WO2019224887A1 - Film photosensible de type transfert, substrat d'électrode avec film durci en résine et panneau tactile - Google Patents

Film photosensible de type transfert, substrat d'électrode avec film durci en résine et panneau tactile Download PDF

Info

Publication number
WO2019224887A1
WO2019224887A1 PCT/JP2018/019536 JP2018019536W WO2019224887A1 WO 2019224887 A1 WO2019224887 A1 WO 2019224887A1 JP 2018019536 W JP2018019536 W JP 2018019536W WO 2019224887 A1 WO2019224887 A1 WO 2019224887A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrode
substrate
film
cured resin
electrode substrate
Prior art date
Application number
PCT/JP2018/019536
Other languages
English (en)
Japanese (ja)
Inventor
吉田　英樹
Original Assignee
日立化成株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日立化成株式会社 filed Critical 日立化成株式会社
Priority to PCT/JP2018/019536 priority Critical patent/WO2019224887A1/fr
Publication of WO2019224887A1 publication Critical patent/WO2019224887A1/fr

Links

Images

Classifications

    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings

Definitions

  • the present invention relates to a transfer type photosensitive film, an electrode substrate with a cured resin film, and a touch panel.
  • a projected capacitive touch panel In general, in a projected capacitive touch panel, a plurality of X electrodes and a plurality of Y electrodes orthogonal to the X electrodes have a two-layer structure in order to express two-dimensional coordinates based on the X and Y axes. Forming. As a material for these electrodes, ITO (Indium-Tin-Oxide) is the mainstream.
  • a metal wiring such as copper is formed in the frame region in order to transmit a touch position detection signal.
  • a corrosive component such as moisture or salt may enter the sensing region from the inside when touching the fingertip.
  • the metal wiring corrodes, and there is a risk of an increase in electrical resistance between the electrode and the driving circuit, or disconnection.
  • a capacitive projection type touch panel in which an insulating film and a corrosive component impermeable film are formed on a metal is disclosed (for example, Patent Document 1).
  • a silicon dioxide layer is formed on a metal by a plasma chemical vapor deposition method (plasma CVD method), and the surface is nitrided to prevent corrosion of the metal.
  • plasma CVD method plasma chemical vapor deposition method
  • this method uses a plasma CVD method, there is a problem that a high temperature treatment is required, a base material is limited, and a manufacturing cost is increased.
  • Patent Document 2 discloses a transfer film having a photosensitive transparent resin layer containing a binder polymer, a photopolymerizable compound and a photopolymerization initiator as a transfer film for a transparent protective layer of a capacitive input device. Proposed. According to such a transfer film, the resin cured film can be easily provided on the touch sensor substrate.
  • the surface member including the cover glass and the touch sensor substrate are bonded through the transparent adhesive layer.
  • a visibility improving film OCA: Optical Clear Adhesive
  • OCA Optical Clear Adhesive
  • peeling may occur at the interface between the cured resin film and the OCA. It has also been found that such peeling tends to occur as the area of the substrate increases.
  • the present invention relates to an electrode substrate with a cured resin film that hardly peels off from a transparent adhesive layer even under high temperature and high humidity, a touch panel including the same, and a transparent adhesive layer even under high temperature and high humidity. It is an object of the present invention to provide a transfer type photosensitive film capable of forming a cured resin film that hardly causes peeling.
  • the present inventors have found that a resin cured film having a linear expansion coefficient ratio with respect to the base material is not more than a specific value is provided on the electrode substrate on which the electrode is provided on the base material.
  • the present inventors have found that the peeling between the transparent adhesive layer and the cured resin film can be suppressed even in a large area substrate even under high temperature and high humidity, and the present invention has been completed.
  • the present invention is an electrode substrate comprising a base material and an electrode provided on the main surface of the base material, the electrode substrate having a resin cured film provided on the electrode, Provided is an electrode substrate with a cured resin film, wherein the ratio [ ⁇ A / ⁇ B ] of the linear expansion coefficient ⁇ A (ppm / ° C.) and the base material linear expansion coefficient ⁇ B (ppm / ° C.) is 1.2 or less. .
  • the electrode substrate with a cured resin film according to the present invention has a transparent adhesive layer and a cured resin film even when the cured resin film and a predetermined member are bonded via a transparent adhesive layer even under high temperature and high humidity. Peeling can be suppressed.
  • the area of the main surface on which the electrode of the base material is provided may be 50 cm 2 or more, 270 cm 2 or more, 620 cm 2 or more, or 1100 cm 2 or more. In this case, the reliability of the electrode substrate having a large area can be ensured.
  • the ratio [T A / T B ] of the thickness T A ( ⁇ m) of the cured resin film and the thickness T B ( ⁇ m) of the base material may be 0.08 or more. In this case, the reliability of the thinned electrode substrate can be ensured.
  • the base material may contain a cycloolefin polymer.
  • a substrate having high optical properties such as high transparency and low birefringence, and excellent physical properties such as low deflection, so that it is easy to cope with an increase in size.
  • the linear expansion coefficient ⁇ A of the cured resin film is preferably 51 to 77 ppm / ° C. from the viewpoint of long-term reliability.
  • the cured resin film may have a particle-containing region containing metal oxide particles on the substrate side.
  • the particle-containing region can function as an optical adjustment layer.
  • the projected capacitive touch panel has a large color difference due to the difference in optical reflection characteristics between the portion where the transparent electrode pattern is formed and the portion where the transparent electrode pattern is not formed.
  • the reflected light intensity increases between the substrate and the transparent electrode, or between the OCA and the transparent electrode pattern that bonds the cover glass and the transparent electrode pattern used when modularizing, and the transmittance of the screen is increased. There is also a problem of lowering.
  • the above electrode substrate with a cured resin film by having a particle-containing region, the color difference between the portion where the transparent electrode pattern is formed and the portion where it is not formed is reduced, It is possible to prevent a decrease in the transmittance of the screen.
  • the electrode substrate can be a touch sensor substrate. That is, the present invention can provide a touch sensor substrate with a cured resin film.
  • the present invention also provides a touch panel surface member, an electrode substrate with a cured resin film according to the present invention in which the electrode substrate is a touch sensor substrate, and a transparent adhesive layer for bonding the cured resin film of the touch panel surface member and the touch sensor substrate.
  • the touch panel of the present invention can be excellent in reliability because the cured resin film and the transparent adhesive layer are hardly peeled even under high temperature and high humidity.
  • linear expansion coefficient alpha O of the transparent adhesive layer is 600 ⁇ 1200ppm / °C.
  • the transparent adhesive layer may contain N-vinylpyrrolidone.
  • N-vinylpyrrolidone a polymer obtained by blending N-vinylpyrrolidone as an adhesion assistant, it is possible to suppress peeling between the cured resin film and the transparent adhesive layer. Become.
  • the present invention is also a transfer type photosensitive film used for providing a cured resin film on an electrode of an electrode substrate having a substrate and an electrode provided on the main surface of the substrate, and a support film;
  • the first transfer type photosensitive film of the present invention a cured resin film that hardly peels off from the transparent adhesive layer even under high temperature and high humidity can be easily provided on the electrode substrate.
  • the linear expansion coefficient ⁇ C after curing of the photosensitive resin layer is preferably 51 to 77 ppm / ° C. from the viewpoint of long-term reliability.
  • the present invention is also a transfer type photosensitive film used for providing a cured resin film on an electrode of an electrode substrate having a substrate and an electrode provided on the main surface of the substrate, and a support film;
  • a photosensitive resin layer containing a binder polymer, a photopolymerizable compound and a photopolymerization initiator provided on the support film;
  • a particle-containing layer containing metal oxide particles provided on the photosensitive resin layer;
  • a second transfer type photosensitive film having a thickness of 1.2 or less is provided.
  • the linear expansion coefficient ⁇ D after curing of the photosensitive resin layer and the particle-containing layer is preferably 51 to 77 ppm / ° C. from the viewpoint of long-term reliability.
  • the electrode substrate may be a touch sensor substrate.
  • the area of the main surface on which the base electrode is provided is 50 cm 2 or more, 270 cm 2 or more, 620 cm 2 or more, or 1100 cm 2 or more. It may be used for providing a cured resin film on the electrode.
  • the electrode substrate with a cured resin film that hardly peels off from the transparent adhesive layer even under high temperature and high humidity, the touch panel including the same, and the transparent adhesive even under high temperature and high humidity It is possible to provide a transfer type photosensitive film capable of forming a cured resin film that hardly peels off from the layer.
  • FIG. 1A is a schematic cross-sectional view showing an embodiment of an electrode substrate with a cured resin film according to the present invention
  • FIG. 1B shows another embodiment of the electrode substrate with a cured resin film according to the present invention.
  • 1 is a schematic cross-sectional view showing an embodiment of a touch panel according to the present invention.
  • FIG. 3 (a) is a schematic cross-sectional view showing an embodiment of the transfer type photosensitive film according to the present invention
  • FIG. 3 (b) shows another embodiment of the transfer type photosensitive film according to the present invention.
  • It is a schematic cross section which shows a form.
  • (meth) acrylic acid means acrylic acid or methacrylic acid
  • (meth) acrylate means acrylate or a corresponding methacrylate.
  • a or B only needs to include one of A and B, or may include both.
  • the term “layer” includes a structure formed in a part in addition to a structure formed in the entire surface when observed as a plan view.
  • the term “process” is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term “process” is used as long as the intended action of the process is achieved. included.
  • the numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • each component in the composition is the sum of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means quantity.
  • the exemplary materials may be used alone or in combination of two or more unless otherwise specified.
  • the upper limit value or lower limit value of a numerical range of a certain step may be replaced with the upper limit value or lower limit value of the numerical range of another step.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
  • the electrode substrate with a cured resin film of this embodiment is an electrode substrate including a base material and an electrode provided on the main surface of the base material, and the electrode substrate is a resin cured film provided on the electrode.
  • the a linear expansion coefficient of the resin cured film ⁇ a (ppm / °C) and the ratio of the linear expansion coefficient of the substrate ⁇ B (ppm / °C) [ ⁇ a / ⁇ B] is 1.2 or less.
  • FIG. 1A is a schematic cross-sectional view showing an embodiment of an electrode substrate with a cured resin film
  • FIG. 1B is a schematic sectional view showing another embodiment of an electrode substrate with a cured resin film.
  • An electrode substrate 100 with a cured resin film shown in FIG. 1A includes an electrode substrate 3 including a base material 1 and an electrode 2 provided on the main surface of the base material 1, and an electrode 2 of the electrode substrate 3.
  • the resin cured film 10 provided on the top is provided.
  • the electrode substrate 101 with a cured resin film shown in FIG. 1B is a cured resin film except that the cured resin film 10 has a particle-containing region 20 containing metal oxide particles on the substrate 1 side.
  • a configuration similar to that of the attached electrode substrate 100 is provided.
  • the substrate 1 examples include plastic substrates such as cycloolefin polymer, polycarbonate, polyethylene terephthalate, triacetyl cellulose, and polyethylene.
  • the material of the base material is a cycloolefin polymer or a polycarbonate from the viewpoint of optical characteristics.
  • the substrate includes a film.
  • the thickness of the substrate 1 is not particularly limited, but can be set to 10 to 100 ⁇ m from the viewpoint of thinning the electrode substrate.
  • the thickness of the substrate 1 can be 80 to 100 ⁇ m, 60 to 80 ⁇ m, 30 to 60 ⁇ m, or 10 to 30 ⁇ m.
  • the base material 1 preferably has a transmittance in the wavelength region of 400 to 700 nm of 80% or more, more preferably 85% or more, and 90% or more. Is more preferable.
  • the area of the main surface on which the base electrode is provided may be 50 cm 2 or more. In this case, the reliability of the electrode substrate having a large area can be ensured. Interfacial delamination between the cured resin film and OCA tends to occur as the area of the electrode substrate increases. However, according to the electrode substrate with a cured resin film of this embodiment, sufficient interfacial delamination with OCA is achieved. While suppressing, it can respond to the enlargement of an electrode substrate. In view of a large area, the area of the main surface of the electrode base material is provided, may also be 270 cm 2 or more, may also be 620 cm 2 or more, it may be 1100 cm 2 or more.
  • Examples of the electrode 2 include electrodes such as ITO, Cu, Al, and Mo.
  • the electrode may be a transparent electrode, a metal wiring, a connection terminal, or the like.
  • the electrode substrate 3 having the above-described base material and electrodes can be appropriately applied depending on the application, and may be a touch sensor substrate of a touch panel, a force sensor substrate, an electromagnetic wave shield substrate, or the like.
  • the cured resin film 10 can contain a cured product of the photosensitive resin composition, and can be formed using a transfer type photosensitive film described later.
  • the case where the resin cured film 10 has the particle-containing region 20 can also be formed using a transfer type photosensitive film described later.
  • the particle-containing region 20 can function as an optical adjustment layer, can reduce a color difference between a portion where an electrode is formed and a portion where an electrode is not formed, and can prevent a bone appearance phenomenon and a decrease in transmittance.
  • the ratio of the linear expansion coefficient of the resin cured film 10 ⁇ A (ppm / °C) and the linear expansion coefficient of the substrate 1 ⁇ B (ppm / °C) [ ⁇ A / ⁇ B] is 1.2
  • the composition of the photosensitive resin composition can be set so as to be as follows. When the resin cured film has a particle-containing region, the linear expansion coefficient of the resin cured film including the particle-containing region is set as the linear expansion coefficient of the resin cured film.
  • the linear expansion coefficient refers to a value calculated based on the elongation at 50 ° C. to 60 ° C.
  • ⁇ A / ⁇ B is preferably 1.2 or less, and more preferably 1.1 or less, from the viewpoint of long-term reliability. Further, ⁇ A / ⁇ B is preferably 0.8 or more, and more preferably 0.9 or more, from the viewpoint of long-term reliability.
  • the linear expansion coefficient ⁇ A of the cured resin film 10 is preferably 51 to 77 ppm / ° C., and more preferably 57 to 71 ppm / ° C.
  • the linear expansion coefficient ⁇ B of the base material 1 of the base material 1 is preferably 50 to 80 ppm / ° C., and more preferably 55 to 75 ppm / ° C.
  • the ratio of the thickness T A of the resin cured film 10 ([mu] m) and of the substrate 1 the thickness T B ( ⁇ m) [T A / T B] may be not less than 0.14. In this case, the reliability of the thinned electrode substrate can be ensured.
  • the resin cured film 10 comprising the particle-containing region 20 the T A also includes the thickness of the particle-containing region 20.
  • T A / T B is 0.08 or more, more preferably 0.10 or more. Even in this case, when the cured resin film and the predetermined member are bonded via the transparent adhesive layer, peeling occurs between the transparent adhesive layer and the cured resin film even under high temperature and high humidity. This can be suppressed.
  • T A / T B is preferably 0.6 or less, and more preferably 0.2 or less.
  • the touch panel of this embodiment includes a touch panel surface member, an electrode substrate with a cured resin film of the present embodiment as a touch sensor substrate, and a transparent adhesive layer that bonds the touch panel surface member and the cured resin film of the touch sensor substrate.
  • FIG. 2 is a schematic cross-sectional view showing an embodiment of the touch panel.
  • the touch panel 200 shown in FIG. 2 bonds the cover glass 30 as a touch panel surface member, the electrode substrate 101 with a cured resin film of the present embodiment as a touch sensor substrate, and the cover glass 30 and the cured resin film 10 of the touch sensor substrate. And a transparent adhesive layer 32.
  • the cured resin film 10 having the particle-containing region 20 is formed across a portion where the touch panel electrode 2 is formed and a portion where the electrode 2 is not formed. According to the cured resin film 10, the function of protecting the touch panel electrode (transparent electrode, lead-out wiring, connection electrode, and connection terminal) and the function of preventing the visible bone phenomenon in the sensing region formed from the transparent electrode pattern can be achieved simultaneously. Can do.
  • the touch panel surface member can have a member other than the cover glass 30.
  • a plastic plate or the like can be used instead of the cover glass.
  • the touch panel surface member may have a member other than the cover glass, such as a decorative layer.
  • the transparent adhesive layer 32 can be formed using a known visibility improving film (OCA) used for bonding members together. Moreover, a transparent adhesive layer can also be formed using the transparent adhesive film (or transparent adhesive film) which consists of an adhesive resin composition.
  • OCA visibility improving film
  • the transparent adhesive layer preferably has a linear expansion coefficient ⁇ O of 600 to 1200 ppm / ° C.
  • the transparent adhesive layer may contain N-vinylpyrrolidone. Even when the transparent adhesive layer is formed of a polymer obtained by blending N-vinylpyrrolidone as an adhesion assistant, it is possible to suppress peeling between the cured resin film and the transparent adhesive layer.
  • the thickness of the transparent adhesive layer 32 is not particularly limited, but may be 150 to 200 ⁇ m, 100 to 150 ⁇ m, 50 to 100 ⁇ m, or 10 to 50 ⁇ m from the viewpoint of followability and adhesiveness.
  • the electrode substrate with a cured resin film provided in the touch panel of this embodiment can be prepared using, for example, a transfer type photosensitive film.
  • the transfer type photosensitive film of the first embodiment is a transfer type photosensitive film used for providing a cured resin film on an electrode of an electrode substrate having a substrate and an electrode provided on the main surface of the substrate. And a photosensitive resin layer containing a binder polymer, a photopolymerizable compound and a photopolymerization initiator provided on the support film, and a linear expansion coefficient ⁇ C after curing of the photosensitive resin layer.
  • the ratio [ ⁇ C / ⁇ B ] of (ppm / ° C.) and the linear expansion coefficient ⁇ B (ppm / ° C.) of the substrate is 1.2 or less.
  • the transfer type photosensitive film of the second embodiment is a transfer type photosensitive film used for providing a cured resin film on an electrode of an electrode substrate having a substrate and an electrode provided on the main surface of the substrate.
  • a support film, a photosensitive resin layer containing a binder polymer, a photopolymerizable compound and a photopolymerization initiator provided on the support film, and metal oxide particles provided on the photosensitive resin layer And a linear expansion coefficient ⁇ D (ppm / ° C.) after curing of the photosensitive resin layer and the particle-containing layer, and a linear expansion coefficient ⁇ B (ppm / ° C.) of the substrate.
  • the ratio [ ⁇ D / ⁇ B ] is 1.2 or less.
  • the linear expansion coefficient after curing of the photosensitive resin layer, and the linear expansion coefficient after curing of the photosensitive resin layer and the particle-containing layer are sufficient for the photosensitive resin layer and the photosensitive resin layer and the particle-containing layer.
  • it can be measured by the following procedure. First, a sample in which a photosensitive resin layer is provided on a PET base material so as to have a thickness of 40 ⁇ m ⁇ 10 ⁇ m is prepared. In the case with a particle-containing layer, a sample is prepared in which the particle-containing layer and the photosensitive resin layer are provided so that the total thickness is 40 ⁇ m ⁇ 10 ⁇ m.
  • the sample is cut into a size of 4 mm ⁇ 30 mm, exposed to 80 mJ / cm 2 with a parallel light exposure machine, and then cured with UV irradiation at 375 mJ / cm 2 in a UV conveyor furnace.
  • the PET substrate is peeled off to obtain a sample for measuring the linear expansion coefficient.
  • the linear expansion coefficient can be measured using a thermomechanical measurement apparatus “TMA / SS7100” (manufactured by Hitachi High-Tech Science Co., Ltd.). Specifically, the linear expansion coefficient measurement sample was heated from 30 ° C. to 100 ° C.
  • FIG. 3A is a schematic cross-sectional view showing an embodiment of a transfer type photosensitive film according to the first embodiment
  • FIG. 3B is a transfer type photosensitive film according to the second embodiment. It is a schematic cross section which shows one Embodiment of a conductive film.
  • the transfer type photosensitive film 50 shown in FIG. 3A includes a support film 40, a photosensitive resin layer 42 made of a photosensitive resin composition provided on the support film 40, and a photosensitive resin layer 42. And a protective film provided on the surface.
  • the transfer type photosensitive film 51 shown in FIG. 3B is provided with a particle-containing layer 44 containing metal oxide particles on the opposite side of the photosensitive resin layer 42 from the support film 40. Has the same configuration as that of the transfer type photosensitive film 50.
  • a polymer film As the support film 40, a polymer film can be used.
  • the material of the polymer film include polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, polyethersulfone, and cycloolefin polymer.
  • the thickness of the support film 40 is preferably 5 to 100 ⁇ m, preferably 10 to 70 ⁇ m, from the viewpoints of ensuring coverage and suppressing a reduction in resolution when irradiated with actinic rays through the support film 40. Is more preferably 15 to 40 ⁇ m, and particularly preferably 15 to 35 ⁇ m.
  • the photosensitive resin layer 42 includes a binder polymer (hereinafter also referred to as (A) component), a photopolymerizable compound (hereinafter also referred to as (B) component), and a photopolymerization initiator (hereinafter also referred to as (C) component). ) And a photosensitive resin composition.
  • A binder polymer
  • B photopolymerizable compound
  • C photopolymerization initiator
  • ком ⁇ онен polymer As the component (A), a copolymer containing a structural unit derived from (a1) (meth) acrylic acid and a structural unit derived from (a2) (meth) acrylic acid alkyl ester is preferable.
  • the alkyl of the alkyl ester here includes an alkyl group having a substituent and a cycloalkyl group.
  • the content of the structural unit derived from (meth) acrylic acid is the blending amount of (meth) acrylic acid based on the total mass of monomers constituting the component (A) from the viewpoint of rust prevention and developability. Is preferably 10 to 50% by mass, more preferably 30% by mass or less from the viewpoint of rust prevention, and preferably 10% by mass or more from the viewpoint of developability.
  • (a2) (meth) acrylic acid alkyl ester examples include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, ( Examples include methacrylic acid cyclohexyl and (meth) acrylic acid hydroxyl ethyl ester.
  • the content of the structural unit derived from the (meth) acrylic acid alkyl ester is such that the blending amount of the (meth) acrylic acid alkyl ester based on the total mass of the monomer constituting the component (A) is 90% by mass or less. It is preferable that it is 89 mass% or less, and it is still more preferable that it is 88 mass% or less.
  • the component (A) preferably has a group containing an alicyclic structure in the side chain.
  • a group can be introduced by a monomer containing a group having an alicyclic structure in the side chain.
  • a monomer for example, cyclohexyl (meth) acrylate exemplified as the component (a2) can be used.
  • the amount of the monomer containing a group having an alicyclic structure in the side chain is preferably 10 to 20% by mass, and preferably 20 to 30% by mass based on the total mass of the monomers constituting the component (A). More preferably, it is more preferably 30 to 40% by mass.
  • the copolymer may further contain other monomers that can be copolymerized with the component (a1) and / or the component (a2) in the structural unit.
  • Examples of the other monomer that can be copolymerized with the component (a1) and / or the component (a2) include (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, and (meth) acrylic.
  • Acid diethylaminoethyl ester (meth) acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate , (Meth) acrylamide, (meth) acrylonitrile, diacetone (meth) acrylamide, styrene, and vinyltoluene.
  • the above monomers may be used alone or in combination of two or more.
  • the weight average molecular weight of the binder polymer as component (A) is preferably 10,000 to 200,000, more preferably 15,000 to 150,000, and more preferably 30,000 to 200,000 from the viewpoint of resolution. 150,000 is more preferable, 30,000 to 100,000 is particularly preferable, and 40,000 to 100,000 is very preferable.
  • the measurement conditions of a weight average molecular weight shall be the same measurement conditions as the Example of this-application specification.
  • the acid value of the binder polymer as the component (A) is preferably 75 to 200 mgKOH / g, more preferably 75 to 150 mgKOH / g, and more preferably 75 to 120 mgKOH in terms of excellent rust prevention and patterning properties. More preferably, it is / g.
  • an acid value can be measured by the method described in the Example of this specification.
  • Photopolymerizable compound As the photopolymerizable compound as component (B), a photopolymerizable compound having an ethylenically unsaturated group can be used.
  • Examples of the photopolymerizable compound having an ethylenically unsaturated group include a monofunctional vinyl monomer, a bifunctional vinyl monomer, and a polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups.
  • Examples of the monofunctional vinyl monomer include (meth) acrylic acid, (meth) acrylic acid alkyl ester, and those co-polymerized as monomers used for the synthesis of a copolymer which is a preferred example of the component (A). Examples thereof include polymerizable monomers.
  • bifunctional vinyl monomer examples include polyethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenol A polyoxyethylene polyoxypropylene di (meth) acrylate (2 , 2-bis (4- (meth) acryloxypolyethoxypolypropoxyphenyl) propane), bisphenol A diglycidyl ether di (meth) acrylate, a compound having a hydroxyl group and an ethylenically unsaturated group (for example, ⁇ -hydroxyethyl acrylate) , ⁇ -hydroxyethyl methacrylate and the like) and a polyvalent carboxylic acid (such as phthalic anhydride) and the like.
  • polyethylene glycol di (meth) acrylate trimethylolpropane di (meth) acrylate
  • polypropylene glycol di (meth) acrylate bisphenol A polyoxyethylene polyoxypropylene
  • the photosensitive resin composition of the present embodiment preferably contains a compound having a tricyclodecane skeleton or a tricyclodecene skeleton from the viewpoint of improving the adhesion to the electrode.
  • a compound having a tricyclodecane skeleton or a tricyclodecene skeleton from the viewpoint of improving the adhesion to the electrode.
  • Examples of such a compound include di (meth) acrylate compounds represented by the following general formula (B-1).
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group
  • X represents a divalent group having a tricyclodecane skeleton or a tricyclodecene skeleton
  • R 3 and R 4 each independently represents an alkylene group having 1 to 4 carbon atoms
  • n and m each independently represents an integer of 0 to 2
  • p and q each independently represents an integer of 0 or more.
  • P + q 0 to 10 is selected.
  • R 3 and R 4 are preferably an ethylene group or a propylene group, and more preferably an ethylene group.
  • the propylene group may be either an n-isopropylene group or an isopropylene group.
  • the divalent group having a tricyclodecane skeleton or a tricyclodecene skeleton contained in X has a bulky structure, so that the cured film has a low viscosity. Moisture permeability can be improved.
  • tricyclodecane skeleton and “tricyclodecene skeleton” in the present specification refer to the following structures (where each bond is an arbitrary position).
  • a tricyclodecane skeleton such as tricyclodecane dimethanol di (meth) acrylate is used from the viewpoint of low moisture permeability of the obtained cured resin film and improved adhesion to an electrode.
  • a compound having is preferred. These are available as DCP and A-DCP (both manufactured by Shin-Nakamura Chemical Co., Ltd.).
  • the ratio of the compound having a tricyclodecane skeleton or a tricyclodecene skeleton is 100 parts by mass of the total amount of the photopolymerizable compounds contained in the photosensitive resin composition from the viewpoint of improving the adhesion to the electrode.
  • the amount is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, and further preferably 80 parts by mass or more.
  • Examples of the polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups include trimethylolpropane tri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, Polyhydric alcohols such as dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetraacrylate, and ⁇ , ⁇ -unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, etc.) Compound obtained by reaction; Compound obtained by addition reaction of glycidyl group-containing compound such as trimethylolpropane triglycidyl ether tri (meth) acrylate and ⁇ , ⁇ -unsaturated carboxylic acid; Diglycerin (meta Diglycerol
  • the photosensitive resin composition of the present embodiment preferably contains a polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups from the viewpoint of improving adhesion to the electrode.
  • a polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups from the viewpoint of improving adhesion to the electrode.
  • it has a (meth) acrylate compound having a skeleton derived from pentaerythritol, a (meth) acrylate compound having a skeleton derived from dipentaerythritol, and a skeleton derived from trimethylolpropane.
  • (meth) acrylate having a skeleton derived from dipentaerythritol means an esterified product of dipentaerythritol and (meth) acrylic acid, and the esterified product is a compound modified with an alkyleneoxy group.
  • the number of ester bonds in one molecule is preferably 6, but a compound having 1 to 5 ester bonds may be mixed.
  • the (meth) acrylate compound having a skeleton derived from trimethylolpropane means an esterified product of trimethylolpropane and (meth) acrylic acid, and the esterified product is a compound modified with an alkyleneoxy group.
  • the number of ester bonds in one molecule is preferably 3, but a compound having 1 to 2 ester bonds may be mixed.
  • the (meth) acrylate compound having a skeleton derived from trimethylolpropane a compound obtained by dimerizing a trimethylolpropane di (meth) acrylate compound may be used.
  • the above compounds can be used alone or in combination of two or more.
  • the proportion of the monomer having at least three polymerizable ethylenically unsaturated groups is, from the viewpoint of reliability, of 100 parts by mass of the total amount of the photopolymerizable compound contained in the photosensitive resin composition 20 parts by mass or more, preferably 30 parts by mass or more, and more preferably 40 parts by mass or more.
  • the content of the component (A) and the component (B) in the photosensitive resin composition of the present embodiment is such that the component (A) is 35 to 35 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). 85 parts by mass, component (B) is preferably 15 to 65 parts by mass, component (A) is preferably 40 to 80 parts by mass, and component (B) is more preferably 20 to 60 parts by mass, More preferably, the component (B) is 30 to 50 parts by mass, the component (A) is 55 to 65 parts by mass, and the component (B) is 35 to 45 parts by mass. Is particularly preferred.
  • the content of the component (A) and the component (B) is (A) relative to 100 parts by mass of the total amount of the component (A) and the component (B).
  • the component is preferably 35 parts by mass or more, more preferably 40 parts by mass or more, still more preferably 50 parts by mass or more, and particularly preferably 55 parts by mass or more.
  • the photopolymerization initiator is not particularly limited as long as it can cure the photosensitive resin layer by irradiation with actinic rays. From the viewpoint of transparency and reliability, acylphosphine oxide photopolymerization initiators and oxime ester photopolymerization initiators are preferred.
  • Acylphosphine oxide photoinitiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6- Mention may be made of trimethylbenzoyl-phosphinate.
  • the acylphosphine oxide photopolymerization initiator is available as IRGACURE TPO, IRGACURE 819, IRGACURE TPO-L (above, product name manufactured by BASF Japan Ltd.). By using an acylphosphine oxide photopolymerization initiator, a sufficient polymerization reaction rate can be obtained in the photosensitive resin layer, and pattern appearance can be suppressed.
  • Examples of the oxime ester photopolymerization initiator include a compound represented by the following general formula (1), a compound represented by the following general formula (2), or a compound represented by the following general formula (3).
  • R 11 and R 12 each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group or a tolyl group, and having 1 to 8 carbon atoms
  • An alkyl group, a cycloalkyl group having 4 to 6 carbon atoms, a phenyl group or a tolyl group is preferable, and an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms, a phenyl group or a tolyl group is preferable.
  • R 13 represents —H, —OH, —COOH, —O (CH 2 ) OH, —O (CH 2 ) 2 OH, —COO (CH 2 ) OH or —COO (CH 2 ) 2 OH; It is preferably H, —O (CH 2 ) OH, —O (CH 2 ) 2 OH, —COO (CH 2 ) OH, or —COO (CH 2 ) 2 OH, and —H, —O (CH 2 ) 2 OH or —COO (CH 2 ) 2 OH is more preferable.
  • R 14 each independently represents an alkyl group having 1 to 6 carbon atoms, and is preferably a propyl group.
  • R 15 represents NO 2 or ArCO (wherein Ar represents an aryl group), and Ar is preferably a tolyl group.
  • R 16 and R 17 each independently represent an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group, preferably a methyl group, a phenyl group, or a tolyl group.
  • R 18 represents an alkyl group having 1 to 6 carbon atoms, and is preferably an ethyl group.
  • R 19 is an organic group having an acetal bond, and is preferably a substituent corresponding to R 19 in a compound represented by the formula (3-1) described later.
  • R 20 and R 21 each independently represents an alkyl group having 1 to 12 carbon atoms, a phenyl group or a tolyl group, preferably a methyl group, a phenyl group or a tolyl group, and more preferably a methyl group.
  • R 22 represents a hydrogen atom or an alkyl group.
  • the compound represented by the general formula (1) is available as IRGACURE OXE 01 (manufactured by BASF Japan Ltd., product name).
  • the compound represented by the above general formula (2) is available as DFI-091 (product name, manufactured by Daito Chemix Co., Ltd.).
  • the compound represented by the general formula (3) is available as Adekaoptomer N-1919 (product name, manufactured by ADEKA Corporation).
  • an acyl phosphine oxide photopolymerization initiator and an oxime ester photopolymerization initiator in combination.
  • the moisture permeability of the formed resin cured film can be further reduced.
  • the mass ratio of the acylphosphine oxide photopolymerization initiator and the oxime ester compound is 8: 1 to 0.5: 1 from the viewpoint of pattern appearance, reliability, color, and curability. More preferably, the ratio is 4: 1 to 2: 1.
  • the content of the component (C) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B) in terms of excellent photosensitivity and resolution. It is more preferably from 5 to 5 parts by mass, further preferably from 1 to 3 parts by mass, and particularly preferably from 1 to 2 parts by mass.
  • a triazole compound having a mercapto group, a tetrazole compound having a mercapto group, a thiadiazole compound having a mercapto group At least one compound selected from the group consisting of a triazole compound having an amino group and a tetrazole compound having an amino group can be further contained.
  • the triazole compound having a mercapto group include 3-mercapto-triazole (manufactured by Wako Pure Chemical Industries, Ltd., product name: 3MT).
  • the thiadiazole compound having a mercapto group include 2-amino-5-mercapto-1,3,4-thiadiazole (product name: ATT, manufactured by Wako Pure Chemical Industries, Ltd.).
  • triazole compound having an amino group examples include, for example, benzotriazole, 1H-benzotriazole-1-acetonitrile, benzotriazole-5-carboxylic acid, 1H-benzotriazole-1-methanol, carboxybenzotriazole, and the like substituted with an amino group.
  • examples thereof include compounds in which an amino group is substituted for a triazole compound containing a mercapto group such as 3-mercaptotriazole and 5-mercaptotriazole.
  • tetrazole compound having an amino group examples include 5-amino-1H-tetrazole, 1-methyl-5-amino-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 1-carboxymethyl-5-amino- Examples include tetrazole. These tetrazole compounds may be water-soluble salts thereof. Specific examples include alkali metal salts of 1-methyl-5-amino-tetrazole such as sodium, potassium and lithium.
  • the content thereof is preferably 0.05 to 5.0 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). 0.1 to 2.0 parts by mass is more preferable, 0.2 to 1.0 part by mass is further preferable, and 0.3 to 0.8 part by mass is particularly preferable.
  • composition forming the photosensitive resin layer As other additives, adhesiveness such as a phosphate ester having an ethylenically unsaturated group, a silane coupling agent, etc., as necessary.
  • Each can be contained in an amount of about 0.01 to 20 parts by mass with respect to 100 parts by mass in total. These can be used alone or in combination of two or more.
  • the thickness of the photosensitive resin layer may be 1 to 15 ⁇ m, preferably 2 to 10 ⁇ m, more preferably 3 to 8 ⁇ m, further preferably 4 to 6 ⁇ m, and more preferably 5 to 6 ⁇ m. It is particularly preferred. When the thickness is 1 to 15 ⁇ m, there are few defects at the time of coating, and film formation with excellent transparency is possible. Further, the thickness of the photosensitive resin layer after curing (that is, the thickness of the cured resin film) is also preferably within the above range.
  • the particle-containing layer 44 is a layer containing metal oxide particles.
  • the particle-containing layer 44 can have a refractive index relatively higher than that of the photosensitive resin layer 42 by containing metal oxide particles.
  • the particle-containing layer 44 preferably has a refractive index in the range of 1.40 to 1.90, more preferably 1.50 to 1.90, and more preferably 1.53 to 1.85 at 633 nm. More preferably, it is particularly preferably 1.55 to 1.75.
  • grain containing layer contains a sclerosing
  • the refractive index at 633 nm of the particle-containing layer 44 is within the above range, various members (for example, modularized) used on the cured resin film when the cured resin film is provided on a transparent electrode pattern such as ITO.
  • the refractive index is intermediate between the cover glass and the transparent electrode layer used to bond the transparent electrode pattern), and the optical part is formed at the part where the transparent electrode pattern such as ITO is formed and the part where it is not formed. It is possible to reduce the color difference due to simple reflection and prevent the appearance of bones. Moreover, it becomes possible to reduce the reflected light intensity of the whole screen, and to suppress the transmittance
  • the refractive index of a transparent electrode such as ITO is preferably 1.80 to 2.10, more preferably 1.85 to 2.05, and even more preferably 1.90 to 2.00.
  • the refractive index of the member such as the transparent adhesive layer is preferably 1.45 to 1.55, more preferably 1.47 to 1.53, and 1.48 to 1.51. Is more preferable.
  • the particle-containing layer 44 preferably has a minimum light transmittance of 80% or more in a wavelength region of 450 to 650 nm, more preferably 85% or more, and further preferably 90% or more.
  • the minimum light transmittance in the wavelength region of 450 to 650 nm of the particle-containing layer after curing is preferably within the above range.
  • the particle-containing layer 44 can contain the above-mentioned (A) component, (B) component, and (C) component, and can further contain the above-described additives as necessary.
  • the particle-containing layer 44 is not necessarily required to contain a photopolymerization component such as the component (B) or the component (C), and the particle-containing layer is formed using a photopolymerization component that migrates from an adjacent photosensitive resin layer by layer formation. It can also be photocured.
  • the particle-containing layer 44 contains metal oxide particles (hereinafter also referred to as (E) component).
  • the metal oxide particles preferably contain metal oxide particles having a refractive index of 1.50 or more at a wavelength of 633 nm.
  • the metal oxide particles include particles made of metal oxides such as zirconium oxide, titanium oxide, tin oxide, zinc oxide, indium tin oxide, indium oxide, aluminum oxide, and yttrium oxide. Among these, particles of zirconium oxide or titanium oxide are preferable from the viewpoint of suppressing the bone appearance phenomenon.
  • the zirconium oxide particles when the material of the transparent electrode is ITO, it is preferable to use zirconium oxide nanoparticles from the viewpoint of improving the refractive index and adhesion between the ITO and the transparent substrate.
  • the particle size distribution Dmax is preferably 40 nm or less.
  • Zirconium oxide nanoparticles are OZ-S30K (product name, manufactured by Nissan Chemical Industries, Ltd.), OZ-S40K-AC (product name, manufactured by Nissan Chemical Industries, Ltd.), SZR-K (zirconium oxide methyl ethyl ketone dispersion, Sakai Chemical Co., Ltd.). Kogyo Co., Ltd., product name) and SZR-M (zirconium oxide methanol dispersion, Sakai Chemical Industry Co., Ltd., product name) are commercially available.
  • the particle-containing layer 44 may contain titanium oxide nanoparticles as the component (E).
  • the particle size distribution Dmax is preferably 50 nm or less, more preferably 10 to 50 nm.
  • oxide particles or sulfide particles containing atoms such as Mg, Al, Si, Ca, Cr, Cu, Zn, and Ba can be used. These can be used alone or in combination of two or more.
  • organic compounds such as a compound having a triazine ring, a compound having an isocyanuric acid skeleton, and a compound having a fluorene skeleton can also be used.
  • the refractive index in wavelength 633nm can be improved.
  • the thickness of the particle-containing layer 44 may be 0.01 to 1 ⁇ m, preferably 0.03 to 0.5 ⁇ m, more preferably 0.04 to 0.3 ⁇ m, and 0.07 to 0.5 ⁇ m.
  • the thickness is more preferably 0.25 ⁇ m, particularly preferably 0.05 to 0.2 ⁇ m.
  • the thickness of the particle-containing layer 44 (that is, the particle-containing region) after curing is also preferably within the above range.
  • the refractive index of the particle-containing layer 44 can be obtained as follows using ETA-TCM (product name, manufactured by AudioDev GmbH). It can. The following measurement is performed under the condition of 25 ° C. (1) A coating solution for forming a particle-containing layer is uniformly applied on a glass substrate having a thickness of 0.7 mm, a length of 10 cm and a width of 10 cm using a spin coater, and is heated for 3 minutes with a hot air convection dryer at 100 ° C. Dry to remove the solvent and form a particle-containing layer.
  • ETA-TCM product name, manufactured by AudioDev GmbH
  • the sample is allowed to stand for 30 minutes in a box dryer (model number: NV50-CA, manufactured by Mitsubishi Electric Corporation) heated to 140 ° C. to obtain a sample for refractive index measurement having a particle-containing layer.
  • a box dryer model number: NV50-CA, manufactured by Mitsubishi Electric Corporation
  • the refractive index at a wavelength of 633 nm is measured for the obtained sample for refractive index measurement using ETA-TCM (product name, manufactured by AudioDev GmbH).
  • the refractive index in a single photosensitive resin layer can also be measured by the same method.
  • the value of the outermost surface layer on the protective film side of the particle-containing layer is used.
  • Examples of the protective film 46 include polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, polyethylene-vinyl acetate copolymer, polyethylene-vinyl acetate copolymer film, and a laminated film of these films and polyethylene.
  • the thickness of the protective film 46 is preferably 5 to 100 ⁇ m, but is preferably 70 ⁇ m or less, more preferably 60 ⁇ m or less, and more preferably 50 ⁇ m or less from the viewpoint of storing the transfer type photosensitive film in a roll shape. More preferably, it is particularly preferably 40 ⁇ m or less.
  • a photosensitive resin layer-forming coating solution and a particle-containing layer-forming coating solution are prepared, which are respectively supported by the support film 40 and the protective film 40. It can be formed by applying and drying on the film 46.
  • the transfer-type photosensitive film 51 includes a support film 40 on which the photosensitive resin layer 42 is formed and a protective film 46 on which the particle-containing layer 44 is formed, and the photosensitive resin layer 42 and the particle-containing layer 44 are combined. It can be formed by pasting together in an opposing state.
  • the transfer type photosensitive film 51 is coated with a coating solution containing a coating solution for forming a photosensitive resin layer on the support film 40, dried, and then coated with a particle-containing layer on the photosensitive resin layer 42. It can also be formed by applying a liquid, drying, and attaching a protective film 46.
  • the transfer type photosensitive film 50 can be formed by applying a coating solution containing a coating solution for forming a photosensitive resin layer on the support film 40, drying it, and attaching a protective film 46.
  • the coating solution can be obtained by uniformly dissolving or dispersing each component constituting the photosensitive resin composition according to the present embodiment and the particle-containing layer in a solvent.
  • the solvent used as the coating solution is not particularly limited, and known ones can be used. Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, methanol, ethanol, propanol, butanol, methylene glycol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether , Diethylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, chloroform, methylene chloride and the like.
  • Application methods include doctor blade coating method, Mayer bar coating method, roll coating method, screen coating method, spinner coating method, inkjet coating method, spray coating method, dip coating method, gravure coating method, curtain coating method, and die coating method. Etc.
  • the drying conditions are not particularly limited, but the drying temperature is preferably 60 to 130 ° C., and the drying time is preferably 0.5 to 30 minutes.
  • FIG. 4 is a schematic cross-sectional view for explaining a method of manufacturing an electrode substrate with a cured resin film using the transfer type photosensitive film 51 according to this embodiment. Hereinafter, the method of this embodiment will be described.
  • the particle-containing layer 44, the photosensitive resin layer 42, and the support film 40 are pressure-bonded onto the electrode 2 of the electrode substrate 3 from the particle-containing layer 44 side.
  • the pressing means include a pressing roll.
  • the pressure roll may be provided with a heating means so that it can be heat-pressure bonded.
  • the heating temperature in the case of thermocompression bonding makes it difficult to thermally cure or thermally decompose the constituent components of the photosensitive resin layer 42 or the particle-containing layer 44 from the viewpoint of adhesion between the particle-containing layer 44 and the electrode substrate 3. From the viewpoint, it is preferably 10 to 160 ° C., more preferably 20 to 150 ° C., and further preferably 30 to 150 ° C.
  • the pressure during the thermocompression bonding is 50 to 1 ⁇ 10 5 N / in linear pressure from the viewpoint of suppressing deformation of the electrode substrate 3 while ensuring sufficient adhesion between the particle-containing layer 44 and the electrode substrate 3.
  • m is preferable, 2.5 ⁇ 10 2 to 5 ⁇ 10 4 N / m is more preferable, and 5 ⁇ 10 2 to 4 ⁇ 10 4 N / m is further preferable.
  • the pre-heat treatment of the electrode substrate 3 is not necessarily required.
  • the electrode substrate 3 is further improved in terms of further improving the adhesion between the particle-containing layer 44 and the electrode substrate 3. 3 may be preheated.
  • the treatment temperature at this time is preferably 30 to 150 ° C.
  • the actinic ray L is irradiated to the photosensitive resin layer 42 and the particle-containing layer 44 after the transfer.
  • the support film 40 on the photosensitive resin layer 42 and the particle-containing layer 44 is transparent when irradiated with actinic rays, it can be irradiated with actinic rays as it is. (See FIG. 4B).
  • a known active light source can be used as the active light source.
  • a predetermined portion of the photosensitive resin layer 42 and the particle-containing layer 44 can be irradiated with actinic rays in a pattern via a photomask.
  • the pattern includes a shape in which only a connection portion with another base material is removed in a rectangular shape, a shape in which only a frame portion of the base material is removed, and the like.
  • the irradiation amount of actinic rays is 1 ⁇ 10 2 to 1 ⁇ 10 4 J / m 2 , and heating can be accompanied during irradiation. If the irradiation amount of this actinic ray is 1 ⁇ 10 2 J / m 2 or more, it becomes possible to sufficiently advance photocuring of the photosensitive resin layer and the particle-containing layer, and 1 ⁇ 10 4 J / m 2. If it is below, there exists a tendency which can suppress discoloration of the photosensitive resin layer and particle-containing layer.
  • the cured resin film (refracted) covering part or all of the electrode by removing the unexposed portions of the photosensitive resin layer and the particle-containing layer after irradiation with actinic rays with a developer. Rate adjustment pattern) can be formed.
  • a image development process is performed after irradiation of actinic light, when the support film 40 is laminated
  • the development step can be performed by a known method such as spraying, showering, rocking dipping, brushing, or scrubbing using a known developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent.
  • spray development is preferably performed using an alkaline aqueous solution from the viewpoint of environment and safety.
  • the development temperature and time can be adjusted within a conventionally known range.
  • the electrode substrate 101 with a cured resin film shown in FIG. 1B can be obtained through the above steps.
  • the cured film pattern is formed using the transfer type photosensitive film 51.
  • the transfer type photosensitive film 50 having no particle-containing layer is used, the cured resin film is formed by the same method. be able to.
  • FIG. 5 is a schematic cross-sectional view showing a method for manufacturing the touch panel 200 shown in FIG. 2 using the electrode substrate 101 with a cured resin film obtained above as a touch sensor substrate with a cured resin film.
  • the cover glass 30 provided with the transparent adhesive layer 32 and the electrode substrate with a cured resin film are bonded together so that the transparent adhesive layer 32 and the cured resin film 10 are in close contact.
  • the transparent adhesive layer 32 is provided on the cover glass 30, but the transparent adhesive layer 32 is provided on the resin cured film of the electrode substrate with the resin cured film, and this is bonded to the touch panel surface member. May be.
  • the touch panel of the present embodiment is not limited to the above configuration, and various changes can be made.
  • an electrode substrate provided with electrodes on both main surfaces of the base material may be provided, and a resin cured film may be provided on both surfaces of the electrode substrate.
  • the touch panel back member of the image display element such as liquid crystal or organic EL can be bonded to the electrode substrate with the cured resin film via the transparent adhesive layer.
  • transfer type photosensitive film and the electrode substrate with a cured resin film of the present embodiment described above can be applied to a force sensor substrate, an electromagnetic wave shield substrate, and the like in addition to the touch panel sensor substrate.
  • the weight average molecular weight and acid value of the binder polymer were determined by the following measuring methods.
  • the weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC), and was derived by conversion using a standard polystyrene calibration curve.
  • the measurement conditions for GPC are shown below. ⁇ GPC measurement conditions> Pump: Hitachi L-6000 (manufactured by Hitachi, Ltd., product name) Column: Gelpack GL-R420, Gelpack GL-R430, Gelpack GL-R440 (product name, manufactured by Hitachi Chemical Co., Ltd.) Eluent: Tetrahydrofuran Measurement temperature: 40 ° C Flow rate: 2.05 mL / min Detector: L-3300 (RI detector, manufactured by Hitachi, Ltd., product name)
  • the acid value was measured by a neutralization titration method based on JIS K0070 as shown below. First, the binder polymer solution was heated at 130 ° C. for 1 hour to remove volatile components to obtain a solid content. Then, after precisely weighing 1.0 g of this solid binder polymer, 30 g of acetone was added to this binder polymer, and this was uniformly dissolved to obtain a resin solution. Next, an appropriate amount of an indicator, phenolphthalein, was added to the resin solution, and titration was performed using a 0.1 mol / L aqueous potassium hydroxide solution. And the acid value was computed by following Formula.
  • Acid value 0.1 ⁇ V ⁇ f1 ⁇ 56.1 / (Wp ⁇ I / 100)
  • V represents the titration amount (mL) of the 0.1 mol / L potassium hydroxide aqueous solution used for the measurement
  • f1 represents the factor (concentration conversion factor) of the 0.1 mol / L potassium hydroxide aqueous solution
  • Wp represents the mass (g) of the measured resin solution
  • I represents the ratio (mass%) of the non-volatile content in the measured resin solution.
  • Examples 1 to 9 and Comparative Examples 1 to 6) [Preparation of coating solution for forming photosensitive resin layer]
  • the components shown in Tables 2 and 3 were blended in the blending amounts (unit: parts by mass) shown in the same table and mixed for 15 minutes using a stirrer to prepare a coating solution for forming a photosensitive resin layer.
  • the amount of component (A) indicates the amount of solids.
  • the coating solution was adjusted so that the solid content concentration was 20 to 30% by mass using methyl ethyl ketone as a solvent.
  • A-DCP Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name “A-DCP”)
  • DCP Tricyclodecane dimethanol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name “DCP”)
  • 4G Polyethylene glycol # 200 dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name “4G”)
  • TMPT Trimethylolpropane triacrylate (manufactured by Nippon Kayaku Co., Ltd., product name “TMPT”)
  • UN-21PH Urethane prepolymer (manufactured by NOF Corporation, product name "UN-21PH”)
  • OXE-01 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)] (manufactured by BASF Japan Ltd., product name “IRGACURE OXE 01”)
  • Irg-TPO 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by BASF Japan Ltd., product name “IRGACURE TPO”)
  • ADDITIVE 8032 Octamethylcyclotetrasiloxane (made by Toray Dow Corning Co., Ltd., product name “ADDITIVE 8032”)
  • AW500 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (manufactured by Kawaguchi Chemical Co., Ltd., product name “AW500”)
  • B6030 5-amino-1H-tetrazole (manufactured by Chiyoda Chemical Co., Ltd., product name “B6030”)
  • PM21 Phosphoric acid ester containing a photopolymerizable unsaturated bond (manufactured by Nippon Kayaku Co., Ltd., product name “PM21”)
  • E1 Zirconia nanoparticle dispersion (manufactured by Nissan Chemical Industries, Ltd., product name “OZ-S30K”)
  • the photosensitive resin layer forming coating solution prepared above was uniformly applied onto the support film using a comma coater. The solvent was removed by drying with a hot air convection dryer at 110 ° C. for 3 minutes to form a photosensitive resin layer having a thickness of 8 ⁇ m.
  • a protective film having a particle-containing layer and a support film having a photosensitive resin layer are bonded together at 23 ° C. using a laminator (manufactured by Hitachi Chemical Co., Ltd., product name: HLM-3000 type) to protect the film.
  • a laminator manufactured by Hitachi Chemical Co., Ltd., product name: HLM-3000 type
  • the photosensitive resin layer forming coating solution prepared above was uniformly applied onto the support film using a comma coater. The solvent was removed by drying with a hot air convection dryer at 110 ° C. for 3 minutes to form a photosensitive resin layer having a thickness of 8 ⁇ m.
  • the support film having the obtained photosensitive resin layer and a 30 ⁇ m-thick polypropylene film (manufactured by Oji F-Tex Co., Ltd., product name: ES-201) were bonded together at 23 ° C. as a protective film,
  • a transfer type photosensitive film was prepared in which the photosensitive resin layer and the support film were laminated in this order.
  • the sample was cut into a size of 4 mm ⁇ 30 mm, exposed at 80 mJ / cm 2 with a parallel light exposure machine, and then cured by UV irradiation at 375 mJ / cm 2 in a UV conveyor furnace.
  • the cured sample was heated with a box dryer at 140 ° C. for 30 minutes, and then the PET substrate was peeled off to obtain a sample for measuring linear expansion coefficient.
  • the linear expansion coefficient was measured using a thermomechanical measuring apparatus “TMA / SS7100” (manufactured by Hitachi High-Tech Science Co., Ltd.). Specifically, the linear expansion coefficient measurement sample was heated from 30 ° C. to 100 ° C. for the purpose of removing moisture in the sample while applying a weight of 5 g using TMA / SS7100, and then the temperature of the sample. After being lowered, the mixture was heated from 30 ° C. to 300 ° C. at a temperature rising rate of 5 ° C./min. The slope of the elongation of the sample (resin cured film) between 50 ° C. and 60 ° C. during heating from 30 ° C. to 300 ° C. was measured, and this was used as the linear expansion coefficient.
  • TMA / SS7100 manufactured by Hitachi High-Tech Science Co., Ltd.
  • the linear expansion coefficient of the cycloolefin polymer (COP) substrate was measured in the same manner as described above except that the COP substrate was cut into a size of 4 mm ⁇ 30 mm and used as a measurement sample.
  • the linear expansion coefficient of the transparent adhesive film (OCA) was measured in the same manner as described above except that OCA was cut into a size of 5 mm ⁇ 5 mm and used as a measurement sample. However, the measurement temperature was changed to a condition of heating from 30 ° C. to 200 ° C. at a temperature rising rate of 5 ° C./min.
  • Cyclic olefin polymer (COP) substrates having a thickness of 55 ⁇ m were prepared in three different sizes (width: 16, width: ratio of 9, diagonal length: 10 inches, 15 inches, 20 inches).
  • a photosensitive resin layer of a photosensitive film was laminated on both surfaces of each COP substrate under the conditions of 100 ° C., 0.4 MPa, and 0.6 m / min. When the photosensitive film had a particle-containing layer, the photosensitive resin layer and the particle-containing layer were laminated so that the particle-containing layer was in close contact with the substrate.
  • the laminated photosensitive resin layer was exposed at 60 mJ / cm 2 with a parallel light exposure machine, then irradiated with UV at 375 mJ / cm 2 in a UV conveyor furnace, and further at 140 ° C. with a box dryer.
  • a cured resin film was formed by heating for 30 minutes to obtain a COP substrate with a cured resin film.
  • OCA1 and OCA2 were created by the following method.
  • acrylic acid derivative polymer A4 a copolymer of 2-ethylhexyl acrylate and 2-hydroxyethyl acrylate (weight average molecular weight 150,000) (hereinafter this copolymer was referred to as “acrylic acid derivative polymer A4”). ”).
  • the measurement of the weight average molecular weight was performed using the gel permeation chromatography which used tetrahydrofuran (THF) as a solvent, and it determined using the calibration curve of a standard polystyrene using the following apparatus and measurement conditions.
  • the adhesive resin composition obtained above is dropped onto a polyethylene terephthalate film, and further covered with a polyethylene terephthalate film, and the adhesive resin composition is applied in a sheet form with a roller.
  • a transparent adhesive film was obtained by irradiating with 2 J / cm 2 of ultraviolet rays using an idle fin 3000, high power metal halide lamp (manufactured by Co., Ltd.). The thickness of the transparent adhesive film was adjusted to 150 ⁇ m.
  • a COP substrate with a cured resin film and a glass substrate with a transparent adhesive film were bonded together via a transparent adhesive film. This was heated at 50 ° C. for 30 minutes under a pressure of 0.5 MPa in an autoclave.
  • a laminated sample having a laminated structure of resin cured film / COP substrate (3 types) / cured resin film / OCA (2 types) / glass plate (3 types) was produced.
  • Example 10 A laminated sample was produced in the same manner as in Example 9 except that the thickness of the photosensitive resin layer was changed to 5 ⁇ m in the production of the transfer type photosensitive film.
  • SYMBOLS 1 Base material, 2 ... Electrode, 3 ... Electrode substrate, 10 ... Resin cured film, 20 ... Particle-containing area

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Human Computer Interaction (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials For Photolithography (AREA)

Abstract

L'invention concerne un substrat d'électrode pourvu d'un film durci en résine, comprenant un matériau de base et une électrode disposée sur une surface principale du matériau de base, le substrat d'électrode ayant un film durci en résine disposé sur l'électrode, et le rapport [αA/αB] du coefficient de dilatation linéaire αA (ppm/°C) du film durci en résine au coefficient de dilatation linéaire αB (ppm/°C) du matériau de base est inférieur ou égal à 1,2.
PCT/JP2018/019536 2018-05-21 2018-05-21 Film photosensible de type transfert, substrat d'électrode avec film durci en résine et panneau tactile WO2019224887A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP2018/019536 WO2019224887A1 (fr) 2018-05-21 2018-05-21 Film photosensible de type transfert, substrat d'électrode avec film durci en résine et panneau tactile

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2018/019536 WO2019224887A1 (fr) 2018-05-21 2018-05-21 Film photosensible de type transfert, substrat d'électrode avec film durci en résine et panneau tactile

Publications (1)

Publication Number Publication Date
WO2019224887A1 true WO2019224887A1 (fr) 2019-11-28

Family

ID=68616866

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/019536 WO2019224887A1 (fr) 2018-05-21 2018-05-21 Film photosensible de type transfert, substrat d'électrode avec film durci en résine et panneau tactile

Country Status (1)

Country Link
WO (1) WO2019224887A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10171149A (ja) * 1996-12-09 1998-06-26 Taiho Ind Co Ltd 記録済み透明シートの画像鮮明化方法及び画像鮮明化フィルム
JP2014108541A (ja) * 2012-11-30 2014-06-12 Fujifilm Corp 転写フィルムおよび透明積層体、それらの製造方法、静電容量型入力装置ならびに画像表示装置
WO2016035819A1 (fr) * 2014-09-04 2016-03-10 富士フイルム株式会社 Composition de résine photosensible, procédé de fabrication de film durci, film durci, dispositif d'affichage à cristaux liquides, dispositif d'affichage à électroluminescence organique, et panneau tactile
WO2017104810A1 (fr) * 2015-12-18 2017-06-22 アルプス電気株式会社 Dispositif d'entrée

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10171149A (ja) * 1996-12-09 1998-06-26 Taiho Ind Co Ltd 記録済み透明シートの画像鮮明化方法及び画像鮮明化フィルム
JP2014108541A (ja) * 2012-11-30 2014-06-12 Fujifilm Corp 転写フィルムおよび透明積層体、それらの製造方法、静電容量型入力装置ならびに画像表示装置
WO2016035819A1 (fr) * 2014-09-04 2016-03-10 富士フイルム株式会社 Composition de résine photosensible, procédé de fabrication de film durci, film durci, dispositif d'affichage à cristaux liquides, dispositif d'affichage à électroluminescence organique, et panneau tactile
WO2017104810A1 (fr) * 2015-12-18 2017-06-22 アルプス電気株式会社 Dispositif d'entrée

Similar Documents

Publication Publication Date Title
JP6589953B2 (ja) 感光性エレメント
WO2016181422A1 (fr) Film de réglage d'indice de réfraction photosensible du type à transfert, procédé de formation de modèle d'indice de réfraction et composant électronique
JP2013200577A (ja) 樹脂硬化膜パターンの形成方法、感光性樹脂組成物、感光性エレメント、タッチパネルの製造方法及び樹脂硬化膜
JP2016157451A (ja) 硬化膜付きタッチパネル用基材の製造方法、それに用いる感光性樹脂組成物、感光性エレメント及びタッチパネル
WO2016001955A1 (fr) Film de régulation d'indice de réfraction photosensible de type transfert
JP2019175226A (ja) タッチセンサの保護膜形成用感光性フィルム、タッチセンサの保護膜形成用感光性屈折率調整フィルム、タッチセンサの保護膜の形成方法及びタッチパネル
WO2016132401A1 (fr) Film d'ajustement d'indice de réfraction photosensible du type transfert, procédé de formation d'un motif d'ajustement d'indice de réfraction, et composant électronique
WO2017175642A1 (fr) Film de modulation d'indice de réfraction photosensible, procédé de formation d'un motif de film durci, film durci et composant électronique
JP2018165788A (ja) 転写型感光性フィルム、硬化樹脂パターンの形成方法及びタッチパネル
JP2017181541A (ja) 感光性フィルム、感光性屈折率調整フィルム、屈折率調整パターンの形成方法、硬化膜及び電子部品
WO2019207648A1 (fr) Composition de résine photosensible, film photosensible de type à transfert, substrat ayant un film durci fixé à celui-ci, et dispositif de détection
WO2019224887A1 (fr) Film photosensible de type transfert, substrat d'électrode avec film durci en résine et panneau tactile
JP6943279B2 (ja) 転写型感光性フィルム、硬化膜パターンの形成方法及びタッチパネル
JPWO2017056131A1 (ja) 転写形感光性屈折率調整フィルム
JP2015146038A (ja) 樹脂硬化膜パターンの形成方法、感光性樹脂組成物、感光性エレメント、タッチパネルの製造方法及び樹脂硬化膜
JP2019215395A (ja) 転写型感光性フィルム、硬化膜パターンの形成方法、積層体及びタッチパネル
JP2019035801A (ja) 転写型感光性フィルム、硬化膜パターンの形成方法、硬化膜及び電子部品
JP2019219631A (ja) 転写フィルム、硬化膜及びその形成方法、並びに、電子部品
JP7210091B2 (ja) 転写型感光性フィルム、硬化膜パターンの形成方法、硬化膜及びタッチパネル
JP2018045126A (ja) 真空ラミネート用感光性フィルム、転写型感光性屈折率調整フィルム、及び硬化樹脂パターンの形成方法
WO2019186781A1 (fr) Film de transfert, film durci et procédé de formation associé, et composant électrique
WO2018134883A1 (fr) Composition de résine photosensible, élément photosensible, film protecteur d'électrode de panneau tactile et panneau tactile
WO2019207677A1 (fr) Film photosensible et film de réglage d'indice de réfraction photosensible
JP5790783B2 (ja) 樹脂硬化膜パターンの形成方法、感光性樹脂組成物、感光性エレメント、タッチパネルの製造方法及び樹脂硬化膜
WO2018181722A1 (fr) Film protecteur pour électrode de panneau tactile et panneau tactile

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18920071

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18920071

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP