contact with the photosensitive resin layer Is a transfer film having a surface roughness Rz of less than 0.12 ⁇ m.
  • the photosensitive resin layer provided in the transfer film of the present disclosure includes a binder and a polymerizable monomer, and the ratio of the content of the polymerizable monomer to the content of the binder in the photosensitive resin layer is 0.32 or more on a mass basis. Therefore, the heat dripping property when baking the patterned photosensitive resin layer formed after the development process of the photosensitive resin layer formed by the transfer film is improved, and the low temperature baking process, preferably the heating temperature However, it is easy to form a tapered shape in a patterned cured product formed by a low-temperature baking process of about 140 ° C. to 150 ° C.
  • the ratio of the content of the polymerizable monomer to the content of the binder in the photosensitive resin layer is 0.50 or less on a mass basis, so that the photosensitive resin layer and the photosensitive resin layer are present adjacent to each other. The peelability from the protective film is improved.
  • the content ratio of the binder and the polymerizable monomer in the photosensitive resin layer in the transfer film of the present disclosure within the above appropriate range, the balance between the taper-shaped formability by low-temperature baking and the peelability of the protective film becomes good. Furthermore, even when a protective film having excellent smoothness such that the surface roughness Rz of the surface in contact with the photosensitive resin layer of the protective film is less than 0.12 ⁇ m is used, the photosensitive resin layer can be easily removed from the protective film. Can be peeled off. Further, the surface of the photosensitive resin layer formed by peeling reflects the smooth surface of the protective film, so that the smoothness is excellent, and the decorative pattern formed by the transfer film of the present disclosure is excellent in appearance. It is thought that also plays.
  • the photosensitive resin layer in the transfer film of the present disclosure contains a binder, a polymerizable monomer, and a pigment.
  • a binder a polymerizable monomer
  • a pigment a pigment that is a binder for polymerizable monomer.
  • the photosensitive resin layer contains a binder.
  • the binder is preferably a resin that can be at least partially dissolved by contact with an alkaline solvent, and can be appropriately selected from known resins.
  • the binder for example, the resins described in paragraphs [0025] of JP 2011-95716 A and paragraphs [0033] to [0052] of JP 2010-237589 A can be appropriately selected and used.
  • the binder having a carboxy group As the binder, it is preferable to contain a binder having a carboxy group as the binder.
  • the binder having a carboxy group By containing the binder having a carboxy group, the linearity of the pattern end portion to be formed becomes better, and so-called edge roughness tends to be improved.
  • binder examples include a random copolymer of benzyl (meth) acrylate / (meth) acrylic acid, a random copolymer of styrene / (meth) acrylic acid, and cyclohexyl (meth) acrylate / (meth) acrylic acid.
  • binder Commercially available products may be used as the binder.
  • examples of commercially available products that can be used in one embodiment of the present invention will be given, and the weight average molecular weight (Mw) will also be described.
  • Commercially available products include, for example, Acrybase (registered trademark) FFS-6058 (Mw: 5000) and FF187 (Mw: 30000) manufactured by Fujikura Kasei Co., Ltd. 8KB series such as 13000).
  • a binder having a weight average molecular weight (Mw) in the range of 4000 to 30000 can be used.
  • the Mw of the binder is preferably in the range of 4000 to 25000, and more preferably in the range of 5000 to 10,000.
  • the Mw of the binder used in one embodiment of the present invention is 4000 or more (preferably 5000 or more)
  • the linearity of the pattern to be formed becomes good, and the tack of the pattern to be formed is suppressed.
  • the peelability is further improved.
  • the photosensitive resin layer according to one embodiment of the present invention more preferably contains a binder having an Mw in the range of 5000 to 10,000 in terms of further improving the taper shape productivity.
  • the photosensitive resin layer preferably has a small content of binder having an Mw of 21,000 or more, and the Mw is 21000 with respect to the total solid content of the photosensitive resin layer.
  • the content of the above binder is preferably 12% by mass or less, more preferably 9% by mass or less, and further preferably 0% by mass (that is, not included).
  • the weight average molecular weight of the binder can be measured by gel permeation chromatography (GPC) under the following conditions.
  • the calibration curve is “Standard Sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “A -2500 ",” A-1000 ", and” n-propylbenzene ".
  • the acid value of the binder is preferably 50 mgKOH / g or more from the viewpoint of improving the alkali solubility of the unexposed area during pattern formation and improving the linearity of the pattern.
  • the acid value of the binder is more preferably 70 mgKOH / g or more, and further preferably 100 mgKOH / g or more.
  • the acid value of the binder can be measured, for example, by the following method.
  • Propylene glycol monomethyl ether acetate is added to a resin solution (y (g)) having a solid content concentration (x (%)) and diluted to prepare a sample solution having a solid content concentration of 1 to 10 mass%.
  • a 0.1 mol / L potassium hydroxide / ethanol solution (titer a) was applied to the above sample solution using a potentiometric measuring device (manufactured by Hiranuma Sangyo Co., Ltd., apparatus name “Hiranuma automatic titrator COM-550”).
  • the content of the binder in the photosensitive resin layer is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and more preferably 30% by mass to 50% by mass with respect to the total solid content contained in the photosensitive resin layer. More preferred is mass%.
  • the photosensitive resin layer contains at least one polymerizable monomer.
  • the linearity of the pattern formed becomes favorable because the photosensitive resin layer contains a polymerizable monomer.
  • the polymerizable monomer is a monomer having at least one polymerizable group in the molecule, and the polymerizable group is not particularly limited. Examples of the polymerizable group include an ethylenically unsaturated group and an epoxy group. An ethylenically unsaturated group is preferable, and a (meth) acryloyl group is more preferable.
  • the polymerizable monomer in the photosensitive resin layer preferably includes a so-called polyfunctional polymerizable monomer having two or more polymerizable groups, and more preferably includes a bifunctional polymerizable monomer.
  • a polyfunctional polymerizable monomer it is possible to suppress development residue when developing the photosensitive resin composition.
  • a bifunctional polymerizable monomer it is possible to suppress development residue even in development in a weak alkaline developer (for example, an aqueous sodium carbonate solution).
  • polymerizable monomer examples include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol Di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate Hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyl
  • polyester acrylates described in JP-A No. 52-30490 and polyfunctional (meth) acrylates such as epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid.
  • polyfunctional acrylate is included as a polymerizable monomer.
  • a commercially available product may be used as the polymerizable monomer.
  • examples of commercially available products include tricyclodecane dimethanol diacrylate (A-DCP, Shin-Nakamura Chemical Co., Ltd., bifunctional, molecular weight 304), tricyclodecane dimenanol dimethacrylate (DCP, Shin-Nakamura Chemical Co., Ltd.).
  • the polymerizable monomer preferably includes a polymerizable monomer having a molecular weight of 500 or less.
  • the photosensitive resin layer in one embodiment of the present invention contains a polymerizable monomer having a molecular weight of 500 or less, the taper shape of the cured product in low temperature baking is further improved.
  • the photosensitive resin layer in one embodiment of the present invention may include a polymerizable monomer having a molecular weight exceeding 500.
  • the content of the polymerizable monomer having a molecular weight of 500 or less with respect to the total polymerizable monomers contained in the photosensitive resin layer is preferably 50% by mass or more, The mass% or more is more preferable.
  • the molecular weight of the polymerizable monomer is identified by mass analysis (for example, liquid chromatograph (LC / MS) analysis, gas chromatograph (GC / MS) analysis, fast atom collision chromatograph (FAB / MS analysis), etc.). It can be obtained from the molecular formula.
  • mass analysis for example, liquid chromatograph (LC / MS) analysis, gas chromatograph (GC / MS) analysis, fast atom collision chromatograph (FAB / MS analysis), etc.
  • the content of the polymerizable monomer contained in the photosensitive resin layer is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass with respect to the total solid content of the photosensitive resin layer. % To 30% by mass is more preferable.
  • a polymerizable monomer may be used individually by 1 type, and may be used in combination of 2 or more type. Especially, it is preferable from a viewpoint that the sensitivity in the case of pattern formation improves using it in combination of 2 or more types of polymerizable monomers.
  • the photosensitive resin layer preferably contains a bifunctional polymerizable monomer, and includes a bifunctional polymerizable monomer and a polymerizable monomer other than the bifunctional monomer. More preferably.
  • the bifunctional polymerizability with respect to the total mass of the polymerizable monomer (total amount of the bifunctional polymerizable monomer and the non-bifunctional polymerizable monomer)
  • the mass ratio of the monomer (bifunctional polymerizable monomer / total polymerizable monomer mass) is preferably 50% by mass or more.
  • (bifunctional polymerizable monomer / polymerizable monomer total mass) is 50% by mass or more, it is advantageous in terms of suppression of development residue by a weak alkaline developer (for example, sodium carbonate aqueous solution) and film strength.
  • the content ratio of the polymerizable monomer to the content of the binder in the photosensitive resin layer (hereinafter sometimes referred to as M / B ratio) is in the range of 0.32 to 0.50 on a mass basis. It is preferably 0.32 to 0.49, more preferably 0.35 to 0.40, and still more preferably 0.35 or more and less than 0.40.
  • M / B ratio is 0.32 or more
  • the heat resistance of the patterned photosensitive resin layer is improved, and it becomes easy to form a taper shape of the pattern by a low-temperature baking process. Generation of residue is further suppressed.
  • the M / B ratio is 0.50 or less, the peelability between the photosensitive resin layer and the protective film existing adjacent to the photosensitive resin layer is improved, and the linearity of the formed pattern is further improved. It becomes good.
  • the photosensitive resin layer in the transfer film of the present disclosure contains at least one pigment.
  • a pigment there is no restriction
  • the pigment include known organic pigments and inorganic pigments.
  • a commercially available pigment dispersion for example, a pigment dispersion in which a pigment is dispersed in water, a liquid compound, a pigment-insoluble resin or the like as a dispersion medium
  • a surface-treated pigment for example, a resin or a pigment derivative
  • organic pigments and inorganic pigments include black pigments, white pigments, blue pigments, cyan pigments, green pigments, orange pigments, purple pigments, brown pigments, yellow pigments, red pigments, and magenta pigments.
  • black pigments, white pigments, blue pigments, and the like are preferable and black pigments are more preferable from the viewpoint that the light shielding property of the decorative layer is good.
  • the black pigment is not particularly limited as long as it can exhibit a necessary light shielding property in the formed photosensitive resin layer.
  • a known black pigment for example, a black pigment selected from organic pigments and inorganic pigments can be suitably used.
  • Inorganic pigments include pigments containing metal compounds such as metal pigments and metal oxide pigments.
  • examples of the black pigment include titanium oxide pigments such as carbon black, titanium carbon, iron oxide, and titanium black, graphite, and aniline black. Of these, carbon black is preferred.
  • the CI number of aniline black is C.I. I. Pigment Black 1, and the CI number of carbon black is C.I. I. Pigment Black 7.
  • Carbon black is also available as a commercial product. Examples thereof include black pigment dispersion FDK-911 [trade name: FDK-911] manufactured by Tokyo Ink Co., Ltd.
  • the carbon black is preferably carbon black whose surface is coated with a resin (hereinafter, also referred to as resin-coated carbon black) from the viewpoint that the uniform dispersibility of the carbon black in the photosensitive resin layer becomes better.
  • the coating of carbon black with a resin may be performed as long as at least a part of the surface of carbon black is coated, and the entire surface may be coated.
  • the resin-coated carbon black can be produced, for example, by the method described in paragraphs [0036] to [0042] of Japanese Patent No. 5320652. It is also available as a commercial product, and as a commercial product of resin-coated carbon black.
  • SF Black GB4051 manufactured by Sanyo Dye Co., Ltd. can be mentioned.
  • the particle diameter of the black pigment is preferably 0.001 ⁇ m to 0.3 ⁇ m, more preferably 0.01 ⁇ m to 0.2 ⁇ m in terms of number average particle diameter from the viewpoint of dispersion stability.
  • the term “particle diameter” as used herein refers to the diameter when the electron micrograph image of the particle is a circle of the same area, and the “number average particle diameter” refers to the particle diameter of any 100 particles. The average value of the particle diameters is obtained.
  • the number average particle diameter of the black pigment contained in the photosensitive resin composition is obtained by using a photograph taken at 300,000 times with a transmission electron microscope (JEOL) of the photosensitive resin layer containing the black pigment.
  • the particle diameter of any 100 particles included in the viewing angle can be measured and calculated as an average value of the measured values.
  • Pigment in the photosensitive resin layer (when the photosensitive resin layer contains only a black pigment or a non-black pigment, the content of the black pigment or non-black pigment, or the total of both when containing a black pigment and a non-black pigment
  • the content of (mass) is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and more preferably 30% by mass to 30% by mass relative to the total solid content of the photosensitive resin layer.
  • the content is more preferably 55% by mass, and further preferably 20% by mass to 45% by mass.
  • the content of the black pigment is 10% by mass or more, the optical density of the photosensitive resin layer can be increased while keeping the film thickness thin.
  • the content of the black pigment is 70% by mass or less, the curing sensitivity when patterning the black resin layer is good.
  • the black pigment is desirably used in the photosensitive resin composition as a dispersion.
  • the dispersion can be prepared by adding and dispersing a composition obtained by mixing a black pigment and a pigment dispersant in advance to an organic solvent or vehicle described later.
  • a vehicle refers to a portion of a medium in which a pigment is dispersed when the photosensitive resin composition is in a liquid state.
  • the vehicle is a component that is liquid and binds to a black pigment to form a photosensitive resin layer (for example, a binder). And a medium such as an organic solvent for dissolving and diluting it.
  • the disperser used for dispersing the black pigment is not particularly limited.
  • a kneader described in Kazuzo Asakura, “Encyclopedia of Pigments”, First Edition, Asakura Shoten, 2000, page 438 Known dispersing machines such as a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill can be used.
  • the black pigment which is a dispersoid may be finely pulverized using frictional force by mechanical grinding described on page 310 of the document.
  • a pigment dispersant according to the pigment and solvent which are contained in the photosensitive resin composition for example, a commercially available dispersing agent can be used.
  • pigments other than black examples include organic pigments, for example, pigments described in paragraphs [0030] to [0044] of JP-A-2008-224982, which exhibit hues other than black, C.I. I. Pigment Green 58, C.I. I. Pigment Blue 79 is a pigment in which the chlorine (Cl) substituent is changed to a hydroxyl group (OH).
  • pigments that can be preferably used include the following pigments.
  • the pigment that the photosensitive resin layer in one embodiment of the present invention can contain is not limited to the pigments described below.
  • the photosensitive resin layer in one embodiment of the present invention may contain components other than the binder, the polymerizable monomer, and the pigment described above.
  • Other components contained in the photosensitive resin layer include polymerization initiators, polymerization inhibitors, thiol compounds, dyes, solvents, surfactants, silane coupling agents, UV absorbers, antioxidants, sensitizers, amines Compound etc. are mentioned.
  • the photosensitive resin layer may contain at least one polymerization initiator.
  • the content of the polymerization initiator in the photosensitive resin layer is preferably more than 0% by mass and less than 9% by mass with respect to the total solid content contained in the photosensitive resin layer.
  • the photosensitive resin layer contains a polymerization initiator, the formability of the pattern by exposure and development is further improved.
  • the polymerization initiator is included, if the content of the polymerization initiator is less than 9% by mass, heat dripping is likely to occur during low-temperature baking, and the taper shape of the formed pattern is further improved.
  • the content of the polymerization initiator in the photosensitive resin layer is preferably more than 0% by mass and less than 10% by mass with respect to the total solid content, more preferably 1% by mass to 7% by mass, 2 mass% or more and 6 mass% or less are more preferable.
  • polymerization initiator examples include polymerization initiators described in paragraphs [0031] to [0042] of JP 2011-95716 A, and oxime series described in paragraphs [0064] to [0081] of JP 2015-014783 A.
  • a polymerization initiator is mentioned.
  • the polymerization initiator commercially available products can be used.
  • Examples of commercially available products include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] (trade name: IRGACURE OXE-01, manufactured by BASF), ethane-1-one , [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime) Trade name: IRGACURE OXE-02, manufactured by BASF), 2- (dimethylamino) -2-[(4-Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE 379EG, manufactured by BASF), 2-methyl-1- (4-methylthio Phenyl) -2-morpholinopropan-1-one (trade name: IRGACURE 907, manufactured by BASF), 2-hydroxy-1- ⁇ 4- [4- ( 2-hydroxy-2-methyl-
  • halogen-containing polymerization initiators such as trichloromethyltriazine compounds used for color filter materials and the like from the viewpoint of increasing sensitivity.
  • ⁇ -aminoalkylphenone compounds, ⁇ -hydroxyalkyls are preferred.
  • Oxime polymerization initiators such as phenone compounds and oxime ester compounds are more preferable, and it is particularly preferable to include the oxime polymerization initiator described above from the viewpoint of further improving sensitivity during pattern formation.
  • the content of the polymerization initiator in the photosensitive resin layer is such that the mass ratio (polymerization initiator / polymerizable monomer) to the polymerizable monomer described above is 0.05 to 0.50. From the viewpoint that the taper angle of the patterned cured product formed by the method becomes closer to a rectangle and the precipitation of the polymerization initiator from the photosensitive resin layer is more effectively suppressed, 0.07 to 0.30 is preferable. It is more preferable that
  • the photosensitive resin layer can contain at least one polymerization inhibitor. Generation
  • production of the image development residue is suppressed more because the photosensitive resin layer contains a polymerization inhibitor.
  • a thermal polymerization inhibitor also referred to as a polymerization inhibitor
  • phenothiazine, phenoxidine, and methoxyphenol can be preferably used.
  • the content of the polymerization inhibitor is preferably 0.01% by mass to 3% by mass, and 0.05% by mass with respect to the total solid content of the photosensitive resin layer. Is more preferably 1% by mass, and further preferably 0.1% by mass to 0.8% by mass.
  • the photosensitive resin layer in one embodiment of the present invention contains a polymerization initiator and a polymerization inhibitor
  • the content ratio of the polymerization inhibitor to the polymerization initiator is based on mass. And is preferably from 0 to 0.1, more preferably from 0.02 to 0.05.
  • production of the image development residue is suppressed more as a polymerization inhibitor / polymerization initiator ratio is 0.02 or more.
  • the polymerization inhibitor / polymerization initiator ratio is 0.05 or less, the linearity of the formed pattern becomes better.
  • the preferable range of the content of the polymerization initiator in the photosensitive resin layer varies depending on the presence or absence of the polymerization inhibitor.
  • the polymerization inhibitor when the polymerization initiator is 1% by mass to 3% by mass, the polymerization inhibitor is 0.06% by mass to 0.00%.
  • the polymerization inhibitor when the polymerization initiator is 3% by mass to 6% by mass, the polymerization inhibitor is more preferably 0.15% by mass to 0.3% by mass, and the polymerization initiator is 6% by mass to 9% by mass. In this case, the polymerization inhibitor is more preferably 0.3% by mass to 0.45% by mass.
  • the photosensitive resin layer can contain a thiol compound.
  • the thiol compound may be a monofunctional compound having two or more functional groups, which is the number of thiol groups (also referred to as mercapto groups).
  • the thiol compound is preferably a bifunctional or higher functional compound, more preferably a bifunctional to tetrafunctional compound, more preferably a bifunctional to trifunctional compound. Particularly preferred are compounds.
  • Examples of the monofunctional thiol compound that can be contained in the photosensitive resin layer include N-phenylmercaptobenzimidazole.
  • Examples of the bifunctional or higher functional thiol compound that can be contained in the photosensitive resin layer include 1,4-bis (3-mercaptobutyryloxy) butane (Karenz MT BD1, manufactured by Showa Denko), 1,3,5-tris (3 -Mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (Karenz MT NR1 manufactured by Showa Denko), pentaerythritol tetrakis (3-mercaptobutyrate) ( Karenz MT PE1 Showa Denko), pentaerythritol tetrakis (3-mercaptopropionate) (“PEMP” manufactured by Sakai Chemical Industry Co., Ltd.), and the like.
  • 1,4-bis (3-mercaptobutyryloxy) butane Karenz MT BD1, manufactured by Showa Denko
  • 1,3,5-tris (3 -Mercaptobutyryloxye
  • the photosensitive resin layer can contain a dye as a coloring component in addition to the pigment described above.
  • a dye as a coloring component in addition to the pigment described above.
  • Known dyes for example, known dyes described in documents such as “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published in 1970), or dyes available as commercial products are appropriately selected and used. Can do.
  • the dye examples include azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolates. And dyes such as complexes.
  • the content of the dye is 1 mass with respect to 100 parts by mass of the pigment from the viewpoint that the cured product on the pattern to be formed can exhibit antireflection ability.
  • Part to 40 parts by weight preferably 1 part to 20 parts by weight.
  • the photosensitive resin layer may contain a known additive such as a surfactant.
  • a surfactant examples include surfactants described in paragraph [0017] of Japanese Patent No. 4502784, paragraphs [0060] to [0071] of JP 2009-237362, and JP 2000-310706 A. Other additives described in paragraphs [0058] to [0071] of the above.
  • Surfactants include fluorine-containing surfactants such as MegaFac (registered trademark) F-784-F and F-780 manufactured by DIC Corporation from the viewpoint of improving the film properties during coating formation of the photosensitive resin layer. Is preferably used.
  • the photosensitive resin layer can contain a solvent.
  • the solvent that may be contained in the photosensitive resin layer is not particularly limited, and a commonly used solvent is particularly preferable. Can be used without limitation. Specific examples of the solvent include esters, ethers, ketones, and aromatic hydrocarbons.
  • methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (hereinafter sometimes referred to as PEGMEA), cyclohexanone, cyclohexane Hexanol, methyl isobutyl ketone, ethyl lactate, methyl lactate and the like can be suitably used for the photosensitive resin layer.
  • the solvent may be used alone or in combination of two or more.
  • an organic solvent having a boiling point of 180 ° C. to 250 ° C. (high boiling solvent) can be used as necessary.
  • the film thickness of the photosensitive resin layer in the transfer film of the present disclosure is preferably 0.5 ⁇ m to 10.0 ⁇ m from the viewpoint of design when used as a decorative material, and is 1.0 ⁇ m to 8.0 ⁇ m. More preferably, it is more preferably 1.5 ⁇ m to 5.0 ⁇ m.
  • the transfer film of the present disclosure includes a temporary support, the above-described photosensitive resin layer, and a protective film.
  • the transfer film has a protective film on the side opposite to the side where the temporary support of the photosensitive resin layer is disposed.
  • the protective film is provided in contact with the photosensitive resin layer.
  • the transfer film may have a layer other than the temporary support, the photosensitive resin layer, and the protective film. Examples of other layers include a functional layer and a thermoplastic resin layer.
  • the transfer film can be used to form a decorative pattern on at least one surface of an image display device such as a touch panel, and has a photosensitive resin layer that can be formed into a tapered shape in low-temperature baking.
  • the decorative pattern which is a patterned cured layer formed of a transfer film, has a tapered shape and is excellent in pattern linearity.
  • FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a transfer film according to an embodiment of the present invention.
  • the transfer film 10 shown in FIG. 1 has the temporary support body 12, the photosensitive resin layer 14, and the protective film 16 in this order.
  • the temporary support body 12, the photosensitive resin layer 14, and the protective film 16 show the aspect laminated
  • the transfer film 10 can be used as, for example, a transfer film for forming a decorative pattern, that is, a patterned cured layer, on one surface of an image display device such as a touch panel.
  • a method for producing a decorative pattern by transferring the photosensitive resin layer 14 onto a substrate using the transfer film 10 of the present disclosure will be described later.
  • the transfer film of the present disclosure has a temporary support.
  • a flexible material can be used for forming the temporary support.
  • Examples of the temporary support that can be used for the transfer film include a cycloolefin copolymer film, a polyethylene terephthalate (hereinafter sometimes referred to as “PET”) film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film.
  • PET film is particularly preferred from the viewpoint of handling.
  • the temporary support may be transparent, or may be colored by containing dyed silicon, alumina sol, chromium salt, zirconium salt or the like.
  • the temporary support When the temporary support is transparent, the protective film is peeled off and transferred, and then the photosensitive resin layer is subjected to pattern exposure through the temporary support to form a decorative pattern.
  • the temporary support can be provided with conductivity by the method described in JP-A-2005-221726, and the temporary support provided with conductivity is also suitably used for the transfer film of the present disclosure.
  • the transfer film has a protective film on the surface of the above-described photosensitive resin layer.
  • the surface roughness Rz of the surface of the protective film on the side in contact with the above-described photosensitive resin layer is less than 0.12 ⁇ m, preferably less than 0.1 ⁇ m, and more preferably less than 0.08 ⁇ m. .
  • the lower limit of the surface roughness Rz is not particularly limited and may be 0.01 ⁇ m or more.
  • the surface roughness Rz in the protective film can be measured by the method described below. First, using a three-dimensional optical profiler (New View 7300, manufactured by Zygo), a surface profile of the optical film is obtained under the following conditions.
  • the measurement analysis software uses Microscope Application 8.3.2 Microscope Application.
  • the Surface Map screen is displayed with the above analysis software (MetroPro version 8.3.2-Microscope Application), and histogram data is obtained in the Surface Map screen. From the obtained histogram data, the difference between the upper limit and the lower limit of the distribution height at the peak position is read and is defined as Rz.
  • the protective film a film that can be easily peeled off from the photosensitive resin layer can be used, and a material that is the same as or similar to the material of the temporary support can be suitably selected.
  • protective films described in paragraphs [0083] to [0087] and [0093] of JP-A-2006-259138 can be appropriately used.
  • the protective film is preferably a flexible film.
  • protective films that can be used for transfer films include cycloolefin copolymer films, polyolefin films (for example, polypropylene films), polyester films (for example, polyethylene terephthalate (hereinafter sometimes referred to as “PET”) films, polyethylene films, and the like.
  • PEN film phthalate (hereinafter sometimes referred to as “PEN” film), cellulose triacetate film, polystyrene film, polycarbonate film and the like.
  • PEN film phthalate
  • cellulose triacetate film cellulose triacetate film
  • polystyrene film polystyrene film
  • polycarbonate film polycarbonate film
  • a PET film is more preferable from the viewpoint of easy handling and easy formation of a protective film having a smooth surface.
  • polyester such as PET is excellent in surface smoothness when the film is formed, so that the surface described above can be obtained by a normal film forming method, for example, melt extrusion film forming using a die. A film that is within the roughness range can be obtained. Moreover, the commercially available film which adapts to the said surface roughness can also be applied to a protective film.
  • the transfer film has the above-described photosensitive resin layer and the surface roughness of the protective film is in the above-described range, the taper shape of the decorative pattern formed by the photosensitive resin layer, the protective film, The peelability from the photosensitive resin layer is good with a good balance.
  • the transfer film may have a thermoplastic resin layer described in paragraph No. [0026] of Japanese Patent No. 4502784 between the temporary support and the black resin layer described above. Furthermore, you may have a functional layer further between the photosensitive resin layer as stated above and the thermoplastic resin layer provided arbitrarily, or between the temporary support body and the photosensitive resin layer as stated above. Examples of the functional layer include an oxygen-blocking film having an oxygen-blocking function described in paragraph No. [0027] of Japanese Patent No. 4502784.
  • the oxygen barrier film is preferably a film made of a resin that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkaline solution.
  • the resin used for forming the oxygen barrier film is appropriately selected from known resins. be able to. Among these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is preferable.
  • the dry thickness of the functional layer is generally 0.2 ⁇ m to 5 ⁇ m, preferably 0.5 ⁇ m to 3 ⁇ m, and more preferably 1 ⁇ m to 2.5 ⁇ m.
  • the transfer film may further have a thermoplastic resin layer described in paragraph [0026] of Japanese Patent No. 4502784 between the temporary support and the photosensitive resin layer.
  • a component used for the thermoplastic resin layer an organic polymer substance described in JP-A-5-72724 is preferable.
  • the dry thickness of the thermoplastic resin layer is generally 2 ⁇ m to 30 ⁇ m, preferably 5 ⁇ m to 20 ⁇ m, and particularly preferably 7 ⁇ m to 16 ⁇ m.
  • the transfer film can be produced according to the method for producing a curable transfer material described in paragraphs [0094] to [0098] of JP-A-2006-259138. That is, the method for producing a transfer film includes a step of forming a photosensitive resin layer on a temporary support and a step of providing a protective film on the surface of the photosensitive resin layer. Furthermore, before forming the above-mentioned photosensitive resin layer on the temporary support, it may further include at least one of a step of forming a thermoplastic resin layer and a step of forming a functional layer.
  • the transfer film manufacturing method includes a step of forming a functional layer between the thermoplastic resin layer and the photosensitive resin layer after the step of forming the thermoplastic resin layer described above. It is preferable to contain.
  • a solution thermoplastic resin layer coating solution
  • a functional layer coating solution prepared by adding a resin and an additive to a solvent that does not dissolve the thermoplastic resin layer is applied on the provided thermoplastic resin layer.
  • the functional layer is laminated by drying, and a photosensitive resin composition prepared using a solvent that does not dissolve the functional layer is further applied on the laminated functional layer, and dried to form a photosensitive resin layer. It can be suitably produced by providing a protective film on the surface of the formed photosensitive resin layer.
  • the components contained in the photosensitive resin layer are as described above.
  • the decorative pattern which is one embodiment of the present invention is a cured product of the pattern of the photosensitive resin layer in the transfer film of the present disclosure described above.
  • the decoration pattern of this indication is applicable as a decoration pattern with which a touch panel etc. are provided.
  • the decorative pattern is a pattern formed by patterning the photosensitive resin layer disposed on the surface of the substrate selected from the group consisting of a glass substrate and a resin substrate, and transferred by the transfer film of the present disclosure described above. It is a cured product of the photosensitive resin, and the patterned cured layer corresponds to the decorative pattern which is an embodiment of the present invention.
  • the decorating pattern produced using the transfer film of this indication is manufactured with the manufacturing method of the following decorating patterns.
  • the decorative pattern is manufactured by transferring the photosensitive resin layer of the transfer film of the present disclosure described above onto a substrate selected from the group consisting of a glass substrate and a resin substrate, and the transferred photosensitive resin. Patterning the layer by a photolithography method to form a patterned photosensitive resin layer; applying energy to the formed patterned photosensitive resin layer to form a patterned cured layer; It can carry out suitably by the method containing.
  • Base material As the base material, it is preferable to use a material having no optical distortion and high transparency. From such a viewpoint, a glass substrate and a resin substrate that are highly transparent are preferable. Among these, a resin base material is preferable from the viewpoint of being lightweight and difficult to break. Specific examples of the resin base material include base materials made of resins such as polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate (PC), triacetyl cellulose (TAC), and cycloolefin polymer (COP). it can.
  • PET polyethylene terephthalate
  • PC polyethylene naphthalate
  • PC polycarbonate
  • TAC triacetyl cellulose
  • COP cycloolefin polymer
  • the base material preferably has a refractive index of 1.6 to 1.78 and a film thickness of 50 ⁇ m to 200 ⁇ m from the viewpoint of further improving the visibility of the display image.
  • the substrate may have a single layer structure or a laminated structure of two or more layers.
  • the refractive index means the refractive index of the entire layer of the substrate.
  • the refractive index is a value measured by ellipsometry at a wavelength of 550 nm.
  • the material forming the substrate is not particularly limited.
  • the thickness of a base material means the total thickness of all the layers, when it is a laminated structure of two or more layers.
  • the photosensitive resin layer in the above-mentioned transfer film is transferred to the surface of the substrate, and an exposure process for pattern exposure and a development process for developing unexposed portions are performed.
  • an exposure process for pattern exposure and a development process for developing unexposed portions are performed.
  • the exposure process, the development process, and other processes of the photosensitive resin layer transferred onto the substrate the method described in paragraphs [0035] to [0051] of JP-A-2006-23696 is described in the present invention. In one embodiment, it can be suitably used.
  • An exposure process is a process of exposing the photosensitive resin layer transcribe
  • a mask having a predetermined pattern is disposed above the photosensitive resin layer transferred onto the substrate, that is, between the photosensitive resin layer and the exposure light source, and then the mask and temporary support
  • the exposure light source can be appropriately selected and used as long as it can irradiate light in a wavelength region that can cure the photosensitive resin layer (eg, 365 nm, 405 nm, etc.).
  • an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned.
  • the exposure amount is usually about 5 J / cm 2 to 200 mJ / cm 2 , and preferably about 10 J / cm 2 to 100 mJ / cm 2 .
  • the pattern exposure may be performed after the temporary support is peeled off, or may be exposed before the temporary support is peeled off, and then the temporary support may be peeled off.
  • the pattern exposure may be exposure through a patterned mask or scanning exposure (digital exposure) using a laser or the like.
  • a decorative pattern which is a patterned hardened layer, is formed on the substrate.
  • FIG. 2 is a schematic plan view showing an example of the touch panel 18 including a patterned cured layer (decoration pattern) 20. Since the touch panel 18 includes the decorative pattern 20 having a shape as illustrated in FIG. 2, the wiring arranged on the main body of the touch panel 18 can be concealed.
  • the development process is a process of developing the exposed photosensitive resin layer.
  • the development is a development process in a narrow sense in which an unexposed portion in the photosensitive resin layer subjected to pattern exposure is developed and removed with a developer to form a patterned cured product.
  • Development can be performed using a developer.
  • the developer is not particularly limited, and a known developer such as the developer described in JP-A-5-72724 can be used.
  • the developer is preferably a developer that can dissolve the unexposed photosensitive resin layer.
  • the developer is preferably an aqueous sodium carbonate solution from the viewpoint of buffering properties.
  • a small amount of an organic solvent miscible with water may be added to the developer.
  • organic solvents miscible with water include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, benzyl alcohol And acetone, methyl ethyl ketone, cyclohexanone, ⁇ -caprolactone, ⁇ -butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ⁇ -caprolactam, N-methylpyrrolidone and the like.
  • the concentration of the organic solvent is preferably 0.1% by mass to 30% by mass.
  • a known surfactant can be added to the developer.
  • the concentration of the surfactant is preferably 0.01% by mass to 10% by mass.
  • the development method described above may be any of paddle development, shower development, shower development + spin development, dip development, and the like.
  • shower development will be described.
  • a pattern-like cured product can be formed by removing an uncured portion by spraying a developer onto the exposed photosensitive resin layer by shower. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like.
  • the developer temperature is preferably 20 ° C. to 40 ° C.
  • the pH of the developer is preferably 8 to 13.
  • the method for producing a decorative pattern may have a post-processing step of imparting energy to the formed cured pattern after the development step described above to further accelerate the curing.
  • the post-treatment process by applying energy, the crosslink density of the patterned cured product is improved, and the strength of the decorative pattern, which is the produced patterned cured product, is further improved.
  • the energy application treatment include heat treatment and actinic ray irradiation treatment.
  • the actinic ray irradiation include full-surface exposure with ultraviolet rays. From the viewpoint of the effect of promoting curing by post-treatment and the simplicity of the process, the energy application is preferably a heat treatment described in detail below.
  • the heat treatment in the method for producing a decorative pattern is performed after the development step, and includes a step of heat treatment at 130 ° C. to 170 ° C. (post-bake step). Production of a decoration pattern that forms a decoration pattern after other members such as an electrode pattern, lead-out wiring, a light-shielding conductive film, and an overcoat layer are formed on the substrate in advance by heat treatment at such a temperature. Also in the method, heat treatment can be performed without adversely affecting other members.
  • the temperature of the heat treatment step is more preferably 140 ° C. to 160 ° C., and further preferably 140 ° C. to 150 ° C.
  • the effect of the patterned cured product is promoted by heat treatment, and further, the patterned cured product is sunk by low-temperature baking at 140 ° C. to 150 ° C., and the decorative pattern is tapered.
  • a shape is formed.
  • the time for the heat treatment step is preferably 1 minute to 60 minutes, more preferably 10 minutes to 60 minutes, and further preferably 20 minutes to 50 minutes.
  • the peelability between the protective film and the photosensitive resin layer is good, and by the low-temperature baking process as described above,
  • the patterned cured product quickly forms a tapered shape, and the decorative pattern, which is the formed cured product of the tapered shape, has excellent concealment properties such as appearance and wiring when provided in a touch panel or the like.
  • a touch panel is provided with the above-mentioned decoration pattern.
  • the decoration pattern is arranged on the outermost surface of the touch panel.
  • a surface capacitive touch panel, a projected capacitive touch panel, a resistive touch panel, and the like can be given. Details will be described later as a resistive touch panel and a capacitive touch panel.
  • the touch panel includes so-called touch sensors and touch pads.
  • the layer structure of the touch panel sensor electrode part in the touch panel is a bonding method in which two transparent electrodes are bonded, a method in which transparent electrodes are provided on both surfaces of a single substrate, a single-sided jumper or through-hole method, or a single-area layer method. Either is acceptable.
  • the projected capacitive touch panel is preferably AC (alternating current) driving rather than DC (direct current) driving, and more preferably a driving method in which the voltage application time to the electrodes is short.
  • the resistive film type touch panel is a resistive film type touch panel including the decorative pattern described above.
  • the resistive touch panel has a basic configuration in which conductive films of a pair of upper and lower substrates having a conductive film are disposed via a spacer at a position where the conductive films face each other.
  • the configuration of the resistive touch panel is known, and any known technique can be applied without any limitation.
  • the capacitive touch panel is a capacitive touch panel including the decorative pattern described above.
  • Examples of the capacitive touch panel system include a surface capacitive type and a projected capacitive type.
  • the projected capacitive touch panel has a basic arrangement in which an X-axis electrode (hereinafter also referred to as an X electrode) and a Y-axis electrode (hereinafter also referred to as a Y electrode) orthogonal to the X electrode are disposed via an insulator. Consists of configuration. More specifically, as an aspect in which the X electrode and the Y electrode are formed on different surfaces on a single substrate, the X electrode, the insulator layer, and the Y electrode are formed in this order on the single substrate.
  • a mode in which an X electrode is formed on one substrate and a Y electrode is formed on another substrate is the above basic configuration. It is done.
  • the configuration of the capacitive touch panel is publicly known, and the publicly known technology can be applied without any limitation in one embodiment of the present invention.
  • Black pigment dispersion manufactured by Tokyo Ink Co., Ltd., black pigment dispersion FDK-911 (trade name: FDK-911)
  • Green pigment dispersion and Red pigment dispersion A green pigment or a red pigment, a dispersant, a polymer, and a solvent were mixed so as to have the following composition, and a pigment dispersion was obtained using a three roll and bead mill.
  • Green pigment Pigment Green 58 (DIC Corporation, FASTOGEN Green A110) Red pigment: Pigment Red 254 (BASF, Irgaphor Red BT-CF)
  • thermoplastic resin layer was formed by applying and drying a coating solution for a thermoplastic resin layer having the following formulation H1 on a 75 ⁇ m-thick polyethylene terephthalate film temporary support using a slit nozzle.
  • a functional layer coating solution having the following formulation P1 was applied onto the above-described thermoplastic resin layer and dried to obtain a functional layer.
  • the above-mentioned composition for forming a photosensitive resin layer was applied on a functional layer and dried to obtain a photosensitive resin layer.
  • a protective film was pressure-bonded to the surface of the photosensitive resin layer.
  • a transfer film having a temporary support, a thermoplastic resin layer, a functional layer (oxygen barrier film), a photosensitive resin layer containing the photosensitive resin composition described in each column of each example or comparative example, and a protective film. Respectively.
  • the following two types were used for the protective film.
  • PET film Polyethylene terephthalate film with a thickness of 16 ⁇ m
  • Formulation P1- PVA205 32.2 parts by mass (polyvinyl alcohol, manufactured by Kuraray Co., Ltd., saponification degree 88%, polymerization degree 550) ⁇ 14.9 parts by mass of polyvinylpyrrolidone (manufactured by ISP Japan, K-30) ⁇ Distilled water 524 mass parts ⁇ Methanol 429 mass parts
  • the protective films of the various transfer films prepared above are peeled off, and the transfer film is overlaid so that the photosensitive resin layer of the transfer film is in contact with the base material (colorless polyester film having a thickness of 200 ⁇ m).
  • a laminate having a resin layer was obtained.
  • a mask is placed on a temporary support disposed on the opposite side of the substrate of the photosensitive resin layer stacked on the substrate, and is photosensitive by a metal halide lamp (wavelength: 365 nm) from above the mask.
  • the resin layer was exposed. After the exposure, the temporary support was peeled off, and the exposed photosensitive resin layer was immersed in a 1% by mass aqueous sodium carbonate solution for development. Then, it heated at 145 degreeC for 30 minute (s) in oven, and heat-processed at low temperature, and obtained the frame-shaped decorating pattern which is the hardened
  • FIG. 3 is a diagram illustrating the angle ( ⁇ ) at the end of the decorative pattern (decorative layer) 21 provided on the substrate 22.
  • a to C are practical ranges.
  • the inner surface of the frame of the frame-shaped decoration pattern is observed using a laser microscope (VK-9500, manufactured by Keyence Corporation; objective lens 50 times), and the surface shape of the surface of the decoration pattern in the field of view is observed. did. It is preferable that the surface shape looks smooth.
  • a or B is in the practical range, and is preferably A.
  • B The observation range is smooth and there are no visible irregularities.
  • C Irregularities such as black spots (convex portions) or craters (concave portions) can be visually recognized within the observation range.
  • Edge roughness The inner surface of the frame of the frame-shaped decorative pattern is observed using a laser microscope (VK-9500, manufactured by Keyence Corporation; objective lens 50 times), and the most swollen portion (in the edge position in the field of view) ( The absolute value of the difference between the top of the mountain) and the most constricted portion (bottom of the valley) was obtained, and the average value of the five observed locations was calculated as edge roughness. The smaller the value of the edge roughness, the sharper the contour of the decorative pattern is, and the higher the linearity, the better.
  • a to C are practical ranges, preferably A or B, and more preferably A. ⁇ Evaluation criteria>
  • B Edge roughness is 2 ⁇ m or more and less than 5 ⁇ m.
  • C Edge roughness is 5 ⁇ m or more and less than 10 ⁇ m.
  • D Edge roughness is 10 ⁇ m or more.
  • the transfer films of the examples have good peelability when the protective film is peeled off from the photosensitive resin layer during transfer. Furthermore, according to the transfer film of an Example, it turns out that a decorating pattern with a favorable taper angle, surface shape, and pattern linearity can be formed.
PCT/JP2017/020305 2016-05-31 2017-05-31 転写フィルム、加飾パターン及びタッチパネル WO2017209193A1 (ja)

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