WO2020012651A1 - Method for manufacturing photosensitive film roll for sensing device, and photosensitive film roll for sensing device - Google Patents

Method for manufacturing photosensitive film roll for sensing device, and photosensitive film roll for sensing device Download PDF

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Publication number
WO2020012651A1
WO2020012651A1 PCT/JP2018/026575 JP2018026575W WO2020012651A1 WO 2020012651 A1 WO2020012651 A1 WO 2020012651A1 JP 2018026575 W JP2018026575 W JP 2018026575W WO 2020012651 A1 WO2020012651 A1 WO 2020012651A1
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Prior art keywords
photosensitive
photosensitive film
film
resin layer
film roll
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PCT/JP2018/026575
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French (fr)
Japanese (ja)
Inventor
智紀 寺脇
田仲　裕之
雅彦 海老原
征志 南
匠 渡邊
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日立化成株式会社
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Priority to PCT/JP2018/026575 priority Critical patent/WO2020012651A1/en
Publication of WO2020012651A1 publication Critical patent/WO2020012651A1/en

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    • 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
    • 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

Definitions

  • the present invention relates to a method for manufacturing a photosensitive film roll for a sensing device and a photosensitive film roll for a sensing device.
  • a liquid crystal display element and a touch panel are used.
  • a projected capacitive touch panel a plurality of X electrodes and a plurality of Y electrodes orthogonal to the X electrodes are formed in order to represent two-dimensional coordinates by an X axis and a Y axis.
  • ITO Indium-Tin-Oxide, indium tin oxide
  • the frame region of the touch panel is a region where the touch position cannot be detected, reducing the area of the frame region is an important factor for improving the product value.
  • metal wiring such as copper is formed in the frame area to transmit a detection signal of a touch position.
  • a corrosive component such as moisture or salt may enter the sensing area from the inside.
  • a corrosive component enters the inside of the touch panel, the metal wiring is corroded, and there is a risk of an increase in electrical resistance between the electrode and the driving circuit or a disconnection.
  • a method of forming a protective film on a substrate for a touch panel using a photosensitive resin composition is known.
  • a method of providing a protective film for example, a resist film
  • a method of providing a photosensitive resin layer containing a photosensitive resin composition on a predetermined substrate, and exposing and developing the photosensitive resin layer is known.
  • the photosensitive resin layer is laminated on a substrate using a photosensitive element (photosensitive film) including a support film and a photosensitive resin layer made of a photosensitive resin composition provided on the support film.
  • a known method is known (for example, see Patent Document 1 below).
  • the photosensitive film is generally stored and used in the form of a roll (photosensitive film roll) in which a long photosensitive film is wound around a core.
  • a roll photosensitive film roll
  • a dent may be formed on the photosensitive resin layer.
  • the photosensitive film roll is wound around the core with a certain amount of tension so as not to cause a winding deviation.At this time, foreign matter such as resin chips is caught between the photosensitive films, and the foreign matter is exposed to light. It is considered that a dent is formed in the photosensitive resin layer by digging into the photosensitive film and making a press mark. In particular, as the photosensitive film is wound closer to the core, the tightening force is more likely to be applied, so that a dent is likely to occur in the photosensitive resin layer.
  • dents in the photosensitive resin layer have not been regarded as a problem. In view of the above, the presence of a dent in the photosensitive resin layer is a serious problem.
  • the present invention has been made in view of the above-mentioned problems of the related art, and can suppress the occurrence of a dent and a winding shift, a method of manufacturing a photosensitive film roll used for a sensing device such as a touch panel, and Another object of the present invention is to provide a photosensitive film roll used for a sensing device.
  • the present invention provides a long photosensitive comprising a support film, a photosensitive resin layer disposed on the support film, and a protective film disposed on the photosensitive resin layer.
  • a method for manufacturing a photosensitive film roll for a sensing device comprising winding the photosensitive film into a roll, comprising a winding step of winding the photosensitive film around a core to obtain a photosensitive film roll,
  • the total thickness of the film and the protective film is less than 100 ⁇ m, and the length L1 of the photosensitive film for 100 turns from the core measured by unwinding the photosensitive film roll, and the diameter of the core
  • Provided is a method for manufacturing a photosensitive film roll, wherein the winding in the winding step is performed so that the ratio (L1 / D1) to D1 is 250 to 320.
  • the photosensitive film in which the total thickness of the support film and the protective film is less than 100 ⁇ m is wound in the winding step such that the ratio (L1 / D1) is 250 to 320.
  • the ratio (L1 / D1) is 250 to 320.
  • the length L2 of the photosensitive film for 100 turns outside the photosensitive film roll measured by unwinding the photosensitive film roll, and the position of the 100th turn from the outside of the photosensitive film roll It is preferable to perform winding in the above winding step so that the ratio (L2 / D2) to the diameter D2 becomes 250 to 350.
  • the number of turns of the photosensitive film roll may be 500 to 1000 turns.
  • the effects of the present invention are more effectively exhibited.
  • the photosensitive film may further include a second resin layer containing metal oxide particles disposed between the photosensitive resin layer and the protective film. Even when the photosensitive film including the second resin layer is wound into a roll, the occurrence of dents and winding deviation can be sufficiently suppressed. The difference in optical reflection characteristics between the part where the transparent electrode pattern is formed and the part where the transparent electrode pattern is not formed increases the color difference, and when the module is modularized, the transparent electrode pattern is reflected on the screen, so-called ⁇ bone view '' There is a problem of "phenomenon". According to the photosensitive film, the problem of the bone appearance phenomenon can be improved by providing the second resin layer.
  • the present invention also provides a long photosensitive film comprising a support film, a photosensitive resin layer disposed on the support film, and a protective film disposed on the photosensitive resin layer, and a roll around a core.
  • a photosensitive film roll for a sensing device wound in a shape, wherein the total thickness of the support film and the protective film is less than 100 ⁇ m, and the core is measured by unwinding the photosensitive film roll.
  • the photosensitive film roll since the total thickness of the support film and the protective film is less than 100 ⁇ m and the ratio (L1 / D1) is 250 to 320, the occurrence of dents and misalignment occurs. Is sufficiently suppressed. In particular, in the vicinity of the core where a dent is likely to occur in the photosensitive resin layer, the occurrence of a dent is suppressed while the occurrence of a winding shift is suppressed.
  • the photosensitive film roll has a length L2 of the photosensitive film corresponding to 100 turns outside the photosensitive film roll measured by unwinding the photosensitive film roll, and the 100th turn from the outside of the photosensitive film roll. It is preferable that the ratio (L2 / D2) to the diameter D2 at the position is 250 to 350.
  • the number of turns of the photosensitive film roll may be 500 to 1000 turns. In the photosensitive film roll having the number of windings within the above range, the effects of the present invention are more effectively exhibited.
  • the photosensitive film may further include a second resin layer containing metal oxide particles disposed between the photosensitive resin layer and the protective film. Even in a photosensitive film roll obtained by winding a photosensitive film having such a second resin layer into a roll, the occurrence of dents and winding deviation is sufficiently suppressed. Further, according to the photosensitive film having the second resin layer, the problem of the bone appearance phenomenon can be improved.
  • production of a dent and a winding gap are provided. be able to.
  • FIG. 1 is a perspective view schematically illustrating a photosensitive film roll according to an embodiment of the present disclosure.
  • FIG. 2 is a schematic cross-sectional view showing one embodiment of a photosensitive film constituting a photosensitive film roll.
  • FIG. 9 is a schematic cross-sectional view illustrating another embodiment of the photosensitive film constituting the photosensitive film roll. It is a schematic top view which shows one Embodiment of a touch panel.
  • FIG. 3 is a diagram illustrating a dent formed on a photosensitive resin layer.
  • (meth) acrylic acid means acrylic acid or methacrylic acid
  • (meth) acrylate means acrylate or methacrylate corresponding thereto.
  • a or B may include one of A and B, and may include both.
  • the term “layer” also includes a partially formed structure in addition to a partially formed structure when observed as a plan view.
  • step is used not only for an independent step but also for the case where the intended action of the step is achieved even if it cannot be clearly distinguished from other steps. 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.
  • the content of each component in the composition when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified, the total of the plurality of substances present in the composition Means quantity.
  • the exemplified materials may be used alone or in combination of two or more.
  • the upper limit or lower limit of the numerical range of a certain stage may be replaced with the upper limit or lower limit of the numerical range of another stage.
  • the upper limit or the lower limit of the numerical range may be replaced with the value shown in the embodiment.
  • FIG. 1 is a perspective view schematically illustrating a photosensitive film roll according to an embodiment of the present disclosure.
  • the photosensitive film roll 100 according to the present embodiment is a roll formed by winding the photosensitive film 1 around a core 50.
  • the photosensitive film roll 100 is obtained by winding the photosensitive film 1 around the core 50 by 100 turns or more.
  • the photosensitive film roll 100 has a ratio (L1 / D1) of the length L1 of the photosensitive film 1 corresponding to 100 turns from the core 50 measured by unwinding the roll to the diameter D1 of the core 50 (L1 / D1) of 250 to 100. 320.
  • R1 in FIG. 1 indicates the 100th round from the winding core 50.
  • the length L1 is the length in the winding direction from the photosensitive film 1 to the core 50 in the 100th round R1 from the core 50 when the photosensitive film 1 is completely unwound from the photosensitive film roll 100. It was done. Since the photosensitive film 1 is wound with a certain degree of tension, it may contract in the winding direction after being unwound. In this case, the length L1 is a length measured after the unwound photosensitive film 1 shrinks.
  • the photosensitive film 1 When the ratio (L1 / D1) is 250 or more, the photosensitive film 1 is wound in a state in which the tightening force is reduced, and even when a foreign substance is mixed between the photosensitive films 1. In addition, the force with which the foreign matter is pressed against the photosensitive resin layer by the tightening of the winding is sufficiently reduced, and the occurrence of dents on the photosensitive resin layer can be suppressed. Further, in the photosensitive film roll 100, the closer to the winding core 50, the more easily the tightening force is applied to the photosensitive film 1 and the more easily a dent is formed. (L1 / D1) obtained from the diameter D1 of the core 50 must be 250 or more.
  • the ratio (L1 / D1) is preferably 260 or more, or 270 or more.
  • the ratio (L1 / D1) is 320 or less, the photosensitive film 1 is in a state of being wound with sufficient tension, and it is possible to sufficiently suppress the occurrence of a winding deviation.
  • the photosensitive film 1 wound thereafter tends to cause a winding shift in a chain.
  • (L1 / D1) obtained from the length L1 of the photosensitive film 1 for the circumference and the diameter D1 of the winding core 50 needs to be 320 or less.
  • the ratio (L1 / D1) is preferably 300 or less, or 290 or less.
  • the photosensitive film roll 100 has a length L2 of the photosensitive film 1 corresponding to 100 turns outside the photosensitive film roll 100 measured by unwinding the photosensitive film roll 100, and a position of the 100th turn R2 from the outside of the photosensitive film roll 100.
  • the ratio (L2 / D2) to the diameter D2 is preferably 250 to 350.
  • the length L2 is the length in the winding direction of the photosensitive film 1 for the outer 100 turns when the photosensitive film 1 is unwound 100 times or more from the outside of the photosensitive film roll 100 from the photosensitive film roll 100. Is measured. Note that the length L2 is a length measured after the unwinding photosensitive film 1 shrinks, similarly to the length L1.
  • the diameter D2 is a diameter measured on the photosensitive film roll after unwinding the photosensitive film 1 for the outer 100 turns.
  • the diameter D2 may be measured in a state of the photosensitive film roll 100 before unwinding the photosensitive film 1 for the outer 100 turns. There is almost no change in the diameter D2 before and after unwinding the photosensitive film 1 for the outer 100 turns.
  • the ratio (L2 / D2) is 250 or more, the occurrence of dents on the photosensitive resin layer can be more sufficiently suppressed.
  • the ratio (L2 / D2) is more preferably 280 or more, or 300 or more.
  • the ratio (L2 / D2) is 350 or less, it is possible to sufficiently suppress the occurrence of winding deviation.
  • the ratio (L2 / D2) is more preferably 340 or less.
  • L1, L2, D1 and D2 are all the same unit.
  • the magnitude relationship between the ratio (L1 / D1) and the ratio (L2 / D2) is not particularly limited, but even if the ratio (L1 / D1) is smaller than the ratio (L2 / D2). Good.
  • the ratio (L1 / D1) is smaller, the vicinity of the winding core becomes tighter than the vicinity of the outermost periphery of the photosensitive film roll 100, and the occurrence of a winding deviation near the winding core is further suppressed. Can be.
  • the number of turns of the photosensitive film roll 100 is 100 or more rounds in order to obtain the ratio (L1 / D1), but may be 200 or more rounds or 500 to 1000 rounds.
  • the number of windings is within the above range, the effect of suppressing the occurrence of dents and winding deviation is more effectively exhibited.
  • the number of windings is less than 200 turns, in the photosensitive film roll 100, the area of the photosensitive film 1 for 100 turns from the winding core 50 and the area of the photosensitive film 1 for the outer 100 turns are one. Copies may be duplicated. That is, in FIG. 1, the 100th round R2 from the outside may be located on the inner side (the core 50 side) from the 100th round R1 from the core 50.
  • FIG. 2 is a schematic cross-sectional view showing one embodiment of the photosensitive film constituting the photosensitive film roll.
  • FIG. 3 is a schematic sectional view showing another embodiment of the photosensitive film constituting the photosensitive film roll.
  • the photosensitive film 1 constituting the photosensitive film roll 100 includes a support film 10, a photosensitive resin layer 20 disposed on the support film 10, and a photosensitive resin layer 20 disposed on the photosensitive resin layer 20. And a protective film 40.
  • the photosensitive film 1 of the present embodiment can be used as a transfer type photosensitive film.
  • the photosensitive film includes a support film 10, a photosensitive resin layer 20 disposed on the support film 10, and metal oxide particles disposed on the photosensitive resin layer 20.
  • a photosensitive film (photosensitive refractive index adjusting film) 2 including a second resin layer 30 to be formed and a protective film 40 disposed on the second resin layer 30 may be used. That is, in the photosensitive film roll 100 shown in FIG. 1, a photosensitive refractive index adjusting film 2 may be used instead of the photosensitive film 1.
  • the photosensitive refractive index adjusting film 2 of the present embodiment can be used as a transfer type photosensitive refractive index adjusting film.
  • a cured film having a function of protecting a metal wiring in a frame of a touch panel or a transparent electrode of the touch panel can be formed.
  • the photosensitive refractive index adjusting film 2 for example, a function of protecting a metal wiring in a frame of the touch panel or a transparent electrode of the touch panel, and a function of making the transparent electrode pattern invisible or improving the visibility of the touch screen are provided.
  • a cured film that satisfies the conditions can be formed at a time.
  • a polymer film As the support film 10, 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 10 is preferably from 5 to 70 ⁇ m, and more preferably from 10 to 70 ⁇ m, from the viewpoint of ensuring coverage and suppressing a decrease in resolution when irradiating active light through the support film 10. More preferably, it is more preferably 15 to 40 ⁇ m, and particularly preferably 15 to 35 ⁇ m.
  • the photosensitive resin layer (first resin layer) 20 includes (A) a binder polymer (hereinafter also referred to as a component (A)), (B) a photopolymerizable compound (hereinafter also referred to as a component (B)), Photosensitive resin composition containing (C) a photopolymerization initiator (hereinafter also referred to as component (C)) and (E) a phosphoric ester having an ethylenically unsaturated bond (hereinafter also referred to as component (E)). It is preferably formed from an object.
  • a binder polymer having a carboxyl group is preferably used from the viewpoint of enabling patterning by alkali development.
  • the component (A) is preferably a copolymer having a structural unit derived from (meth) acrylic acid and an alkyl (meth) acrylate.
  • the copolymer may contain, in a structural unit, another monomer copolymerizable with the (meth) acrylic acid or the alkyl (meth) acrylate. Specific examples include glycidyl (meth) acrylate, benzyl (meth) acrylate, and styrene.
  • Component (A) may have an ethylenically unsaturated group.
  • the component (A) having an ethylenically unsaturated group is not included in the component (B) in this specification.
  • alkyl (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and (meth) acryl. Acid hydroxyl ethyl ester and the like.
  • the component (A) includes (meth) acrylic acid, glycidyl (meth) acrylate, benzyl (meth) acrylate, and styrene from the viewpoint of alkali developability (particularly with respect to an aqueous inorganic alkali solution), patterning properties, and transparency.
  • a structural unit derived from at least one compound selected from the group consisting of, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate Is preferred.
  • the component (A) preferably has a weight average molecular weight of 10,000 to 200,000, more preferably 15,000 to 150,000, and more preferably 30,000 to 150,000, from the viewpoint of resolution. More preferably, it is particularly preferably from 30,000 to 100,000, and most preferably from 40,000 to 100,000.
  • the weight average molecular weight can be measured by the gel permeation chromatography method described in the examples of the present specification.
  • the acid value of the component (A) is preferably at least 75 mgKOH / g from the viewpoint of easily forming a cured film (protective film) having a desired shape by alkali development.
  • the acid value of the component (A) is preferably from 75 to 200 mgKOH / g, and more preferably from 75 to 150 mgKOH / g, from the viewpoint of achieving both easy control of the cured film shape and rust prevention of the cured film. More preferably, it is more preferably 75 to 120 mgKOH / g.
  • the acid value can be measured by a neutralization titration method based on JIS K0070.
  • An example of a specific measurement method is shown below.
  • the binder polymer solution is heated at 130 ° C. for 1 hour to remove volatile components and obtain a solid component.
  • 30 g of acetone is added to the binder polymer and uniformly dissolved to obtain a resin solution.
  • an appropriate amount of phenolphthalein as an indicator is added to the resin solution, and neutralization titration is performed using a 0.1 mol / L aqueous solution of potassium hydroxide.
  • the acid value is calculated by the following equation.
  • Acid value 0.1 ⁇ V ⁇ f1 ⁇ 56.1 / (Wp ⁇ I / 100)
  • V is the titer (mL) of the 0.1 mol / L aqueous potassium hydroxide solution used for titration
  • f1 is the factor (concentration conversion coefficient) of the 0.1 mol / L aqueous potassium hydroxide solution
  • Wp is the measured resin solution.
  • I represents the ratio (% by mass) of the nonvolatile content in the resin solution measured.
  • a photopolymerizable compound having an ethylenically unsaturated group can be used.
  • the photopolymerizable compound having an ethylenically unsaturated group include, for example, a monofunctional vinyl monomer having one polymerizable ethylenically unsaturated group in a molecule, and having two polymerizable ethylenically unsaturated groups in a molecule.
  • Examples include bifunctional vinyl monomers or polyfunctional vinyl monomers having at least three polymerizable ethylenically unsaturated groups in the molecule.
  • Examples of the monofunctional vinyl monomer having one polymerizable ethylenically unsaturated group in the molecule include those exemplified as monomers used in the synthesis of a copolymer which is a preferred example of the component (A). No.
  • the bifunctional vinyl monomer having two polymerizable ethylenically unsaturated groups in the molecule may include a compound having a tricyclodecane skeleton or a tricyclodecene skeleton.
  • a di (meth) acrylate compound represented by the following general formula (1) it is preferable to include a di (meth) acrylate compound represented by the following general formula (1) as a compound having a tricyclodecane skeleton or a tricyclodecene skeleton.
  • R 31 and R 32 each independently represent a hydrogen atom or a methyl group
  • X represents a tricyclodecane skeleton or a divalent group having a tricyclodecene skeleton
  • R 33 and R 33 R 34 each independently represents an alkylene group having 1 to 4 carbon atoms
  • n and m each independently represent an integer of 0 to 2
  • p and q each independently represent an integer of 0 or more
  • p + q 0 to 10.
  • the divalent group having a tricyclodecane skeleton or a tricyclodecene skeleton contained in X has a bulky structure, so that the cured film has low moisture permeability. And the corrosion inhibition of the metal wiring and the transparent electrode can be improved.
  • the “tricyclodecane skeleton” and “tricyclodecene skeleton” in the present specification refer to the following structures, respectively (the bond is an arbitrary position).
  • a compound having a tricyclodecane skeleton or a tricyclodecene skeleton a compound having a tricyclodecane skeleton such as tricyclodecane dimethanol di (meth) acrylate is preferable from the viewpoint of low moisture permeability of the obtained cured film pattern.
  • These are available as DCP and A-DCP (both manufactured by Shin-Nakamura Chemical Co., Ltd.).
  • Examples of the bifunctional vinyl monomer having two polymerizable ethylenically unsaturated groups in the molecule other than the compound having a tricyclodecane skeleton or a tricyclodecene skeleton include polyethylene glycol di (meth) acrylate and trimethylolpropane. Examples thereof include di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2,2-bis (4- (meth) acryloxypolyethoxypolypropoxyphenyl) propane, and bisphenol A diglycidyl ether di (meth) acrylate.
  • the polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups in the molecule a conventionally known polyfunctional vinyl monomer can be used without any particular limitation.
  • the polyfunctional vinyl monomer may be a (meth) acrylate compound having a skeleton derived from trimethylolpropane such as trimethylolpropane tri (meth) acrylate; tetramethylolmethane (Meth) acrylate compounds having a skeleton derived from tetramethylolmethane such as tri (meth) acrylate and tetramethylolmethanetetra (meth) acrylate; derived from pentaerythritol such as pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate (Meth) acrylate compounds having
  • a bifunctional vinyl monomer having a saturated group is used in combination, the ratio is not particularly limited, but from the viewpoint of preventing photocuring and electrode corrosion, at least three polymerizable ethylenically unsaturated groups in the molecule.
  • the content of the component (A) and the component (B) is preferably 35 to 85 parts by mass, more preferably 40 to 50 parts by mass based on 100 parts by mass of the total of the components (A) and (B).
  • the amount is more preferably 80 parts by mass, further preferably 50 to 70 parts by mass, and particularly preferably 55 to 65 parts by mass.
  • the component (A) is preferably 35 parts by mass or more based on 100 parts by mass of the total amount of the components (A) and (B). , 40 parts by mass or more, more preferably 50 parts by mass or more, particularly preferably 55 parts by mass or more.
  • a conventionally known photopolymerization initiator can be used without any particular limitation, but it is preferable to use a highly transparent photopolymerization initiator.
  • the component (C) preferably contains an oxime ester compound and / or a phosphine oxide compound from the viewpoint of forming a resin cured film pattern with sufficient resolution even on a base material even if the thickness is 10 ⁇ m or less.
  • the phosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
  • R 11 and R 12 each independently represent 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;
  • 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. More preferably, it is a methyl group, a cyclopentyl group, a phenyl group or a tolyl group.
  • 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; H, —O (CH 2 ) OH, —O (CH 2 ) 2 OH, —COO (CH 2 ) OH, or —COO (CH 2 ) 2 OH, preferably —H, —O (CH 2) ) 2 OH or —COO (CH 2 ) 2 OH.
  • R 14 each independently represent an alkyl group having 1 to 6 carbon atoms, preferably a propyl group.
  • R 15 represents NO 2 or ArCO (where 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, and is 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.
  • R 20 and R 21 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, and more preferably a methyl group.
  • R 22 represents a hydrogen atom or an alkyl group.
  • the compound represented by the general formula (2) is available as IRGACURE OXE 01 (product name, manufactured by BASF Corporation).
  • the compound represented by the general formula (4) is available, for example, as ADEKA OPTOMER N-1919 (product name, manufactured by ADEKA Corporation).
  • 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) from the viewpoint of excellent photosensitivity and resolution.
  • the amount is more preferably from 5 to 5 parts by mass, further preferably from 1 to 3 parts by mass, particularly preferably from 1 to 2 parts by mass.
  • the photosensitive resin composition according to the present embodiment has a triazole compound having a mercapto group, a tetrazole compound having a mercapto group, a thiadiazole compound having a mercapto group, and an amino group, from the viewpoint of further improving the rust resistance of the cured film. It is preferable that the composition further contains at least one compound selected from the group consisting of a triazole compound and a tetrazole compound having an amino group (hereinafter, also referred to as a component (D)).
  • the triazole compound having a mercapto group include 3-mercapto-triazole (manufactured by Wako Pure Chemical Industries, Ltd., product name: 3MT).
  • Examples of 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 benzotriazole, 1H-benzotriazole-1-acetonitrile, benzotriazole-5-carboxylic acid, 1H-benzotriazole-1-methanol, carboxybenzotriazole, and the like, in which the amino group is substituted.
  • 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- Tetrazole and the like.
  • These tetrazole compounds may be water-soluble salts thereof. Specific examples include sodium, potassium and lithium alkali metal salts of 1-methyl-5-amino-tetrazole.
  • the content is preferably 0.05 to 5.0 parts by mass based on 100 parts by mass of the total of the components (A) and (B).
  • the amount is more preferably 0.1 to 2.0 parts by mass, further preferably 0.2 to 1.0 part by mass, and particularly preferably 0.3 to 0.8 part by mass.
  • the photosensitive resin composition according to the present embodiment preferably contains (E) a phosphate ester containing an ethylenically unsaturated bond from the viewpoint of improving adhesion to a substrate.
  • a phosphate ester containing an ethylenically unsaturated bond is treated as a component (E) instead of a component (B).
  • the content of the component (E) is from 0.1 to 5.0 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B) from the viewpoint of improving the adhesion to the substrate and suppressing the generation of the development residue.
  • the amount is preferably 0 parts by mass, more preferably 0.2 to 3.0 parts by mass.
  • an adhesion imparting agent such as a silane coupling agent, a rust preventive, a leveling agent, and a plasticizer.
  • the content can be about 01 to 20 parts by mass.
  • the above-mentioned "resin composition forming a photosensitive resin layer” refers to a composition not containing a solvent described below, and the content of each component is a content relative to the total amount of components other than the solvent described below. is there.
  • the refractive index of the photosensitive resin layer 20 at a wavelength of 633 nm is usually 1.40 to 1.49.
  • the thickness of the photosensitive resin layer 20 is sufficiently effective as a protective film, and is preferably 15 ⁇ m or less in terms of thickness after drying, in order to sufficiently embed steps on the surface of the substrate with a transparent electrode pattern, The thickness is more preferably 2 to 10 ⁇ m, and still more preferably 3 to 8 ⁇ m. Further, the thickness of the photosensitive resin layer 20 after curing is preferably within the above range.
  • the second resin layer (refractive index adjusting layer) 30 is a layer containing metal oxide particles.
  • the second resin layer 30 can have a relatively higher refractive index than the photosensitive resin layer 20 by containing the metal oxide particles.
  • the refractive index of the second resin layer 30 at 633 nm is preferably in the range of 1.40 to 1.90, more preferably 1.50 to 1.90, and preferably 1.53 to 1.85. Is more preferably 1.55 to 1.75.
  • the refractive index of the second resin layer at 633 nm after curing is preferably within the above range.
  • the refractive index at 633 nm of the second resin layer 30 is within the above range, when a cured film pattern is provided on a transparent electrode pattern such as ITO, various members used on the cured film pattern (for example, a module) Between the cover glass used to form the transparent electrode pattern and the refractive index of the transparent electrode pattern (OCA), which is the optical value between the portion where the transparent electrode pattern such as ITO is formed and the portion where the transparent electrode pattern is not formed. The color difference due to reflection can be reduced, and the bone appearance phenomenon can be prevented. Further, it is possible to reduce the intensity of the reflected light on the entire screen, and it is possible to suppress a decrease in transmittance on the screen.
  • OCA refractive index of the transparent electrode pattern
  • the refractive index of a transparent electrode such as ITO is preferably from 1.80 to 2.10, more preferably from 1.85 to 2.05, and even more preferably from 1.90 to 2.00.
  • the refractive index of a member such as OCA is preferably from 1.45 to 1.55, more preferably from 1.47 to 1.53, even more preferably from 1.48 to 1.51. .
  • the second resin layer 30 has a minimum light transmittance of preferably at least 80%, more preferably at least 85%, even more preferably at least 90% in a wavelength range of 450 to 650 nm.
  • the minimum light transmittance of the second resin layer after curing in a wavelength region of 450 to 650 nm is preferably within the above range.
  • the second resin layer 30 can contain the component (A), the component (B) and the component (C). If necessary, the component (D) and / or the component (E) can be used. Further, it can be contained.
  • the second resin layer 30 does not necessarily need to contain a photopolymerization component such as the component (B) and the component (C), and utilizes the photopolymerization component that migrates from the adjacent resin layer by forming the layer to form the second resin layer.
  • the layers can also be photocured.
  • the second resin layer 30 contains metal oxide particles (hereinafter also referred to as component (F)).
  • the metal oxide particles preferably contain metal oxide particles having a refractive index of 1.50 or more at a wavelength of 633 nm. This makes it possible to improve the transparency of the second resin layer and the refractive index at a wavelength of 633 nm when the photosensitive refractive index adjusting film is prepared. Further, the developability can be improved while suppressing adsorption to the substrate.
  • 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, zirconium oxide or titanium oxide particles 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.
  • the second resin layer 30 may contain titanium oxide nanoparticles as the component (F). Further, among the titanium oxide nanoparticles, 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 in addition to the metal oxide particles.
  • an organic compound such as a compound having a triazine ring, a compound having an isocyanuric acid skeleton, and a compound having a fluorene skeleton.
  • an organic compound such as a compound having a triazine ring, a compound having an isocyanuric acid skeleton, and a compound having a fluorene skeleton.
  • the thickness of the second resin layer 30 may be 0.01 to 1 ⁇ m, preferably 0.03 to 0.5 ⁇ m, more preferably 0.04 to 0.3 ⁇ m, The thickness is more preferably 0.05 to 0.25 ⁇ m, and particularly preferably 0.05 to 0.2 ⁇ m. When the thickness is 0.01 to 1 ⁇ m, it is possible to further reduce the above-described reflected light intensity of the entire screen. It is also preferable that the thickness of the second resin layer after curing is within the above range.
  • the second resin layer 30 is interposed between the base material and the photosensitive resin layer 20 because the photosensitive resin layer 20 has the specific composition described above. Even in such a case, the various effects described above can be obtained.
  • the refractive index of a single photosensitive resin layer can also be measured by the same method.
  • Examples of the protective film 40 include films of polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, polyethylene-vinyl acetate copolymer, polyethylene-vinyl acetate copolymer, and laminated films of these films and polyethylene.
  • the total thickness of the support film 10 and the protective film 40 needs to be less than 100 ⁇ m, preferably 20 to 80 ⁇ m, and more preferably 30 to 70 ⁇ m. Is more preferable, and further preferably 40 to 60 ⁇ m. If the total thickness is larger than 100 ⁇ m, the value of the length L1 in the photosensitive film roll 100 becomes too large, and the ratio (L1 / D1) becomes too large. May be 250 or more, a dent may occur in the photosensitive resin layer. Therefore, the total thickness of the support film 10 and the protective film 40 needs to be less than 100 ⁇ m from the viewpoint of suppressing a dent and a winding deviation in the photosensitive film roll 100.
  • the minimum value of the total light transmittance (Tt) in the visible light region of a wavelength of 400 to 700 nm is preferably 90.00% or more, more preferably 90.50% or more, and 90.70. % Is more preferable. If the total light transmittance in the general visible light wavelength range of 400 to 700 nm is 90.00% or more, when protecting the transparent electrode in the sensing area of the touch panel (touch sensor), an image is displayed in the sensing area. It is possible to sufficiently suppress a decrease in quality, hue, and luminance.
  • a coating solution containing a photosensitive resin composition and a coating solution containing the second resin composition are prepared. These can be formed by applying and drying these on the support film 10 and the protective film 40, respectively. Then, the photosensitive refractive index adjusting film 2 is formed by combining the support film 10 on which the photosensitive resin layer 20 is formed and the protective film 40 on which the second resin layer 30 is formed with the photosensitive resin layer 20 and the second resin layer 30. It can be formed by bonding together in a state where the resin layer 30 faces the resin layer 30.
  • the photosensitive refractive index adjusting film 2 is formed by applying a coating solution containing a photosensitive resin composition on the support film 10 and drying it, and then containing the second resin composition on the photosensitive resin layer 20. It can also be formed by applying a coating solution to be applied, drying and applying a protective film 40.
  • the photosensitive film 1 without the second resin layer 30 is coated on the support film 10 with a coating solution containing the photosensitive resin composition, dried, and then protected on the photosensitive resin layer 20. It can be formed by attaching the film 40.
  • Application methods include doctor blade coating, Meyer bar coating, roll coating, screen coating, spinner coating, inkjet coating, spray coating, dip coating, gravure coating, curtain coating, and die coating. And the like.
  • the drying conditions are not particularly limited, but the drying temperature is preferably from 60 to 130 ° C, and the drying time is preferably from 0.5 to 30 minutes.
  • the method of manufacturing a photosensitive film roll according to the present embodiment includes a winding step of winding the long photosensitive film 1 around a core 50 to obtain a photosensitive film roll 100, and includes a support film 10 and a protective film. 40, the total thickness of which is less than 100 ⁇ m, and the ratio of the length L1 of the photosensitive film 1 for 100 turns from the core 50 measured by unwinding the photosensitive film roll 100 to the diameter D1 of the core.
  • This is a method in which winding is performed in a winding step so that (L1 / D1) is 250 to 320.
  • the photosensitive film 1 may be a photosensitive refractive index adjusting film 2.
  • the length of the photosensitive film 1 in the winding direction is not particularly limited, but it is necessary that the photosensitive film 1 can be wound 100 times or more around the winding core 50.
  • the length is preferably such that it can be wound, and more preferably the length that can be wound 500 to 1000 times around the winding core 50.
  • the specific length in the winding direction of the photosensitive film 1 is, for example, 100 to 1000 m, preferably 200 to 800 m, and more preferably 300 to 500 m. When the length of the photosensitive film 1 in the winding direction is within the above range, the effect of suppressing the occurrence of dents and winding deviation is more effectively achieved.
  • the width of the photosensitive film 1 (the length in the direction perpendicular to the winding direction) is not particularly limited, but is usually 10 to 1500 cm, preferably 20 to 500 cm, and more preferably 30 to 100 cm. When the width of the photosensitive film 1 is in the above range, the effect of suppressing the occurrence of dents and winding deviation is more effectively exhibited.
  • the diameter of the photosensitive film roll 100 in a state where the photosensitive film 1 is completely wound up is not particularly limited, but is usually 5 to 100 cm, preferably 10 to 50 cm, more preferably 15 to 30 cm. When the diameter of the photosensitive film roll 100 is within the above range, the effect of suppressing the occurrence of dents and winding deviation is more effectively achieved.
  • the core 50 is a cylindrical core.
  • the material of the core 50 include a paper tube, a wooden tube, a plastic tube, and a metal tube, but a metal tube is preferable from the viewpoint of being able to withstand the pressure during winding.
  • the material of the core is plastic
  • examples of the plastic include polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer).
  • the diameter D1 of the core 50 is not particularly limited, but is usually 1 to 50 cm, preferably 3 to 30 cm, and more preferably 5 to 10 cm. When the diameter D1 of the core 50 is within the above range, the effect of suppressing the occurrence of dents and winding deviation is more effectively achieved.
  • winding is performed so that the ratio (L1 / D1) becomes 250 to 320. Details of the ratio (L1 / D1) are as described in the description of the photosensitive film roll 100, and the preferable range is also as described above.
  • the winding step is performed by unwinding the photosensitive film roll 100 and measuring the length L2 of the photosensitive film 1 for 100 turns outside the photosensitive film roll 100 and 100 turns from the outside of the photosensitive film roll 100. Winding is preferably performed so that the ratio (L2 / D2) of the eye position to the diameter D2 is 250 to 350.
  • the details of the ratio (L2 / D2) are as described in the description of the photosensitive film roll 100, and the preferable range is also as described above.
  • the values of the ratio (L1 / D1) and the ratio (L2 / D2) are determined by, for example, a method of adjusting the winding tension at the time of winding and a method of adjusting the thickness and the material of the photosensitive film 1 or the like. It can be in a desired range.
  • the winding tension is preferably from 120 to 220 N / m, and more preferably from 140 to 200 N / m, from the viewpoint of setting the values of the ratio (L1 / D1) and the ratio (L2 / D2) within the above-described preferable ranges. Is more preferable, and it is still more preferable to be 160 to 180 N / m.
  • the winding tension is preferably controlled in accordance with the winding diameter so that the tension on the photosensitive film 1 from the start to the end of the winding is kept constant. However, the tension is changed during the winding. Is also good. When the tension is changed during winding, it is preferable that the winding tension before and after the change both fall within the above-described preferable range.
  • the support film 10 be on the outside and the protective film 40 be wound on the core 50 side.
  • an end face separator may be provided on the end face of the photosensitive film roll 100 from the viewpoint of end face protection.
  • the end face separator it is preferable to use a moisture-proof end face separator from the viewpoint of edge fusion resistance.
  • the obtained photosensitive film roll 100 is wrapped and stored in a black sheet having low moisture permeability.
  • the photosensitive film roll 100 according to the present embodiment is used for a sensing device such as a touch panel, and is used, for example, for forming a protective film for protecting a transparent electrode and a metal wiring of the sensing device. In these sensing devices, high visibility of the touch screen is required. However, since the photosensitive film roll 100 according to the present embodiment suppresses the occurrence of dents on the photosensitive resin layer 20, It is possible to suppress a decrease in visibility due to the above.
  • FIG. 4 is a schematic top view showing one embodiment of a touch panel on which a protective film is formed using the photosensitive film roll 100 according to the present embodiment.
  • FIG. 4 illustrates an example of a capacitive touch panel.
  • the touch panel shown in FIG. 4 has a touch screen 102 for detecting touch position coordinates on one surface of a transparent substrate 101, and a transparent electrode 103 and a transparent electrode 104 for detecting a change in capacitance in this area are transparent. It is provided on a substrate 101.
  • the transparent substrate 101 for example, a substrate such as a glass plate, a plastic plate, and a ceramic plate used for a touch panel (touch sensor) is exemplified.
  • an insulating layer or an index matching layer may be provided on the transparent base material 101 between the base material and the electrode.
  • the index matching layer may have a composition similar to that of the second resin layer 30 described above.
  • Photopolymerizable compound pentaerythritol tetraacrylate (Shin-Nakamura Chemical Co., Ltd., product name: A-TMMT)
  • Photopolymerization initiator 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)] (BASF Corporation, product name: IRGACURE OXE 01)
  • Rust inhibitor 5-amino-1H-te
  • Example 1 Using a comma coater, the photosensitive resin composition was uniformly applied to a 16 ⁇ m-thick PET film (support film, product name: FB40, manufactured by Toray Industries, Inc.) and then heated at 100 ° C. using a hot air convection dryer. After drying for 3 minutes to remove the solvent, a photosensitive resin layer was formed. The thickness of the photosensitive resin layer after drying was 8 ⁇ m. Then, a 30 ⁇ m-thick polypropylene film (protective film, manufactured by Oji F-Tex Co., Ltd., product name: E-201F) is attached to the photosensitive resin layer, so that the support film, the photosensitive resin layer, and the protective film are in this order.
  • a 30 ⁇ m-thick polypropylene film (protective film, manufactured by Oji F-Tex Co., Ltd., product name: E-201F) is attached to the photosensitive resin layer, so that the support film, the photosensitive resin layer, and the protective film are in this order
  • Example 2 A long transfer type photosensitive film was obtained in the same manner as in Example 1 except that the protective film was changed to a PET film having a thickness of 16 ⁇ m (manufactured by Toray Industries, Inc., product name: FB40). The photosensitive film was wound around a core under the same conditions as in Example 1 to obtain a photosensitive film roll.
  • Example 4 A long transfer photosensitive film was obtained in the same manner as in Example 1 except that the thickness of the photosensitive resin layer after drying was 15 ⁇ m. The photosensitive film was wound around a core under the same conditions as in Example 1 to obtain a photosensitive film roll.
  • Example 3 The support film was changed to a 50 ⁇ m-thick PET film (manufactured by Toyobo Co., Ltd., product name: A4100), and the protective film was changed to a 50 ⁇ m-thick PET film (manufactured by Toyobo Co., product name: A4100).
  • a long transfer type photosensitive film was obtained in the same manner as in Example 1 except that the total length of the film was changed to 200 m.
  • the photosensitive film was wound around a core under the same conditions as in Example 1 to obtain a photosensitive film roll.
  • FIG. 5A is a laser microscope photograph of the dent
  • FIG. 5B is a graph showing the height (depth) and width of the dent and projection. Points a, b, and c in FIG. 5A and points a, b, and c in FIG. 5B respectively indicate the same point.
  • SYMBOLS 1 ... photosensitive film, 2 ... photosensitive refractive index adjustment film, 10 ... support film, 20 ... photosensitive resin layer, 30 ... second resin layer, 40 ... protective film, 50 ... core, 100 ... photosensitive film Roll, 101: Transparent substrate, 102: Sensing area, 103, 104: Transparent electrode, 105: Lead wiring, 106: Connection electrode, 107: Connection terminal, 123: Cured film pattern (cured film).

Abstract

This method for manufacturing a photosensitive film roll for a sensing device, in which an elongate photosensitive film provided with a supporting film, a photosensitive resin layer disposed on the supporting film, and a protective film disposed on the photosensitive resin layer is wound in a roll shape, includes a winding process for obtaining the photosensitive film roll by winding the photosensitive film onto a winding core, wherein the total thickness of the supporting film and the protective film is less than 100 μm, and the winding in the winding process is performed in such a way that a ratio (L1/D1) of a length L1 of 100 turns of the photosensitive film from the winding core, measured by unwinding the photosensitive film roll, to a diameter D1 of the winding core is 250 to 320.

Description

センシングデバイス用感光性フィルムロールの製造方法及びセンシングデバイス用感光性フィルムロールMethod of manufacturing photosensitive film roll for sensing device and photosensitive film roll for sensing device
　本発明は、センシングデバイス用感光性フィルムロールの製造方法及びセンシングデバイス用感光性フィルムロールに関する。 The present invention relates to a method for manufacturing a photosensitive film roll for a sensing device and a photosensitive film roll for a sensing device.
　パソコン及びテレビ等の大型電子機器、カーナビゲーション、携帯電話、スマートフォン、電子辞書等の小型電子機器、ＯＡ（Ｏｆｆｉｃｅ　Ａｕｔｏｍａｔｉｏｎ、オフィスオートメーション）・ＦＡ（Ｆａｃｔｏｒｙ　Ａｕｔｏｍａｔｉｏｎ、ファクトリーオートメーション）機器等の表示機器などには液晶表示素子及びタッチパネル（タッチセンサー）が用いられている。 Large electronic devices such as personal computers and televisions, small electronic devices such as car navigation systems, mobile phones, smartphones, and electronic dictionaries, display devices such as OA (Office Automation) and FA (Factory Automation) devices, etc. A liquid crystal display element and a touch panel (touch sensor) are used.
　タッチパネルは各種の方式が実用化されているが、近年、投影型静電容量方式のタッチパネルの利用が進んでいる。一般に、投影型静電容量方式のタッチパネルでは、Ｘ軸とＹ軸による２次元座標を表現するために、複数のＸ電極と、該Ｘ電極に直交する複数のＹ電極が形成される。これらの電極の材料として、ＩＴＯ（Ｉｎｄｉｕｍ－Ｔｉｎ－Ｏｘｉｄｅ、酸化インジウムスズ）が主流である。 Various types of touch panels have been put to practical use, but in recent years, the use of projected capacitive touch panels has been increasing. In general, in a projected capacitive touch panel, a plurality of X electrodes and a plurality of Y electrodes orthogonal to the X electrodes are formed in order to represent two-dimensional coordinates by an X axis and a Y axis. As a material for these electrodes, ITO (Indium-Tin-Oxide, indium tin oxide) is mainly used.
　ところで、タッチパネルの額縁領域はタッチ位置を検出できない領域であるから、その額縁領域の面積を狭くすることが製品価値を向上させるための重要な要素である。一般的に額縁領域には、タッチ位置の検出信号を伝えるために銅等の金属配線が形成されている。 By the way, since the frame region of the touch panel is a region where the touch position cannot be detected, reducing the area of the frame region is an important factor for improving the product value. Generally, metal wiring such as copper is formed in the frame area to transmit a detection signal of a touch position.
　しかし、タッチパネルは、指先等に接触される際に水分、塩分等の腐食成分がセンシング領域から内部に侵入することがある。タッチパネルの内部に腐食成分が侵入すると、上記金属配線が腐食し、電極と駆動用回路との間の電気抵抗の増加又は断線の恐れがある。 However, when the touch panel is brought into contact with a fingertip or the like, a corrosive component such as moisture or salt may enter the sensing area from the inside. When a corrosive component enters the inside of the touch panel, the metal wiring is corroded, and there is a risk of an increase in electrical resistance between the electrode and the driving circuit or a disconnection.
　金属配線の腐食を防ぐために、タッチパネル用基材上に感光性樹脂組成物を用いて保護膜を形成する方法が知られている。例えば、必要な箇所に保護膜（例えばレジスト膜）を設ける方法として、感光性樹脂組成物を含む感光性樹脂層を所定の基板上に設けて、この感光性樹脂層を露光及び現像する方法が知られている。また、感光性樹脂層は、支持フィルムと、該支持フィルム上に設けられた感光性樹脂組成物からなる感光性樹脂層と、を備える感光性エレメント（感光性フィルム）を用いて基板上にラミネートする方法が知られている（例えば、下記特許文献１参照）。 方法 In order to prevent corrosion of metal wiring, a method of forming a protective film on a substrate for a touch panel using a photosensitive resin composition is known. For example, as a method of providing a protective film (for example, a resist film) at a necessary portion, a method of providing a photosensitive resin layer containing a photosensitive resin composition on a predetermined substrate, and exposing and developing the photosensitive resin layer is known. Are known. The photosensitive resin layer is laminated on a substrate using a photosensitive element (photosensitive film) including a support film and a photosensitive resin layer made of a photosensitive resin composition provided on the support film. A known method is known (for example, see Patent Document 1 below).
国際公開第２０１３／０８４８７３号International Publication No. WO 2013/084873
　感光性フィルムは一般的に、長尺の感光性フィルムを巻芯に巻き取った巻回物（感光性フィルムロール）の形で保管及び使用される。しかしながら、感光性フィルムロールの形にした場合、感光性樹脂層に打痕が生じる場合があるという問題がある。 The photosensitive film is generally stored and used in the form of a roll (photosensitive film roll) in which a long photosensitive film is wound around a core. However, when the photosensitive film roll is formed, there is a problem that a dent may be formed on the photosensitive resin layer.
　感光性フィルムロールは、巻きズレが生じないようにある程度の張力をかけて巻芯に巻き取られるが、その際に樹脂の切り屑等の異物が感光性フィルム間に巻き込まれ、その異物が感光性フィルムにめり込んで押し跡を付けることによって、感光性樹脂層に打痕が生じると考えられる。特に、巻芯に近い位置に巻かれた感光性フィルムほど、巻き締まりの力がかかりやすいため、感光性樹脂層に打痕が生じやすい。これまで、視認性が問題とならない用途、及び、永久膜の形成以外の用途では、感光性樹脂層の打痕は問題視されていなかったが、例えばタッチパネル用途では、タッチ画面の視認性及び美観の観点から、感光性樹脂層に打痕が存在するのは大きな問題となる。 The photosensitive film roll is wound around the core with a certain amount of tension so as not to cause a winding deviation.At this time, foreign matter such as resin chips is caught between the photosensitive films, and the foreign matter is exposed to light. It is considered that a dent is formed in the photosensitive resin layer by digging into the photosensitive film and making a press mark. In particular, as the photosensitive film is wound closer to the core, the tightening force is more likely to be applied, so that a dent is likely to occur in the photosensitive resin layer. Until now, in applications where visibility is not a problem, and in applications other than the formation of a permanent film, dents in the photosensitive resin layer have not been regarded as a problem. In view of the above, the presence of a dent in the photosensitive resin layer is a serious problem.
　本発明は、上記従来技術の有する課題に鑑みてなされたものであり、打痕及び巻きズレの発生を抑制することができる、タッチパネル等のセンシングデバイスに用いられる感光性フィルムロールの製造方法、及び、センシングデバイスに用いられる感光性フィルムロールを提供することを目的とする。 The present invention has been made in view of the above-mentioned problems of the related art, and can suppress the occurrence of a dent and a winding shift, a method of manufacturing a photosensitive film roll used for a sensing device such as a touch panel, and Another object of the present invention is to provide a photosensitive film roll used for a sensing device.
　上記目的を達成するために、本発明は、支持フィルムと、上記支持フィルム上に配置された感光性樹脂層と、上記感光性樹脂層上に配置された保護フィルムと、を備える長尺の感光性フィルムをロール状に巻き取った、センシングデバイス用感光性フィルムロールの製造方法であって、上記感光性フィルムを巻芯に巻き取って感光性フィルムロールを得る巻取工程を有し、上記支持フィルム及び上記保護フィルムの合計の厚さが１００μｍ未満であり、上記感光性フィルムロールを巻き出して測定される上記巻芯から１００周分の感光性フィルムの長さＬ１と、上記巻芯の直径Ｄ１との比（Ｌ１／Ｄ１）が２５０～３２０となるように、上記巻取工程における巻き取りを行う、感光性フィルムロールの製造方法を提供する。 In order to achieve the above object, the present invention provides a long photosensitive comprising a support film, a photosensitive resin layer disposed on the support film, and a protective film disposed on the photosensitive resin layer. A method for manufacturing a photosensitive film roll for a sensing device, comprising winding the photosensitive film into a roll, comprising a winding step of winding the photosensitive film around a core to obtain a photosensitive film roll, The total thickness of the film and the protective film is less than 100 μm, and the length L1 of the photosensitive film for 100 turns from the core measured by unwinding the photosensitive film roll, and the diameter of the core Provided is a method for manufacturing a photosensitive film roll, wherein the winding in the winding step is performed so that the ratio (L1 / D1) to D1 is 250 to 320.
　上記製造方法によれば、支持フィルム及び保護フィルムの合計の厚さが１００μｍ未満である感光性フィルムについて、上記比（Ｌ１／Ｄ１）が２５０～３２０となるように巻取工程における巻き取りを行うことにより、打痕及び巻きズレの発生が抑制された感光性フィルムロールを得ることができる。特に、感光性樹脂層に打痕が生じやすい巻芯付近において、巻きズレの発生を抑制しつつ、打痕の発生を抑制することができる。 According to the above manufacturing method, the photosensitive film in which the total thickness of the support film and the protective film is less than 100 μm is wound in the winding step such that the ratio (L1 / D1) is 250 to 320. Thereby, it is possible to obtain a photosensitive film roll in which the occurrence of dents and winding deviation is suppressed. In particular, in the vicinity of the core where a dent is likely to occur in the photosensitive resin layer, the occurrence of a dent can be suppressed while suppressing the occurrence of winding deviation.
　上記製造方法では、上記感光性フィルムロールを巻き出して測定される上記感光性フィルムロールの外側１００周分の感光性フィルムの長さＬ２と、上記感光性フィルムロールの外側から１００周目の位置の直径Ｄ２との比（Ｌ２／Ｄ２）が２５０～３５０となるように、上記巻取工程における巻き取りを行うことが好ましい。 In the above manufacturing method, the length L2 of the photosensitive film for 100 turns outside the photosensitive film roll measured by unwinding the photosensitive film roll, and the position of the 100th turn from the outside of the photosensitive film roll It is preferable to perform winding in the above winding step so that the ratio (L2 / D2) to the diameter D2 becomes 250 to 350.
　これにより、感光性フィルムロールにおける打痕及び巻きズレの発生をより十分に抑制することができる。特に、感光性フィルムロールの最外周に近い位置ほど、巻き締まりの力が感光性フィルムにかかりにくいため巻きズレが生じやすいが、上記条件を満たすように巻取工程を行うことにより、最外周付近の巻きズレの発生を十分に抑制することができる。 This makes it possible to more sufficiently suppress the occurrence of dents and winding deviations in the photosensitive film roll. In particular, as the position closer to the outermost periphery of the photosensitive film roll, the winding tightening force is less likely to be applied to the photosensitive film, so that winding deviation is likely to occur, but by performing the winding process so as to satisfy the above conditions, the outermost periphery is reduced. Can be sufficiently suppressed.
　上記製造方法において、上記感光性フィルムロールの巻き数は５００～１０００周であってもよい。巻き数が上記範囲内である感光性フィルムロールにおいて、本発明の効果がより一層有効に奏される。 に お い て In the above manufacturing method, the number of turns of the photosensitive film roll may be 500 to 1000 turns. In the photosensitive film roll having the number of windings within the above range, the effects of the present invention are more effectively exhibited.
　上記製造方法において、上記感光性フィルムは、上記感光性樹脂層と上記保護フィルムとの間に配置された金属酸化物粒子を含有する第二の樹脂層を更に備えていてもよい。このような第二の樹脂層を備える感光性フィルムをロール状に巻き取る場合においても、打痕及び巻きズレの発生を十分に抑制することができる、また、投影型静電容量方式のタッチパネルは、透明電極パターンが形成された部分と、形成されていない部分との光学的な反射特性の違いにより色差が大きくなり、モジュール化した際に透明電極パターンが画面上に映りこむ、いわゆる「骨見え現象」の問題がある。上記感光性フィルムによれば、第二の樹脂層を備えることで、骨見え現象の問題を改善することができる。 In the production method, the photosensitive film may further include a second resin layer containing metal oxide particles disposed between the photosensitive resin layer and the protective film. Even when the photosensitive film including the second resin layer is wound into a roll, the occurrence of dents and winding deviation can be sufficiently suppressed. The difference in optical reflection characteristics between the part where the transparent electrode pattern is formed and the part where the transparent electrode pattern is not formed increases the color difference, and when the module is modularized, the transparent electrode pattern is reflected on the screen, so-called `` bone view '' There is a problem of "phenomenon". According to the photosensitive film, the problem of the bone appearance phenomenon can be improved by providing the second resin layer.
　本発明はまた、支持フィルムと、上記支持フィルム上に配置された感光性樹脂層と、上記感光性樹脂層上に配置された保護フィルムと、を備える長尺の感光性フィルムを巻芯にロール状に巻き取った、センシングデバイス用感光性フィルムロールであって、上記支持フィルム及び上記保護フィルムの合計の厚さが１００μｍ未満であり、上記感光性フィルムロールを巻き出して測定される上記巻芯から１００周分の感光性フィルムの長さＬ１と、上記巻芯の直径Ｄ１との比（Ｌ１／Ｄ１）が２５０～３２０である、感光性フィルムロールを提供する。 The present invention also provides a long photosensitive film comprising a support film, a photosensitive resin layer disposed on the support film, and a protective film disposed on the photosensitive resin layer, and a roll around a core. A photosensitive film roll for a sensing device, wound in a shape, wherein the total thickness of the support film and the protective film is less than 100 μm, and the core is measured by unwinding the photosensitive film roll. A photosensitive film roll, wherein the ratio (L1 / D1) of the length L1 of the photosensitive film to the diameter D1 of the core from 250 to 320 turns is from 250 to 320.
　上記感光性フィルムロールによれば、支持フィルム及び保護フィルムの合計の厚さが１００μｍ未満であり、且つ、上記比（Ｌ１／Ｄ１）が２５０～３２０であることにより、打痕及び巻きズレの発生が十分に抑制される。特に、感光性樹脂層に打痕が生じやすい巻芯付近において、巻きズレの発生が抑制されながら、打痕の発生が抑制される。 According to the photosensitive film roll, since the total thickness of the support film and the protective film is less than 100 μm and the ratio (L1 / D1) is 250 to 320, the occurrence of dents and misalignment occurs. Is sufficiently suppressed. In particular, in the vicinity of the core where a dent is likely to occur in the photosensitive resin layer, the occurrence of a dent is suppressed while the occurrence of a winding shift is suppressed.
　上記感光性フィルムロールは、上記感光性フィルムロールを巻き出して測定される上記感光性フィルムロールの外側１００周分の感光性フィルムの長さＬ２と、上記感光性フィルムロールの外側から１００周目の位置の直径Ｄ２との比（Ｌ２／Ｄ２）が２５０～３５０であることが好ましい。 The photosensitive film roll has a length L2 of the photosensitive film corresponding to 100 turns outside the photosensitive film roll measured by unwinding the photosensitive film roll, and the 100th turn from the outside of the photosensitive film roll. It is preferable that the ratio (L2 / D2) to the diameter D2 at the position is 250 to 350.
　これにより、感光性フィルムロールにおける打痕及び巻きズレの発生がより十分に抑制される。特に、感光性フィルムロールの最外周に近い位置ほど、巻き締まりの力が感光性フィルムにかかりにくいため巻きズレが生じやすいが、上記条件を満たす感光性フィルムロールによれば、最外周付近の巻きズレの発生が十分に抑制される。 Thereby, occurrence of a dent and a winding deviation in the photosensitive film roll is more sufficiently suppressed. In particular, as the position closer to the outermost periphery of the photosensitive film roll, it is difficult for the tightening force to be applied to the photosensitive film, so that winding deviation is likely to occur. The occurrence of displacement is sufficiently suppressed.
　上記感光性フィルムロールの巻き数は５００～１０００周であってもよい。巻き数が上記範囲内である感光性フィルムロールにおいて、本発明の効果がより一層有効に奏される。 巻 き The number of turns of the photosensitive film roll may be 500 to 1000 turns. In the photosensitive film roll having the number of windings within the above range, the effects of the present invention are more effectively exhibited.
　上記感光性フィルムロールにおいて、上記感光性フィルムは、上記感光性樹脂層と上記保護フィルムとの間に配置された金属酸化物粒子を含有する第二の樹脂層を更に備えていてもよい。このような第二の樹脂層を備える感光性フィルムをロール状に巻き取った感光性フィルムロールにおいても、打痕及び巻きズレの発生が十分に抑制される。また、第二の樹脂層を備える感光性フィルムによれば、骨見え現象の問題を改善することができる。 In the photosensitive film roll, the photosensitive film may further include a second resin layer containing metal oxide particles disposed between the photosensitive resin layer and the protective film. Even in a photosensitive film roll obtained by winding a photosensitive film having such a second resin layer into a roll, the occurrence of dents and winding deviation is sufficiently suppressed. Further, according to the photosensitive film having the second resin layer, the problem of the bone appearance phenomenon can be improved.
　本発明によれば、打痕及び巻きズレの発生を抑制することができる、タッチパネル等のセンシングデバイスに用いられる感光性フィルムロールの製造方法、及び、センシングデバイスに用いられる感光性フィルムロールを提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the photosensitive film roll used for a sensing device, such as a touch panel, and the photosensitive film roll used for a sensing device which can suppress generation | occurrence | production of a dent and a winding gap are provided. be able to.
本開示の一実施形態に係る感光性フィルムロールを模式的に示す斜視図である。1 is a perspective view schematically illustrating a photosensitive film roll according to an embodiment of the present disclosure. 感光性フィルムロールを構成する感光性フィルムの一実施形態を示す模式断面図である。FIG. 2 is a schematic cross-sectional view showing one embodiment of a photosensitive film constituting a photosensitive film roll. 感光性フィルムロールを構成する感光性フィルムの他の一実施形態を示す模式断面図である。FIG. 9 is a schematic cross-sectional view illustrating another embodiment of the photosensitive film constituting the photosensitive film roll. タッチパネルの一実施形態を示す模式上面図である。It is a schematic top view which shows one Embodiment of a touch panel. 感光性樹脂層に形成された打痕を示す図である。FIG. 3 is a diagram illustrating a dent formed on a photosensitive resin layer.
　以下、場合により図面を参照しつつ、本発明を実施するための形態について詳細に説明する。ただし、本発明は以下の実施形態に限定されるものではない。なお、本明細書において、「（メタ）アクリル酸」とは、アクリル酸又はメタクリル酸を意味し、「（メタ）アクリレート」とは、アクリレート又はそれに対応するメタクリレートを意味する。「Ａ又はＢ」とは、ＡとＢのどちらか一方を含んでいればよく、両方とも含んでいてもよい。 Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the drawings as necessary. However, the present invention is not limited to the following embodiments. In this specification, “(meth) acrylic acid” means acrylic acid or methacrylic acid, and “(meth) acrylate” means acrylate or methacrylate corresponding thereto. “A or B” may include one of A and B, and may include both.
　また、本明細書において「層」との語は、平面図として観察したときに、全面に形成されている形状の構造に加え、一部に形成されている形状の構造も包含される。また、本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。また、「～」を用いて示された数値範囲は、「～」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。 に お い て In this specification, the term “layer” also includes a partially formed structure in addition to a partially formed structure when observed as a plan view. Further, in this specification, the term "step" is used not only for an independent step but also for the case where the intended action of the step is achieved even if it cannot be clearly distinguished from other steps. 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.
　更に、本明細書において組成物中の各成分の含有量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。また、例示材料は特に断らない限り単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Further, in the present specification, the content of each component in the composition, when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified, the total of the plurality of substances present in the composition Means quantity. Unless otherwise specified, the exemplified materials may be used alone or in combination of two or more.
　また、本明細書中に段階的に記載されている数値範囲において、ある段階の数値範囲の上限値又は下限値は、他の段階の数値範囲の上限値又は下限値に置き換えてもよい。また、本明細書中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。 上限 In addition, in the numerical ranges described in stages in this specification, the upper limit or lower limit of the numerical range of a certain stage may be replaced with the upper limit or lower limit of the numerical range of another stage. In the numerical ranges described in this specification, the upper limit or the lower limit of the numerical range may be replaced with the value shown in the embodiment.
＜感光性フィルム及び感光性フィルムロール＞
　図１は、本開示の一実施形態に係る感光性フィルムロールを模式的に示す斜視図である。図１に示すように、本実施形態に係る感光性フィルムロール１００は、感光性フィルム１を巻芯５０に巻き取ってなる巻回物である。感光性フィルムロール１００は、感光性フィルム１を巻芯５０に１００周以上巻き取ったものである。 <Photosensitive film and photosensitive film roll>
FIG. 1 is a perspective view schematically illustrating a photosensitive film roll according to an embodiment of the present disclosure. As shown in FIG. 1, the photosensitive film roll 100 according to the present embodiment is a roll formed by winding the photosensitive film 1 around a core 50. The photosensitive film roll 100 is obtained by winding the photosensitive film 1 around the core 50 by 100 turns or more.
　感光性フィルムロール１００は、これを巻き出して測定される巻芯５０から１００周分の感光性フィルム１の長さＬ１と、巻芯５０の直径Ｄ１との比（Ｌ１／Ｄ１）が２５０～３２０であるものである。ここで、図１中のＲ１は、巻芯５０から１００周目を示している。長さＬ１は、感光性フィルムロール１００から感光性フィルム１を全て巻き出した時の、巻芯５０から１００周目Ｒ１の感光性フィルム１から巻芯５０までの巻き取り方向の長さを測定したものである。なお、感光性フィルム１はある程度の張力をかけて巻き取られているため、巻き出した後に巻き取り方向に収縮してもよい。その場合、長さＬ１は、巻き出した感光性フィルム１が収縮した後に測定される長さである。 The photosensitive film roll 100 has a ratio (L1 / D1) of the length L1 of the photosensitive film 1 corresponding to 100 turns from the core 50 measured by unwinding the roll to the diameter D1 of the core 50 (L1 / D1) of 250 to 100. 320. Here, R1 in FIG. 1 indicates the 100th round from the winding core 50. The length L1 is the length in the winding direction from the photosensitive film 1 to the core 50 in the 100th round R1 from the core 50 when the photosensitive film 1 is completely unwound from the photosensitive film roll 100. It was done. Since the photosensitive film 1 is wound with a certain degree of tension, it may contract in the winding direction after being unwound. In this case, the length L1 is a length measured after the unwound photosensitive film 1 shrinks.
　比（Ｌ１／Ｄ１）が２５０以上である場合、感光性フィルム１は巻き締まりの力が緩和された状態で巻き取られた状態となり、感光性フィルム１間に異物が混入した場合であっても、巻き締まりにより異物が感光性樹脂層に押し付けられる力が十分に低減され、感光性樹脂層への打痕の発生を抑制することができる。また、感光性フィルムロール１００では巻芯５０に近いほど巻き締まりの力が感光性フィルム１にかかりやすく、打痕が生じやすいため、巻芯５０から１００周分の感光性フィルム１の長さＬ１と巻芯５０の直径Ｄ１とから求められる上記（Ｌ１／Ｄ１）が２５０以上であることが必要である。上記と同様の観点から、比（Ｌ１／Ｄ１）は２６０以上、又は、２７０以上であることが好ましい。一方、比（Ｌ１／Ｄ１）が３２０以下である場合、感光性フィルム１が十分な張力をかけて巻き取られた状態となり、巻きズレが発生することを十分に抑制することができる。特に、巻芯５０に近い位置で巻きズレが生じると、それ以降に巻かれた感光性フィルム１にも連鎖的に巻きズレが生じやすくなるため、これを防止するために、巻芯５０から１００周分の感光性フィルム１の長さＬ１と巻芯５０の直径Ｄ１とから求められる上記（Ｌ１／Ｄ１）が３２０以下であることが必要である。上記と同様の観点から、比（Ｌ１／Ｄ１）は３００以下、又は、２９０以下であることが好ましい。 When the ratio (L1 / D1) is 250 or more, the photosensitive film 1 is wound in a state in which the tightening force is reduced, and even when a foreign substance is mixed between the photosensitive films 1. In addition, the force with which the foreign matter is pressed against the photosensitive resin layer by the tightening of the winding is sufficiently reduced, and the occurrence of dents on the photosensitive resin layer can be suppressed. Further, in the photosensitive film roll 100, the closer to the winding core 50, the more easily the tightening force is applied to the photosensitive film 1 and the more easily a dent is formed. (L1 / D1) obtained from the diameter D1 of the core 50 must be 250 or more. From the same viewpoint as above, the ratio (L1 / D1) is preferably 260 or more, or 270 or more. On the other hand, when the ratio (L1 / D1) is 320 or less, the photosensitive film 1 is in a state of being wound with sufficient tension, and it is possible to sufficiently suppress the occurrence of a winding deviation. In particular, if the winding shift occurs at a position close to the core 50, the photosensitive film 1 wound thereafter tends to cause a winding shift in a chain. (L1 / D1) obtained from the length L1 of the photosensitive film 1 for the circumference and the diameter D1 of the winding core 50 needs to be 320 or less. From the same viewpoint as above, the ratio (L1 / D1) is preferably 300 or less, or 290 or less.
　感光性フィルムロール１００は、これを巻き出して測定される感光性フィルムロール１００の外側１００周分の感光性フィルム１の長さＬ２と、感光性フィルムロール１００の外側から１００周目Ｒ２の位置の直径Ｄ２との比（Ｌ２／Ｄ２）が２５０～３５０であることが好ましい。長さＬ２は、感光性フィルムロール１００から感光性フィルム１を、感光性フィルムロール１００の外側から１００周以上巻き出した時の、外側１００周分の感光性フィルム１の巻き取り方向の長さを測定したものである。なお、長さＬ２は、長さＬ１と同様に、巻き出した感光性フィルム１が収縮する場合、収縮後に測定される長さである。直径Ｄ２は、外側１００周分の感光性フィルム１を巻き出した後の感光性フィルムロールにおいて測定される直径である。ここで、直径Ｄ２は、外側１００周分の感光性フィルム１を巻き出す前の感光性フィルムロール１００の状態で測定してもよい。外側１００周分の感光性フィルム１を巻き出す前後において、直径Ｄ２の変動はほぼ無い。 The photosensitive film roll 100 has a length L2 of the photosensitive film 1 corresponding to 100 turns outside the photosensitive film roll 100 measured by unwinding the photosensitive film roll 100, and a position of the 100th turn R2 from the outside of the photosensitive film roll 100. The ratio (L2 / D2) to the diameter D2 is preferably 250 to 350. The length L2 is the length in the winding direction of the photosensitive film 1 for the outer 100 turns when the photosensitive film 1 is unwound 100 times or more from the outside of the photosensitive film roll 100 from the photosensitive film roll 100. Is measured. Note that the length L2 is a length measured after the unwinding photosensitive film 1 shrinks, similarly to the length L1. The diameter D2 is a diameter measured on the photosensitive film roll after unwinding the photosensitive film 1 for the outer 100 turns. Here, the diameter D2 may be measured in a state of the photosensitive film roll 100 before unwinding the photosensitive film 1 for the outer 100 turns. There is almost no change in the diameter D2 before and after unwinding the photosensitive film 1 for the outer 100 turns.
　比（Ｌ２／Ｄ２）が２５０以上である場合、感光性樹脂層への打痕の発生をより十分に抑制することができる。上記と同様の観点から、比（Ｌ２／Ｄ２）は２８０以上、又は、３００以上であることがより好ましい。一方、比（Ｌ２／Ｄ２）が３５０以下である場合、巻きズレが発生することを十分に抑制することができる。また、感光性フィルムロール１００の最外周に近い位置ほど、巻き締まりの力が感光性フィルム１にかかりにくいため巻きズレが生じやすいが、比（Ｌ２／Ｄ２）が３５０以下であることで、最外周付近の巻きズレの発生を十分に抑制することができる。上記と同様の観点から、比（Ｌ２／Ｄ２）は３４０以下であることがより好ましい。 When the ratio (L2 / D2) is 250 or more, the occurrence of dents on the photosensitive resin layer can be more sufficiently suppressed. From the same viewpoint as above, the ratio (L2 / D2) is more preferably 280 or more, or 300 or more. On the other hand, when the ratio (L2 / D2) is 350 or less, it is possible to sufficiently suppress the occurrence of winding deviation. In addition, as the position closer to the outermost periphery of the photosensitive film roll 100 is more difficult to apply the tightening force to the photosensitive film 1, the winding is likely to be shifted, but the ratio (L2 / D2) is 350 or less, The occurrence of winding deviation near the outer periphery can be sufficiently suppressed. From the same viewpoint as above, the ratio (L2 / D2) is more preferably 340 or less.
　なお、本明細書において、Ｌ１、Ｌ２、Ｄ１及びＤ２の単位は、全て同一の単位である。 In the present specification, the units of L1, L2, D1 and D2 are all the same unit.
　感光性フィルムロール１００において、比（Ｌ１／Ｄ１）と比（Ｌ２／Ｄ２）との大小関係は特に限定されないが、比（Ｌ２／Ｄ２）よりも比（Ｌ１／Ｄ１）の方が小さくてもよい。比（Ｌ１／Ｄ１）の方が小さいと、感光性フィルムロール１００の最外周付近よりも巻芯付近の方が巻き締まった状態となり、巻芯付近での巻きズレの発生をより一層抑制することができる。 In the photosensitive film roll 100, the magnitude relationship between the ratio (L1 / D1) and the ratio (L2 / D2) is not particularly limited, but even if the ratio (L1 / D1) is smaller than the ratio (L2 / D2). Good. When the ratio (L1 / D1) is smaller, the vicinity of the winding core becomes tighter than the vicinity of the outermost periphery of the photosensitive film roll 100, and the occurrence of a winding deviation near the winding core is further suppressed. Can be.
　感光性フィルムロール１００の巻き数は、比（Ｌ１／Ｄ１）を求めることから１００周以上であるが、２００周以上であってもよく、５００～１０００周であってもよい。巻き数が上記範囲内である場合、打痕及び巻きズレの発生を抑制する効果がより有効に奏される。なお、巻き数が２００周未満である場合、感光性フィルムロール１００において、巻芯５０から１００周分の感光性フィルム１の領域と、外側１００周分の感光性フィルム１の領域とは、一部重複していてもよい。すなわち、図１において、外側から１００周目Ｒ２は巻芯５０から１００周目Ｒ１よりも内側（巻芯５０側）に位置していてもよい。 The number of turns of the photosensitive film roll 100 is 100 or more rounds in order to obtain the ratio (L1 / D1), but may be 200 or more rounds or 500 to 1000 rounds. When the number of windings is within the above range, the effect of suppressing the occurrence of dents and winding deviation is more effectively exhibited. When the number of windings is less than 200 turns, in the photosensitive film roll 100, the area of the photosensitive film 1 for 100 turns from the winding core 50 and the area of the photosensitive film 1 for the outer 100 turns are one. Copies may be duplicated. That is, in FIG. 1, the 100th round R2 from the outside may be located on the inner side (the core 50 side) from the 100th round R1 from the core 50.
　図２は、感光性フィルムロールを構成する感光性フィルムの一実施形態を示す模式断面図である。図３は、感光性フィルムロールを構成する感光性フィルムの他の一実施形態を示す模式断面図である。図２に示すように、感光性フィルムロール１００を構成する感光性フィルム１は、支持フィルム１０と、支持フィルム１０上に配置された感光性樹脂層２０と、感光性樹脂層２０上に配置された保護フィルム４０と、を備える。本実施形態の感光性フィルム１は、転写型感光性フィルムとして用いることができる。また、感光性フィルムは、図３に示すように、支持フィルム１０と、支持フィルム１０上に配置された感光性樹脂層２０と、感光性樹脂層２０上に配置された金属酸化物粒子を含有する第二の樹脂層３０と、第二の樹脂層３０上に配置された保護フィルム４０と、を備える感光性フィルム（感光性屈折率調整フィルム）２であってもよい。すなわち、図１に示す感光性フィルムロール１００において、感光性フィルム１に代えて、感光性屈折率調整フィルム２を用いてもよい。本実施形態の感光性屈折率調整フィルム２は、転写型感光性屈折率調整フィルムとして用いることができる。 FIG. 2 is a schematic cross-sectional view showing one embodiment of the photosensitive film constituting the photosensitive film roll. FIG. 3 is a schematic sectional view showing another embodiment of the photosensitive film constituting the photosensitive film roll. As shown in FIG. 2, the photosensitive film 1 constituting the photosensitive film roll 100 includes a support film 10, a photosensitive resin layer 20 disposed on the support film 10, and a photosensitive resin layer 20 disposed on the photosensitive resin layer 20. And a protective film 40. The photosensitive film 1 of the present embodiment can be used as a transfer type photosensitive film. Further, as shown in FIG. 3, the photosensitive film includes a support film 10, a photosensitive resin layer 20 disposed on the support film 10, and metal oxide particles disposed on the photosensitive resin layer 20. A photosensitive film (photosensitive refractive index adjusting film) 2 including a second resin layer 30 to be formed and a protective film 40 disposed on the second resin layer 30 may be used. That is, in the photosensitive film roll 100 shown in FIG. 1, a photosensitive refractive index adjusting film 2 may be used instead of the photosensitive film 1. The photosensitive refractive index adjusting film 2 of the present embodiment can be used as a transfer type photosensitive refractive index adjusting film.
　上記感光性フィルム１を用いることで、例えばタッチパネルの額縁にある金属配線又はタッチパネルの透明電極の保護機能を有する硬化膜を形成することができる。また、上記感光性屈折率調整フィルム２を用いることで、例えばタッチパネルの額縁にある金属配線又はタッチパネルの透明電極の保護機能と、透明電極パターンの不可視化又はタッチ画面の視認性向上の両機能を満たす硬化膜を一括で形成することができる。以下、感光性フィルム１及び感光性屈折率調整フィルム２を構成する各層について詳細に説明する。 硬化 By using the photosensitive film 1, for example, a cured film having a function of protecting a metal wiring in a frame of a touch panel or a transparent electrode of the touch panel can be formed. Further, by using the photosensitive refractive index adjusting film 2, for example, a function of protecting a metal wiring in a frame of the touch panel or a transparent electrode of the touch panel, and a function of making the transparent electrode pattern invisible or improving the visibility of the touch screen are provided. A cured film that satisfies the conditions can be formed at a time. Hereinafter, each layer constituting the photosensitive film 1 and the photosensitive refractive index adjusting film 2 will be described in detail.
（支持フィルム）
　支持フィルム１０としては、重合体フィルムを用いることができる。重合体フィルムの材質としては、例えばポリエチレンテレフタレート、ポリカーボネート、ポリエチレン、ポリプロピレン、ポリエーテルサルフォン、シクロオレフィンポリマー等が挙げられる。 (Support film)
As the support film 10, a polymer film can be used. Examples of the material of the polymer film include polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, polyethersulfone, and cycloolefin polymer.
　支持フィルム１０の厚さは、被覆性の確保と、支持フィルム１０を介して活性光線を照射する際の解像度の低下を抑制する観点から、５～７０μｍであることが好ましく、１０～７０μｍであることがより好ましく、１５～４０μｍであることが更に好ましく、１５～３５μｍであることが特に好ましい。 The thickness of the support film 10 is preferably from 5 to 70 μm, and more preferably from 10 to 70 μm, from the viewpoint of ensuring coverage and suppressing a decrease in resolution when irradiating active light through the support film 10. More preferably, it is more preferably 15 to 40 μm, and particularly preferably 15 to 35 μm.
（感光性樹脂層）
　感光性樹脂層（第一の樹脂層）２０は、（Ａ）バインダーポリマー（以下、（Ａ）成分ともいう）と、（Ｂ）光重合性化合物（以下、（Ｂ）成分ともいう）と、（Ｃ）光重合開始剤（以下、（Ｃ）成分ともいう）と、（Ｅ）エチレン性不飽和結合を有するリン酸エステル（以下、（Ｅ）成分ともいう）とを含有する感光性樹脂組成物から形成されることが好ましい。 (Photosensitive resin layer)
The photosensitive resin layer (first resin layer) 20 includes (A) a binder polymer (hereinafter also referred to as a component (A)), (B) a photopolymerizable compound (hereinafter also referred to as a component (B)), Photosensitive resin composition containing (C) a photopolymerization initiator (hereinafter also referred to as component (C)) and (E) a phosphoric ester having an ethylenically unsaturated bond (hereinafter also referred to as component (E)). It is preferably formed from an object.
　（Ａ）成分としては、アルカリ現像によりパターニングを可能とする観点から、カルボキシル基を有するバインダーポリマーを用いることが好ましい。 As the component (A), a binder polymer having a carboxyl group is preferably used from the viewpoint of enabling patterning by alkali development.
　（Ａ）成分は、（メタ）アクリル酸、及び（メタ）アクリル酸アルキルエステルに由来する構造単位を有する共重合体が好適である。上記共重合体は、上記（メタ）アクリル酸、（メタ）アクリル酸アルキルエステルと共重合し得るその他のモノマーを構造単位に含有していてもよい。具体的には、（メタ）アクリル酸グリシジルエステル、（メタ）アクリル酸ベンジルエステル、スチレン等が挙げられる。 The component (A) is preferably a copolymer having a structural unit derived from (meth) acrylic acid and an alkyl (meth) acrylate. The copolymer may contain, in a structural unit, another monomer copolymerizable with the (meth) acrylic acid or the alkyl (meth) acrylate. Specific examples include glycidyl (meth) acrylate, benzyl (meth) acrylate, and styrene.
　また、（Ａ）成分は、エチレン性不飽和基を有してもよい。なお、エチレン性不飽和基を有する（Ａ）成分は、本明細書においては（Ｂ）成分に含ませないものとする。 成分 Component (A) may have an ethylenically unsaturated group. The component (A) having an ethylenically unsaturated group is not included in the component (B) in this specification.
　上記（メタ）アクリル酸アルキルエステルとしては、（メタ）アクリル酸メチルエステル、（メタ）アクリル酸エチルエステル、（メタ）アクリル酸ブチルエステル、（メタ）アクリル酸－２－エチルヘキシルエステル、（メタ）アクリル酸ヒドロキシルエチルエステル等が挙げられる。 Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and (meth) acryl. Acid hydroxyl ethyl ester and the like.
　（Ａ）成分としては、アルカリ現像性（特に無機アルカリ水溶液に対する）、パターニング性、透明性の観点から、（メタ）アクリル酸、（メタ）アクリル酸グリシジルエステル、（メタ）アクリル酸ベンジルエステル、スチレン、（メタ）アクリル酸メチルエステル、（メタ）アクリル酸エチルエステル、（メタ）アクリル酸ブチルエステル及び（メタ）アクリル酸２－エチルヘキシルエステルからなる群より選択される少なくとも一種の化合物由来の構造単位を有するバインダーポリマーが好ましい。 The component (A) includes (meth) acrylic acid, glycidyl (meth) acrylate, benzyl (meth) acrylate, and styrene from the viewpoint of alkali developability (particularly with respect to an aqueous inorganic alkali solution), patterning properties, and transparency. A structural unit derived from at least one compound selected from the group consisting of, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate Is preferred.
　（Ａ）成分の重量平均分子量は、解像度の観点から、１０，０００～２００，０００であることが好ましく、１５，０００～１５０，０００であることがより好ましく、３０，０００～１５０，０００であることが更に好ましく、３０，０００～１００，０００であることが特に好ましく、４０，０００～１００，０００であることが極めて好ましい。なお、重量平均分子量は、本明細書の実施例に記載したゲルパーミエーションクロマトグラフィー法により測定することができる。 The component (A) preferably has a weight average molecular weight of 10,000 to 200,000, more preferably 15,000 to 150,000, and more preferably 30,000 to 150,000, from the viewpoint of resolution. More preferably, it is particularly preferably from 30,000 to 100,000, and most preferably from 40,000 to 100,000. The weight average molecular weight can be measured by the gel permeation chromatography method described in the examples of the present specification.
　（Ａ）成分の酸価は、所望の形状を有する硬化膜（保護膜）をアルカリ現像で容易に形成する観点から、７５ｍｇＫＯＨ／ｇ以上とすることが好ましい。また、硬化膜形状の制御容易性と硬化膜の防錆性との両立を図る観点から、（Ａ）成分の酸価は、７５～２００ｍｇＫＯＨ／ｇであることが好ましく、７５～１５０ｍｇＫＯＨ／ｇであることがより好ましく、７５～１２０ｍｇＫＯＨ／ｇであることが更に好ましい。 酸 The acid value of the component (A) is preferably at least 75 mgKOH / g from the viewpoint of easily forming a cured film (protective film) having a desired shape by alkali development. The acid value of the component (A) is preferably from 75 to 200 mgKOH / g, and more preferably from 75 to 150 mgKOH / g, from the viewpoint of achieving both easy control of the cured film shape and rust prevention of the cured film. More preferably, it is more preferably 75 to 120 mgKOH / g.
　なお、酸価は、ＪＩＳ　Ｋ００７０に基づいた中和滴定法により測定することができる。具体的な測定方法の例を以下に示す。まず、バインダーポリマーの溶液を１３０℃で１時間加熱し、揮発分を除去して、固形分を得る。そして、上記固形分のバインダーポリマー１ｇを精秤した後、このバインダーポリマーにアセトンを３０ｇ添加し、これを均一に溶解し、樹脂溶液を得る。次いで、指示薬であるフェノールフタレインをその樹脂溶液に適量添加して、０．１ｍｏｌ／Ｌの水酸化カリウム水溶液を用いて中和滴定を行う。そして、次式により酸価を算出する。
　酸価＝０．１×Ｖ×ｆ１×５６．１／（Ｗｐ×Ｉ／１００）
　式中、Ｖは滴定に用いた０．１ｍｏｌ／Ｌ水酸化カリウム水溶液の滴定量（ｍＬ）、ｆ１は０．１ｍｏｌ／Ｌ水酸化カリウム水溶液のファクター（濃度換算係数）、Ｗｐは測定した樹脂溶液の質量（ｇ）、Ｉは測定した上記樹脂溶液中の不揮発分の割合（質量％）を示す。 The acid value can be measured by a neutralization titration method based on JIS K0070. An example of a specific measurement method is shown below. First, the binder polymer solution is heated at 130 ° C. for 1 hour to remove volatile components and obtain a solid component. Then, after precisely weighing 1 g of the solid binder polymer, 30 g of acetone is added to the binder polymer and uniformly dissolved to obtain a resin solution. Then, an appropriate amount of phenolphthalein as an indicator is added to the resin solution, and neutralization titration is performed using a 0.1 mol / L aqueous solution of potassium hydroxide. Then, the acid value is calculated by the following equation.
Acid value = 0.1 × V × f1 × 56.1 / (Wp × I / 100)
In the formula, V is the titer (mL) of the 0.1 mol / L aqueous potassium hydroxide solution used for titration, f1 is the factor (concentration conversion coefficient) of the 0.1 mol / L aqueous potassium hydroxide solution, and Wp is the measured resin solution. And I represents the ratio (% by mass) of the nonvolatile content in the resin solution measured.
　（Ｂ）成分としては、エチレン性不飽和基を有する光重合性化合物を用いることができる。エチレン性不飽和基を有する光重合性化合物としては、例えば分子内に一つの重合可能なエチレン性不飽和基を有する一官能ビニルモノマー、分子内に二つの重合可能なエチレン性不飽和基を有する二官能ビニルモノマー、又は分子内に少なくとも三つの重合可能なエチレン性不飽和基を有する多官能ビニルモノマーが挙げられる。 光 As the component (B), a photopolymerizable compound having an ethylenically unsaturated group can be used. Examples of the photopolymerizable compound having an ethylenically unsaturated group include, for example, a monofunctional vinyl monomer having one polymerizable ethylenically unsaturated group in a molecule, and having two polymerizable ethylenically unsaturated groups in a molecule. Examples include bifunctional vinyl monomers or polyfunctional vinyl monomers having at least three polymerizable ethylenically unsaturated groups in the molecule.
　上記分子内に一つの重合可能なエチレン性不飽和基を有する一官能ビニルモノマーとしては、例えば、上記（Ａ）成分の好適な例である共重合体の合成に用いられるモノマーとして例示したものが挙げられる。 Examples of the monofunctional vinyl monomer having one polymerizable ethylenically unsaturated group in the molecule include those exemplified as monomers used in the synthesis of a copolymer which is a preferred example of the component (A). No.
　上記分子内に二つの重合可能なエチレン性不飽和基を有する二官能ビニルモノマーとしては、硬化膜の透湿度を低減する観点から、トリシクロデカン骨格又はトリシクロデセン骨格を有する化合物を含むことが好ましい。金属配線及び透明電極パターンの腐食抑制の観点から、トリシクロデカン骨格又はトリシクロデセン骨格を有する化合物として、下記一般式（１）で表されるジ（メタ）アクリレート化合物を含むことが好ましい。 As the bifunctional vinyl monomer having two polymerizable ethylenically unsaturated groups in the molecule, from the viewpoint of reducing the moisture permeability of the cured film, it may include a compound having a tricyclodecane skeleton or a tricyclodecene skeleton. preferable. From the viewpoint of inhibiting corrosion of the metal wiring and the transparent electrode pattern, it is preferable to include a di (meth) acrylate compound represented by the following general formula (1) as a compound having a tricyclodecane skeleton or a tricyclodecene skeleton.
Figure JPOXMLDOC01-appb-C000001
 ［一般式（１）中、Ｒ３１及びＲ３２は、それぞれ独立に水素原子又はメチル基を示し、Ｘは、トリシクロデカン骨格又はトリシクロデセン骨格を有する２価の基を示し、Ｒ３３及びＲ３４は、それぞれ独立に炭素数１～４のアルキレン基を示し、ｎ及びｍは、それぞれ独立に０～２の整数を示し、ｐ及びｑは、それぞれ独立に０以上の整数を示し、ｐ＋ｑ＝０～１０となるように選択される。］
Figure JPOXMLDOC01-appb-C000001
 [In the general formula (1), R 31 and R 32 each independently represent a hydrogen atom or a methyl group, X represents a tricyclodecane skeleton or a divalent group having a tricyclodecene skeleton, and R 33 and R 33 R 34 each independently represents an alkylene group having 1 to 4 carbon atoms, n and m each independently represent an integer of 0 to 2, p and q each independently represent an integer of 0 or more, and p + q = 0 to 10. ]
　上記一般式（１）において、Ｒ３３及びＲ３４は、エチレン基又はプロピレン基であることが好ましく、エチレン基であることがより好ましい。また、プロピレン基はｎ－イソプロピレン基及びイソプロピレン基のいずれであってもよい。 In the general formula (1), R 33 and R 34 are preferably an ethylene group or a propylene group, and more preferably an ethylene group. The propylene group may be any of an n-isopropylene group and an isopropylene group.
　上記一般式（１）で表される化合物によれば、Ｘに含まれるトリシクロデカン骨格又はトリシクロデセン骨格を有する２価の基が、嵩高い構造を有することで、硬化膜の低透湿性を実現し、金属配線及び透明電極の腐食抑制性を向上されることができる。ここで、本明細書中における「トリシクロデカン骨格」及び「トリシクロデセン骨格」とは、それぞれ以下の構造（それぞれ、結合手は任意の箇所である）をいう。 According to the compound represented by the general formula (1), the divalent group having a tricyclodecane skeleton or a tricyclodecene skeleton contained in X has a bulky structure, so that the cured film has low moisture permeability. And the corrosion inhibition of the metal wiring and the transparent electrode can be improved. Here, the “tricyclodecane skeleton” and “tricyclodecene skeleton” in the present specification refer to the following structures, respectively (the bond is an arbitrary position).
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　トリシクロデカン骨格又はトリシクロデセン骨格を有する化合物としては、得られる硬化膜パターンの低透湿性の観点から、トリシクロデカンジメタノールジ（メタ）アクリレート等のトリシクロデカン骨格を有する化合物が好ましい。これらは、ＤＣＰ及びＡ－ＤＣＰ（いずれも新中村化学工業株式会社製）として入手可能である。 As the compound having a tricyclodecane skeleton or a tricyclodecene skeleton, a compound having a tricyclodecane skeleton such as tricyclodecane dimethanol di (meth) acrylate is preferable from the viewpoint of low moisture permeability of the obtained cured film pattern. These are available as DCP and A-DCP (both manufactured by Shin-Nakamura Chemical Co., Ltd.).
　（Ｂ）成分における、トリシクロデカン骨格又はトリシクロデセン骨格を有する化合物の割合は、透湿度を低減する観点から、感光性樹脂組成物に含まれる光重合性化合物の合計量１００質量部のうち、５０質量部以上であることが好ましく、７０質量部以上であることがより好ましく、８０質量部以上であることが更に好ましい。 The proportion of the compound having a tricyclodecane skeleton or a tricyclodecene skeleton in the component (B) is preferably 100 parts by mass of the total amount of the photopolymerizable compound contained in the photosensitive resin composition from the viewpoint of reducing the moisture permeability. , 50 parts by mass or more, more preferably 70 parts by mass or more, even more preferably 80 parts by mass or more.
　トリシクロデカン骨格又はトリシクロデセン骨格を有する化合物とは別の、分子内に二つの重合可能なエチレン性不飽和基を有する二官能ビニルモノマーとしては、ポリエチレングリコールジ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、２，２－ビス（４－（メタ）アクリロキシポリエトキシポリプロポキシフェニル）プロパン、ビスフェノールＡジグリシジルエーテルジ（メタ）アクリレート等が挙げられる。 Examples of the bifunctional vinyl monomer having two polymerizable ethylenically unsaturated groups in the molecule other than the compound having a tricyclodecane skeleton or a tricyclodecene skeleton include polyethylene glycol di (meth) acrylate and trimethylolpropane. Examples thereof include di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2,2-bis (4- (meth) acryloxypolyethoxypolypropoxyphenyl) propane, and bisphenol A diglycidyl ether di (meth) acrylate.
　上記分子内に少なくとも三つの重合可能なエチレン性不飽和基を有する多官能ビニルモノマーとしては、従来公知のものを特に制限無く用いることができる。金属配線又は透明電極の腐食防止及び現像性の観点から、上記多官能ビニルモノマーとしては、トリメチロールプロパントリ（メタ）アクリレート等のトリメチロールプロパン由来の骨格を有する（メタ）アクリレート化合物；テトラメチロールメタントリ（メタ）アクリレート、テトラメチロールメタンテトラ（メタ）アクリレート等のテトラメチロールメタン由来の骨格を有する（メタ）アクリレート化合物；ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート等のペンタエリスリトール由来の骨格を有する（メタ）アクリレート化合物；ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等のジペンタエリスリトール由来の骨格を有する（メタ）アクリレート化合物；ジトリメチロールプロパンテトラ（メタ）アクリレート等のジトリメチロールプロパン由来の骨格を有する（メタ）アクリレート化合物；又はジグリセリン由来の骨格を有する（メタ）アクリレート化合物；シアヌル酸由来の骨格を有する（メタ）アクリレート化合物を用いることが好ましい。 従 来 As the polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups in the molecule, a conventionally known polyfunctional vinyl monomer can be used without any particular limitation. From the viewpoints of corrosion prevention and developability of the metal wiring or the transparent electrode, the polyfunctional vinyl monomer may be a (meth) acrylate compound having a skeleton derived from trimethylolpropane such as trimethylolpropane tri (meth) acrylate; tetramethylolmethane (Meth) acrylate compounds having a skeleton derived from tetramethylolmethane such as tri (meth) acrylate and tetramethylolmethanetetra (meth) acrylate; derived from pentaerythritol such as pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate (Meth) acrylate compounds having a skeleton of; dipentaerythritol penta (meth) acrylate, bone derived from dipentaerythritol such as dipentaerythritol hexa (meth) acrylate (Meth) acrylate compounds having a skeleton derived from ditrimethylolpropane such as ditrimethylolpropanetetra (meth) acrylate; or (meth) acrylate compounds having a skeleton derived from diglycerin; cyanuric acid-derived It is preferable to use a (meth) acrylate compound having a skeleton.
　分子内に少なくとも三つの重合可能なエチレン性不飽和基を有するモノマーと、分子内に一つの重合可能なエチレン性不飽和基を有する二官能ビニルモノマー又は分子内に二つの重合可能なエチレン性不飽和基を有する二官能ビニルモノマーを組み合わせて用いる場合、使用する割合に特に制限は無いが、光硬化性及び電極腐食を防止する観点から、分子内に少なくとも三つの重合可能なエチレン性不飽和基を有するモノマーの割合が、感光性樹脂組成物に含まれる光重合性化合物の合計量１００質量部のうち、３０質量部以上であることが好ましく、５０質量部以上であることがより好ましく、７５質量部以上であることが更に好ましい。 A monomer having at least three polymerizable ethylenically unsaturated groups in the molecule and a bifunctional vinyl monomer having one polymerizable ethylenically unsaturated group in the molecule or two polymerizable ethylenically unsaturated groups in the molecule; When a bifunctional vinyl monomer having a saturated group is used in combination, the ratio is not particularly limited, but from the viewpoint of preventing photocuring and electrode corrosion, at least three polymerizable ethylenically unsaturated groups in the molecule. Is preferably at least 30 parts by mass, more preferably at least 50 parts by mass, out of 100 parts by mass of the total amount of the photopolymerizable compound contained in the photosensitive resin composition, and more preferably 75 parts by mass. More preferably, the amount is at least part by mass.
　（Ａ）成分及び（Ｂ）成分の含有量は、（Ａ）成分及び（Ｂ）成分の合計量１００質量部に対し、（Ａ）成分が３５～８５質量部であることが好ましく、４０～８０質量部であることがより好ましく、５０～７０質量部であることが更に好ましく、５５～６５質量部であることが特に好ましい。特に、パターン形成性及び硬化膜の透明性を維持する点では、（Ａ）成分及び（Ｂ）成分の合計量１００質量部に対し、（Ａ）成分が、３５質量部以上であることが好ましく、４０質量部以上であることがより好ましく、５０質量部以上であることが更に好ましく、５５質量部以上であることが特に好ましい。 The content of the component (A) and the component (B) is preferably 35 to 85 parts by mass, more preferably 40 to 50 parts by mass based on 100 parts by mass of the total of the components (A) and (B). The amount is more preferably 80 parts by mass, further preferably 50 to 70 parts by mass, and particularly preferably 55 to 65 parts by mass. In particular, from the viewpoint of maintaining the pattern formability and the transparency of the cured film, the component (A) is preferably 35 parts by mass or more based on 100 parts by mass of the total amount of the components (A) and (B). , 40 parts by mass or more, more preferably 50 parts by mass or more, particularly preferably 55 parts by mass or more.
　（Ｃ）成分としては、従来公知の光重合開始剤を特に制限無く用いることができるが、透明性の高い光重合開始剤を用いることが好ましい。基材上に、厚さが１０μｍ以下の薄膜であっても充分な解像度で樹脂硬化膜パターンを形成する点では、（Ｃ）成分はオキシムエステル化合物及び／又はホスフィンオキサイド化合物を含むことが好ましい。ホスフィンオキサイド化合物としては、２，４，６－トリメチルベンゾイル－ジフェニル－ホスフィンオキサイド等が挙げられる。 As the component (C), a conventionally known photopolymerization initiator can be used without any particular limitation, but it is preferable to use a highly transparent photopolymerization initiator. The component (C) preferably contains an oxime ester compound and / or a phosphine oxide compound from the viewpoint of forming a resin cured film pattern with sufficient resolution even on a base material even if the thickness is 10 μm or less. Examples of the phosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
　オキシムエステル化合物は、下記一般式（２）で表される化合物、下記一般式（３）で表される化合物、又は下記一般式（４）で表される化合物であることが好ましい。 The oxime ester compound is preferably a compound represented by the following general formula (2), a compound represented by the following general formula (3), or a compound represented by the following general formula (4).
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　式（２）中、Ｒ１１及びＲ１２は、それぞれ独立に、炭素数１～１２のアルキル基、炭素数４～１０のシクロアルキル基、フェニル基又はトリル基を示し、炭素数１～８のアルキル基、炭素数４～６のシクロアルキル基、フェニル基又はトリル基であることが好ましく、炭素数１～４のアルキル基、炭素数４～６のシクロアルキル基、フェニル基又はトリル基であることがより好ましく、メチル基、シクロペンチル基、フェニル基又はトリル基であることが更に好ましい。Ｒ１３は、－Ｈ、－ＯＨ、－ＣＯＯＨ、－Ｏ（ＣＨ２）ＯＨ、－Ｏ（ＣＨ２）２ＯＨ、－ＣＯＯ（ＣＨ２）ＯＨ又は－ＣＯＯ（ＣＨ２）２ＯＨを示し、－Ｈ、－Ｏ（ＣＨ２）ＯＨ、－Ｏ（ＣＨ２）２ＯＨ、－ＣＯＯ（ＣＨ２）ＯＨ、又は－ＣＯＯ（ＣＨ２）２ＯＨであることが好ましく、－Ｈ、－Ｏ（ＣＨ２）２ＯＨ、又は－ＣＯＯ（ＣＨ２）２ＯＨであることがより好ましい。 In the formula (2), R 11 and R 12 each independently represent 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; 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. More preferably, it is a methyl group, a cyclopentyl group, a phenyl group or a tolyl group. 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; H, —O (CH 2 ) OH, —O (CH 2 ) 2 OH, —COO (CH 2 ) OH, or —COO (CH 2 ) 2 OH, preferably —H, —O (CH 2) ) 2 OH or —COO (CH 2 ) 2 OH.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　式（３）中、２つのＲ１４は、それぞれ独立に、炭素数１～６のアルキル基を示し、プロピル基であることが好ましい。Ｒ１５は、ＮＯ２又はＡｒＣＯ（ここで、Ａｒはアリール基を示す。）を示し、Ａｒとしては、トリル基が好ましい。Ｒ１６及びＲ１７は、それぞれ独立に、炭素数１～１２のアルキル基、フェニル基、又はトリル基を示し、メチル基、フェニル基又はトリル基であることが好ましい。 In the formula (3), two R 14 each independently represent an alkyl group having 1 to 6 carbon atoms, preferably a propyl group. R 15 represents NO 2 or ArCO (where 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, and is preferably a methyl group, a phenyl group, or a tolyl group.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　式（４）中、Ｒ１８は、炭素数１～６のアルキル基を示し、エチル基であることが好ましい。Ｒ１９はアセタール結合を有する有機基である。Ｒ２０及びＲ２１は、それぞれ独立に、炭素数１～１２のアルキル基、フェニル基又はトリル基を示し、メチル基、フェニル基又はトリル基であることが好ましく、メチル基であることがより好ましい。Ｒ２２は、水素原子又はアルキル基を示す。 In the formula (4), 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. R 20 and R 21 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, and more preferably a methyl group. . R 22 represents a hydrogen atom or an alkyl group.
　上記一般式（２）で表される化合物は、ＩＲＧＡＣＵＲＥ　ＯＸＥ　０１（ＢＡＳＦ株式会社製、製品名）として入手可能である。 The compound represented by the general formula (2) is available as IRGACURE OXE 01 (product name, manufactured by BASF Corporation).
　上記一般式（３）で表される化合物は、ＤＦＩ－０９１（ダイトーケミックス株式会社製、製品名）として入手可能である。 化合物 The compound represented by the above general formula (3) is available as DFI-091 (manufactured by Daito Chemmix, Inc., product name).
　上記一般式（４）で表される化合物は、例えば、アデカオプトマーＮ－１９１９（株式会社ＡＤＥＫＡ製、製品名）として入手可能である。 化合物 The compound represented by the general formula (4) is available, for example, as ADEKA OPTOMER N-1919 (product name, manufactured by ADEKA Corporation).
　（Ｃ）成分の含有量は、光感度及び解像度に優れる点では、（Ａ）成分及び（Ｂ）成分の合計量１００質量部に対し、０．１～１０質量部であることが好ましく、１～５質量部であることがより好ましく、１～３質量部であることが更に好ましく、１～２質量部であることが特に好ましい。 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) from the viewpoint of excellent photosensitivity and resolution. The amount is more preferably from 5 to 5 parts by mass, further preferably from 1 to 3 parts by mass, particularly preferably from 1 to 2 parts by mass.
　本実施形態に係る感光性樹脂組成物は、硬化膜の防錆性をより向上させる観点から、メルカプト基を有するトリアゾール化合物、メルカプト基を有するテトラゾール化合物、メルカプト基を有するチアジアゾール化合物、アミノ基を有するトリアゾール化合物及びアミノ基を有するテトラゾール化合物からなる群より選択される少なくとも一種の化合物（以下、（Ｄ）成分ともいう）を更に含有することが好ましい。メルカプト基を有するトリアゾール化合物としては、例えば、３－メルカプト－トリアゾール（和光純薬工業株式会社製、製品名：３ＭＴ）が挙げられる。また、メルカプト基を有するチアジアゾール化合物としては、例えば、２－アミノ－５－メルカプト－１，３，４－チアジアゾール（和光純薬工業株式会社製、製品名：ＡＴＴ）が挙げられる。 The photosensitive resin composition according to the present embodiment has a triazole compound having a mercapto group, a tetrazole compound having a mercapto group, a thiadiazole compound having a mercapto group, and an amino group, from the viewpoint of further improving the rust resistance of the cured film. It is preferable that the composition further contains at least one compound selected from the group consisting of a triazole compound and a tetrazole compound having an amino group (hereinafter, also referred to as a component (D)). Examples of the triazole compound having a mercapto group include 3-mercapto-triazole (manufactured by Wako Pure Chemical Industries, Ltd., product name: 3MT). Examples of 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.).
　上記アミノ基を有するトリアゾール化合物としては、例えばベンゾトリアゾール、１Ｈ－ベンゾトリアゾール－１－アセトニトリル、ベンゾトリアゾール－５－カルボン酸、１Ｈ－ベンゾトリアゾール－１－メタノール、カルボキシベンゾトリアゾール等にアミノ基が置換した化合物、３－メルカプトトリアゾール、５－メルカプトトリアゾール等のメルカプト基を含むトリアゾール化合物にアミノ基が置換した化合物などが挙げられる。 Examples of the triazole compound having an amino group include benzotriazole, 1H-benzotriazole-1-acetonitrile, benzotriazole-5-carboxylic acid, 1H-benzotriazole-1-methanol, carboxybenzotriazole, and the like, in which the amino group is substituted. Compounds, such as 3-mercaptotriazole and 5-mercaptotriazole, which are substituted with a triazole compound containing a mercapto group and substituted with an amino group.
　上記アミノ基を有するテトラゾール化合物としては、例えば５－アミノ－１Ｈ－テトラゾール、１－メチル－５－アミノ－テトラゾール、１－メチル－５－メルカプト－１Ｈ－テトラゾール、１－カルボキシメチル－５－アミノ－テトラゾール等が挙げられる。これらのテトラゾール化合物は、その水溶性塩であってもよい。具体例としては、１－メチル－５－アミノ－テトラゾールのナトリウム、カリウム、リチウム等のアルカリ金属塩などが挙げられる。 Examples of the tetrazole compound having an amino group include 5-amino-1H-tetrazole, 1-methyl-5-amino-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 1-carboxymethyl-5-amino- Tetrazole and the like. These tetrazole compounds may be water-soluble salts thereof. Specific examples include sodium, potassium and lithium alkali metal salts of 1-methyl-5-amino-tetrazole.
　感光性樹脂組成物が（Ｄ）成分を含有する場合、その含有量は、（Ａ）成分及び（Ｂ）成分の合計量１００質量部に対し、０．０５～５．０質量部が好ましく、０．１～２．０質量部がより好ましく、０．２～１．０質量部が更に好ましく、０．３～０．８質量部が特に好ましい。 When the photosensitive resin composition contains the component (D), the content is preferably 0.05 to 5.0 parts by mass based on 100 parts by mass of the total of the components (A) and (B). The amount is more preferably 0.1 to 2.0 parts by mass, further preferably 0.2 to 1.0 part by mass, and particularly preferably 0.3 to 0.8 part by mass.
　本実施形態に係る感光性樹脂組成物は、基材に対する密着性向上の観点から、（Ｅ）エチレン性不飽和結合を含むリン酸エステルを含有することが好ましい。なお、本明細書において、エチレン性不飽和結合を含むリン酸エステルは、（Ｂ）成分ではなく（Ｅ）成分として扱うこととする。 感光 The photosensitive resin composition according to the present embodiment preferably contains (E) a phosphate ester containing an ethylenically unsaturated bond from the viewpoint of improving adhesion to a substrate. In this specification, a phosphate ester containing an ethylenically unsaturated bond is treated as a component (E) instead of a component (B).
　（Ｅ）成分であるエチレン性不飽和結合を含むリン酸エステルとしては、形成する硬化膜の防錆性を充分確保しつつ、基材及びＩＴＯ電極に対する密着性と金属配線上での現像性とを高水準で両立する観点から、ユニケミカル株式会社製のＰｈｏｓｍｅｒシリーズ（Ｐｈｏｓｍｅｒ－Ｍ、Ｐｈｏｓｍｅｒ－ＣＬ、Ｐｈｏｓｍｅｒ－ＰＥ、Ｐｈｏｓｍｅｒ－ＭＨ、Ｐｈｏｓｍｅｒ－ＰＰ等）、又は日本化薬株式会社製のＫＡＹＡＭＥＲシリーズ（ＰＭ－２１、ＰＭ－２等）が好ましい。 The phosphoric acid ester containing an ethylenically unsaturated bond, which is a component (E), has sufficient adhesiveness to a base material and an ITO electrode and developability on metal wiring while ensuring sufficient rust prevention of a cured film to be formed. From the viewpoint of achieving a high level of compatibility, Unichemical Chemical's Phosmer series (Phosmer-M, Phosmer-CL, Phosmer-PE, Phosmer-MH, Phosmer-PP, etc.) or KAYAMER series of Nippon Kayaku Co., Ltd. (PM-21, PM-2, etc.) are preferred.
　（Ｅ）成分の含有量は、基材に対する密着性向上と、現像残渣の発生抑制の観点から、（Ａ）成分及び（Ｂ）成分の合計量１００質量部に対し、０．１～５．０質量部であることが好ましく、０．２～３．０質量部であることがより好ましい。 The content of the component (E) is from 0.1 to 5.0 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B) from the viewpoint of improving the adhesion to the substrate and suppressing the generation of the development residue. The amount is preferably 0 parts by mass, more preferably 0.2 to 3.0 parts by mass.
　本実施形態に係る感光性樹脂層２０を形成する樹脂組成物には、その他の添加剤として、必要に応じて、シランカップリング剤等の密着性付与剤、防錆剤、レベリング剤、可塑剤、充填剤、消泡剤、難燃剤、安定剤、酸化防止剤、香料、熱架橋剤、重合禁止剤などを（Ａ）成分及び（Ｂ）成分の合計量１００質量部に対し、各々０．０１～２０質量部程度含有させることができる。これらは、単独で又は２種以上を組み合わせて使用できる。なお、上記の「感光性樹脂層を形成する樹脂組成物」とは、後述する溶剤を含まない状態の組成物をいい、各成分の含有量は、後述する溶剤以外の成分全量に対する含有量である。 In the resin composition forming the photosensitive resin layer 20 according to the present embodiment, as other additives, if necessary, an adhesion imparting agent such as a silane coupling agent, a rust preventive, a leveling agent, and a plasticizer. , A filler, an antifoaming agent, a flame retardant, a stabilizer, an antioxidant, a fragrance, a thermal crosslinking agent, a polymerization inhibitor, etc., each in an amount of 0.1 parts by weight based on 100 parts by mass of the total of the components (A) and (B) The content can be about 01 to 20 parts by mass. These can be used alone or in combination of two or more. In addition, the above-mentioned "resin composition forming a photosensitive resin layer" refers to a composition not containing a solvent described below, and the content of each component is a content relative to the total amount of components other than the solvent described below. is there.
　感光性樹脂層２０の波長６３３ｎｍにおける屈折率は、通常１．４０～１．４９である。 (4) The refractive index of the photosensitive resin layer 20 at a wavelength of 633 nm is usually 1.40 to 1.49.
　感光性樹脂層２０の厚さは、保護膜として充分に効果を奏し、且つ透明電極パターン付き基材表面の段差を充分に埋め込む上では、乾燥後の厚さで１５μｍ以下であることが好ましく、２～１０μｍであることがより好ましく、３～８μｍであることが更に好ましい。また、硬化後における感光性樹脂層２０の厚さも上記範囲内であることが好ましい。 The thickness of the photosensitive resin layer 20 is sufficiently effective as a protective film, and is preferably 15 μm or less in terms of thickness after drying, in order to sufficiently embed steps on the surface of the substrate with a transparent electrode pattern, The thickness is more preferably 2 to 10 μm, and still more preferably 3 to 8 μm. Further, the thickness of the photosensitive resin layer 20 after curing is preferably within the above range.
（第二の樹脂層）
　第二の樹脂層（屈折率調整層）３０は、金属酸化物粒子を含有する層である。第二の樹脂層３０は、金属酸化物粒子を含有することにより、感光性樹脂層２０よりも相対的に高い屈折率を有することができる。第二の樹脂層３０は、６３３ｎｍにおける屈折率が１．４０～１．９０の範囲内であることが好ましく、１．５０～１．９０であることがより好ましく、１．５３～１．８５であることが更に好ましく、１．５５～１．７５であることが特に好ましい。また、第二の樹脂層が硬化性成分を含む場合、硬化後における第二の樹脂層の６３３ｎｍにおける屈折率も上記範囲内であることが好ましい。 (Second resin layer)
The second resin layer (refractive index adjusting layer) 30 is a layer containing metal oxide particles. The second resin layer 30 can have a relatively higher refractive index than the photosensitive resin layer 20 by containing the metal oxide particles. The refractive index of the second resin layer 30 at 633 nm is preferably in the range of 1.40 to 1.90, more preferably 1.50 to 1.90, and preferably 1.53 to 1.85. Is more preferably 1.55 to 1.75. When the second resin layer contains a curable component, the refractive index of the second resin layer at 633 nm after curing is preferably within the above range.
　第二の樹脂層３０の６３３ｎｍにおける屈折率が上記範囲内であると、硬化膜パターンをＩＴＯ等の透明電極パターン上に設けた場合に、硬化膜パターン上に使用される各種部材（例えば、モジュール化する際に使用するカバーガラスと透明電極パターンとを接着するＯＣＡ）との屈折率の中間値となり、ＩＴＯ等の透明電極パターンが形成されている部分と形成されていない部分での光学的な反射による色差を小さくすることが可能となり、骨見え現象を防止できる。また、画面全体の反射光強度を低減することが可能となり、画面上の透過率低下を抑制することが可能となる。 When the refractive index at 633 nm of the second resin layer 30 is within the above range, when a cured film pattern is provided on a transparent electrode pattern such as ITO, various members used on the cured film pattern (for example, a module) Between the cover glass used to form the transparent electrode pattern and the refractive index of the transparent electrode pattern (OCA), which is the optical value between the portion where the transparent electrode pattern such as ITO is formed and the portion where the transparent electrode pattern is not formed. The color difference due to reflection can be reduced, and the bone appearance phenomenon can be prevented. Further, it is possible to reduce the intensity of the reflected light on the entire screen, and it is possible to suppress a decrease in transmittance on the screen.
　ＩＴＯ等の透明電極の屈折率は、１．８０～２．１０であることが好ましく、１．８５～２．０５であることがより好ましく、１．９０～２．００であることが更に好ましい。また、ＯＣＡ等の部材の屈折率は１．４５～１．５５であることが好ましく、１．４７～１．５３であることがより好ましく、１．４８～１．５１であることが更に好ましい。 The refractive index of a transparent electrode such as ITO is preferably from 1.80 to 2.10, more preferably from 1.85 to 2.05, and even more preferably from 1.90 to 2.00. . Further, the refractive index of a member such as OCA is preferably from 1.45 to 1.55, more preferably from 1.47 to 1.53, even more preferably from 1.48 to 1.51. .
　第二の樹脂層３０は、４５０～６５０ｎｍの波長域における最小光透過率が８０％以上であることが好ましく、８５％以上であることがより好ましく、９０％以上であることが更に好ましい。また、第二の樹脂層が硬化性成分を含む場合、硬化後における第二の樹脂層の４５０～６５０ｎｍの波長域における最小光透過率も上記範囲内であることが好ましい。 最小 The second resin layer 30 has a minimum light transmittance of preferably at least 80%, more preferably at least 85%, even more preferably at least 90% in a wavelength range of 450 to 650 nm. When the second resin layer contains a curable component, the minimum light transmittance of the second resin layer after curing in a wavelength region of 450 to 650 nm is preferably within the above range.
　第二の樹脂層３０は、上記の（Ａ）成分、（Ｂ）成分及び（Ｃ）成分を含有することができ、必要に応じて、上記（Ｄ）成分及び／又は上記（Ｅ）成分を更に含有することができる。第二の樹脂層３０は（Ｂ）成分、（Ｃ）成分等の光重合成分を必ずしも含有する必要はなく、層形成により隣接する樹脂層から移行する光重合成分を利用して第二の樹脂層を光硬化させることもできる。 The second resin layer 30 can contain the component (A), the component (B) and the component (C). If necessary, the component (D) and / or the component (E) can be used. Further, it can be contained. The second resin layer 30 does not necessarily need to contain a photopolymerization component such as the component (B) and the component (C), and utilizes the photopolymerization component that migrates from the adjacent resin layer by forming the layer to form the second resin layer. The layers can also be photocured.
　第二の樹脂層３０は、金属酸化物粒子（以下、（Ｆ）成分ともいう）を含有する。金属酸化物粒子としては、特に波長６３３ｎｍにおける屈折率が１．５０以上である、金属酸化物粒子を含有することが好ましい。これにより、感光性屈折率調整フィルムを調製した際、第二の樹脂層の透明性及び波長６３３ｎｍにおける屈折率を向上させることが可能となる。また、基材への吸着を抑制しつつ、現像性を向上させることができる。 The second resin layer 30 contains metal oxide particles (hereinafter also referred to as component (F)). The metal oxide particles preferably contain metal oxide particles having a refractive index of 1.50 or more at a wavelength of 633 nm. This makes it possible to improve the transparency of the second resin layer and the refractive index at a wavelength of 633 nm when the photosensitive refractive index adjusting film is prepared. Further, the developability can be improved while suppressing adsorption to the substrate.
　金属酸化物粒子としては、酸化ジルコニウム、酸化チタン、酸化スズ、酸化亜鉛、酸化インジウムスズ、酸化インジウム、酸化アルミウム、酸化イットリウム等の金属酸化物からなる粒子が挙げられる。これらの中でも、骨見え現象抑制の観点から、酸化ジルコニウム又は酸化チタンの粒子が好ましい。 Examples of 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, zirconium oxide or titanium oxide particles are preferable from the viewpoint of suppressing the bone appearance phenomenon.
　酸化ジルコニウム粒子としては、透明電極の材料がＩＴＯの場合、屈折率向上と、ＩＴＯ及び透明基材との密着性の観点から、酸化ジルコニウムナノ粒子を用いることが好ましい。酸化ジルコニウムナノ粒子の中でも、粒度分布Ｄｍａｘが４０ｎｍ以下であることが好ましい。 ジ ル As 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. Among the zirconium oxide nanoparticles, the particle size distribution Dmax is preferably 40 nm or less.
　酸化ジルコニウムナノ粒子は、ＯＺ－Ｓ３０Ｋ（日産化学工業株式会社製、製品名）、ＯＺ－Ｓ４０Ｋ－ＡＣ（日産化学工業株式会社製、製品名）、ＳＺＲ－Ｋ（酸化ジルコニウムメチルエチルケトン分散液、堺化学工業株式会社製、製品名）、ＳＺＲ－Ｍ（酸化ジルコニウムメタノール分散液、堺化学工業株式会社製、製品名）として商業的に入手可能である。 Zirconium oxide nanoparticles are OZ-S30K (Nissan Chemical Industries, Ltd., product name), OZ-S40K-AC (Nissan Chemical Industries, Ltd., product name), SZR-K (Zirconium oxide methyl ethyl ketone dispersion, Sakai Chemical It is commercially available as SZR-M (Zirconium oxide methanol dispersion, product name, manufactured by Sakai Chemical Industry Co., Ltd.).
　第二の樹脂層３０には、（Ｆ）成分として酸化チタンナノ粒子を含有させることも可能である。また、酸化チタンナノ粒子の中でも、粒度分布Ｄｍａｘが５０ｎｍ以下であることが好ましく、１０～５０ｎｍがより好ましい。 (4) The second resin layer 30 may contain titanium oxide nanoparticles as the component (F). Further, among the titanium oxide nanoparticles, the particle size distribution Dmax is preferably 50 nm or less, more preferably 10 to 50 nm.
　（Ｆ）成分として、上記金属酸化物粒子のほかに、例えばＭｇ、Ａｌ、Ｓｉ、Ｃａ、Ｃｒ、Ｃｕ、Ｚｎ、Ｂａ等の原子を含む酸化物粒子又は硫化物粒子を用いることもできる。 As the component (F), oxide particles or sulfide particles containing atoms such as Mg, Al, Si, Ca, Cr, Cu, Zn, and Ba can be used in addition to the metal oxide particles.
　また上記金属酸化物粒子の他に、例えばトリアジン環を有する化合物、イソシアヌル酸骨格を有する化合物、フルオレン骨格を有する化合物等の有機化合物を用いることも可能である。これにより波長６３３ｎｍにおける屈折率を向上させることができる。 In addition to the metal oxide particles, it is also possible to use an organic compound such as a compound having a triazine ring, a compound having an isocyanuric acid skeleton, and a compound having a fluorene skeleton. Thereby, the refractive index at a wavelength of 633 nm can be improved.
　上記第二の樹脂層３０の厚さは、０．０１～１μｍであってもよく、０．０３～０．５μｍであることが好ましく、０．０４～０．３μｍであることがより好ましく、０．０５～０．２５μｍであることが更に好ましく、０．０５～０．２μｍであることが特に好ましい。厚さが０．０１～１μｍであることにより、上述の画面全体の反射光強度をより低減することが可能となる。また、硬化後における第二の樹脂層の厚さも上記範囲内であることが好ましい。 The thickness of the second resin layer 30 may be 0.01 to 1 μm, preferably 0.03 to 0.5 μm, more preferably 0.04 to 0.3 μm, The thickness is more preferably 0.05 to 0.25 μm, and particularly preferably 0.05 to 0.2 μm. When the thickness is 0.01 to 1 μm, it is possible to further reduce the above-described reflected light intensity of the entire screen. It is also preferable that the thickness of the second resin layer after curing is within the above range.
　本実施形態の感光性屈折率調整フィルムは、基材上に、第二の樹脂層３０が基材と接するようにラミネートする場合、すなわち、感光性樹脂層２０と基材との間に第二の樹脂層３０が介在する場合であっても、第二の樹脂層３０の厚さが充分に薄いため、密着性及び解像性等の物性は感光性樹脂層２０の組成の影響を大きく受ける。また、感光性樹脂層２０と第二の樹脂層３０との間で成分の移動が生じることもあり、感光性樹脂層２０の組成が基材に密着する第二の樹脂層３０にも影響する。そのため、本実施形態の感光性屈折率調整フィルムは、感光性樹脂層２０が上述した特定の組成を有することにより、基材と感光性樹脂層２０との間に第二の樹脂層３０が介在する場合であっても、これまでに述べた各種の効果を奏することができる。 The photosensitive refractive index adjusting film of the present embodiment is laminated on a substrate such that the second resin layer 30 is in contact with the substrate, that is, the second resin layer 30 is disposed between the photosensitive resin layer 20 and the substrate. Even when the resin layer 30 is interposed, the physical properties such as adhesion and resolution are greatly affected by the composition of the photosensitive resin layer 20 because the thickness of the second resin layer 30 is sufficiently small. . In addition, components may move between the photosensitive resin layer 20 and the second resin layer 30, and the composition of the photosensitive resin layer 20 also affects the second resin layer 30 that adheres to the base material. . Therefore, in the photosensitive refractive index adjusting film of the present embodiment, the second resin layer 30 is interposed between the base material and the photosensitive resin layer 20 because the photosensitive resin layer 20 has the specific composition described above. Even in such a case, the various effects described above can be obtained.
　第二の樹脂層３０の屈折率は、第二の樹脂層が単層で、厚さが厚さ方向で均一な場合、ＥＴＡ－ＴＣＭ（ＡｕｄｉｏＤｅｖＧｍｂＨ株式会社製、製品名）を用いて以下のように求めることができる。また、以下の測定は、２５℃の条件下で行う。
（１）第二の樹脂層を形成するための塗布液を、厚さ０．７ｍｍ、縦１０ｃｍ×横１０ｃｍのガラス基材上にスピンコーターで均一に塗布し、１００℃の熱風対流式乾燥機で３分間乾燥して溶剤を除去し、第二の樹脂層を形成する。
（２）次いで、１４０℃に加熱した箱型乾燥機（三菱電機株式会社製、型番：ＮＶ５０－ＣＡ）内に３０分間静置し、第二の樹脂層を有する屈折率測定用試料を得る。
（３）次いで、得られた屈折率測定用試料について、ＥＴＡ－ＴＣＭ（ＡｕｄｉｏＤｅｖＧｍｂＨ株式会社製、製品名）にて波長６３３ｎｍにおける屈折率を測定する。 In the case where the second resin layer is a single layer and the thickness is uniform in the thickness direction, the refractive index of the second resin layer 30 is determined as follows using ETA-TCM (manufactured by Audio Dev GmbH, product name). Can be sought. The following measurement is performed under the condition of 25 ° C.
(1) A coating solution for forming a second resin 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 by a spin coater, and a hot air convection dryer at 100 ° C. For 3 minutes to remove the solvent to form a second resin layer.
(2) Then, the sample is allowed to stand in a box-type dryer (manufactured by Mitsubishi Electric Corporation, model number: NV50-CA) heated to 140 ° C. for 30 minutes to obtain a refractive index measurement sample having a second resin layer.
(3) Next, the refractive index of the obtained refractive index measurement sample is measured at a wavelength of 633 nm by ETA-TCM (product name, manufactured by AudioDevGmbH).
　単層の感光性樹脂層における屈折率も同様の方法で測定することができる。なお、感光性屈折率調整フィルムの形態では、感光性樹脂層単層及び第二の樹脂層単層の屈折率を測定することは難しいが、感光性樹脂層の支持フィルム側の最表面層、又は第二の樹脂層の保護フィルム側の最表面層の値から推測することができる。 屈折 The refractive index of a single photosensitive resin layer can also be measured by the same method. In the form of the photosensitive refractive index adjusting film, it is difficult to measure the refractive index of the photosensitive resin layer single layer and the second resin layer single layer, but the outermost surface layer of the photosensitive resin layer on the support film side, Alternatively, it can be estimated from the value of the outermost surface layer on the protective film side of the second resin layer.
（他の層）
　本実施形態の感光性屈折率調整フィルムは、本発明の効果が得られる範囲で、適宜選択した他の層を設けてもよい。上記他の層としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、クッション層、酸素遮蔽層、剥離層、接着層等が挙げられる。上記感光性屈折率調整フィルムは、これらの層を１種単独で有していてもよく、２種以上を有してもよい。また、同種の層を２以上有していてもよい。 (Other layers)
The photosensitive refractive index adjusting film of the present embodiment may be provided with other appropriately selected layers as long as the effects of the present invention can be obtained. The other layer is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include a cushion layer, an oxygen shielding layer, a release layer, and an adhesive layer. The photosensitive refractive index adjusting film may have one of these layers alone, or may have two or more of these layers. Further, two or more layers of the same kind may be provided.
（保護フィルム）
　保護フィルム４０としては、例えばポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ポリカーボネート、ポリエチレン－酢酸ビニル共重合体、ポリエチレン－酢酸ビニル共重合体のフィルム、及び、これらのフィルムとポリエチレンの積層フィルム等が挙げられる。 (Protective film)
Examples of the protective film 40 include films of polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, polyethylene-vinyl acetate copolymer, polyethylene-vinyl acetate copolymer, and laminated films of these films and polyethylene.
　保護フィルム４０の厚さは、５～７０μｍが好ましいが、感光性フィルム１又は感光性屈折率調整フィルム２をロール状に巻いて保管する観点から、６０μｍ以下であることがより好ましく、５０μｍ以下であることが更に好ましく、４０μｍ以下であることが特に好ましい。 The thickness of the protective film 40 is preferably 5 to 70 μm, but is preferably 60 μm or less, more preferably 50 μm or less, from the viewpoint of winding and storing the photosensitive film 1 or the photosensitive refractive index adjusting film 2 in a roll shape. More preferably, it is particularly preferably 40 μm or less.
　感光性フィルム１及び感光性屈折率調整フィルム２において、支持フィルム１０及び保護フィルム４０の合計の厚さは、１００μｍ未満であることが必要であり、２０～８０μｍであることが好ましく、３０～７０μｍであることがより好ましく、４０～６０μｍであることが更に好ましい。この合計の厚さが１００μｍより大きいと、感光性フィルムロール１００において、上記長さＬ１の値が大きくなり過ぎ、それに伴って比（Ｌ１／Ｄ１）も過大となるため、比（Ｌ１／Ｄ１）が２５０以上であっても感光性樹脂層に打痕が生じる場合が起こり得る。そのため、感光性フィルムロール１００における打痕及び巻きズレを抑制する観点から、支持フィルム１０及び保護フィルム４０の合計の厚さは１００μｍ未満とする必要がある。 In the photosensitive film 1 and the photosensitive refractive index adjusting film 2, the total thickness of the support film 10 and the protective film 40 needs to be less than 100 μm, preferably 20 to 80 μm, and more preferably 30 to 70 μm. Is more preferable, and further preferably 40 to 60 μm. If the total thickness is larger than 100 μm, the value of the length L1 in the photosensitive film roll 100 becomes too large, and the ratio (L1 / D1) becomes too large. May be 250 or more, a dent may occur in the photosensitive resin layer. Therefore, the total thickness of the support film 10 and the protective film 40 needs to be less than 100 μm from the viewpoint of suppressing a dent and a winding deviation in the photosensitive film roll 100.
　感光性フィルム１における感光性樹脂層２０、又は、感光性屈折率調整フィルム２における感光性樹脂層２０及び第二の樹脂層３０を硬化させた硬化膜部分（支持フィルム１０及び保護フィルム４０を除く）の、波長４００～７００ｎｍの可視光領域における全光線透過率（Ｔｔ）の最小値は、９０．００％以上であることが好ましく、９０．５０％以上であることがより好ましく、９０．７０％以上であることが更に好ましい。一般的な可視光波長域である４００～７００ｎｍにおける全光線透過率が９０．００％以上であれば、タッチパネル（タッチセンサー）のセンシング領域の透明電極を保護する場合において、センシング領域での画像表示品質、色合い、輝度が低下することを充分抑制することができる。 A cured film portion obtained by curing the photosensitive resin layer 20 in the photosensitive film 1 or the photosensitive resin layer 20 and the second resin layer 30 in the photosensitive refractive index adjusting film 2 (excluding the support film 10 and the protective film 40). ), The minimum value of the total light transmittance (Tt) in the visible light region of a wavelength of 400 to 700 nm is preferably 90.00% or more, more preferably 90.50% or more, and 90.70. % Is more preferable. If the total light transmittance in the general visible light wavelength range of 400 to 700 nm is 90.00% or more, when protecting the transparent electrode in the sensing area of the touch panel (touch sensor), an image is displayed in the sensing area. It is possible to sufficiently suppress a decrease in quality, hue, and luminance.
＜感光性フィルム及び感光性屈折率調整フィルムの製造方法＞
　感光性屈折率調整フィルム２の感光性樹脂層２０、第二の樹脂層３０は、例えば、感光性樹脂組成物を含有する塗布液、及び第二の樹脂組成物を含有する塗布液を調製し、これを各々支持フィルム１０、保護フィルム４０上に塗布、乾燥することで形成できる。そして、感光性屈折率調整フィルム２は、感光性樹脂層２０が形成された支持フィルム１０と、第二の樹脂層３０が形成された保護フィルム４０とを、感光性樹脂層２０と第二の樹脂層３０とが対向した状態で貼り合わせることにより形成できる。また、感光性屈折率調整フィルム２は、支持フィルム１０上に感光性樹脂組成物を含有する塗布液を塗布、乾燥し、その後、感光性樹脂層２０上に、第二の樹脂組成物を含有する塗布液を塗布、乾燥し、保護フィルム４０を貼り付けることにより形成することもできる。一方、第二の樹脂層３０を有さない感光性フィルム１は、支持フィルム１０上に感光性樹脂組成物を含有する塗布液を塗布、乾燥し、その後、感光性樹脂層２０上に、保護フィルム４０を貼り付けることにより形成することができる。 <Method for producing photosensitive film and photosensitive refractive index adjusting film>
For the photosensitive resin layer 20 and the second resin layer 30 of the photosensitive refractive index adjusting film 2, for example, a coating solution containing a photosensitive resin composition and a coating solution containing the second resin composition are prepared. These can be formed by applying and drying these on the support film 10 and the protective film 40, respectively. Then, the photosensitive refractive index adjusting film 2 is formed by combining the support film 10 on which the photosensitive resin layer 20 is formed and the protective film 40 on which the second resin layer 30 is formed with the photosensitive resin layer 20 and the second resin layer 30. It can be formed by bonding together in a state where the resin layer 30 faces the resin layer 30. Further, the photosensitive refractive index adjusting film 2 is formed by applying a coating solution containing a photosensitive resin composition on the support film 10 and drying it, and then containing the second resin composition on the photosensitive resin layer 20. It can also be formed by applying a coating solution to be applied, drying and applying a protective film 40. On the other hand, the photosensitive film 1 without the second resin layer 30 is coated on the support film 10 with a coating solution containing the photosensitive resin composition, dried, and then protected on the photosensitive resin layer 20. It can be formed by attaching the film 40.
　塗布液は、感光性樹脂組成物、第二の樹脂組成物を構成する各成分を溶剤に均一に溶解又は分散することにより得ることができる。 The coating liquid can be obtained by uniformly dissolving or dispersing the components constituting the photosensitive resin composition and the second resin composition in a solvent.
　塗布液として用いる溶剤は、特に制限は無く、公知のものが使用できる。具体的には、アセトン、メチルエチルケトン、メチルイソブチルケトン、トルエン、メタノール、エタノール、プロパノール、ブタノール、メチレングリコール、エチレングリコール、プロピレングリコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールエチルメチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテル、エチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、クロロホルム、塩化メチレン等が挙げられる。 溶 剤 The solvent used as the coating liquid is not particularly limited, and a known solvent 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.
　塗布方法としては、ドクターブレードコーティング法、マイヤーバーコーティング法、ロールコーティング法、スクリーンコーティング法、スピナーコーティング法、インクジェットコーティング法、スプレーコーティング法、ディップコーティング法、グラビアコーティング法、カーテンコーティング法、ダイコーティング法等が挙げられる。 Application methods include doctor blade coating, Meyer bar coating, roll coating, screen coating, spinner coating, inkjet coating, spray coating, dip coating, gravure coating, curtain coating, and die coating. And the like.
　乾燥条件に特に制限は無いが、乾燥温度は、６０～１３０℃とすることが好ましく、乾燥時間は、０．５～３０分とすることが好ましい。 The drying conditions are not particularly limited, but the drying temperature is preferably from 60 to 130 ° C, and the drying time is preferably from 0.5 to 30 minutes.
＜感光性フィルムロールの製造方法＞
　本実施形態に係る感光性フィルムロールの製造方法は、長尺の上記感光性フィルム１を巻芯５０に巻き取って感光性フィルムロール１００を得る巻取工程を有し、支持フィルム１０及び保護フィルム４０の合計の厚さが１００μｍ未満であり、感光性フィルムロール１００を巻き出して測定される巻芯５０から１００周分の感光性フィルム１の長さＬ１と、巻芯の直径Ｄ１との比（Ｌ１／Ｄ１）が２５０～３２０となるように、巻取工程における巻き取りを行う方法である。なお、感光性フィルム１は、感光性屈折率調整フィルム２であってもよい。 <Method of manufacturing photosensitive film roll>
The method of manufacturing a photosensitive film roll according to the present embodiment includes a winding step of winding the long photosensitive film 1 around a core 50 to obtain a photosensitive film roll 100, and includes a support film 10 and a protective film. 40, the total thickness of which is less than 100 μm, and the ratio of the length L1 of the photosensitive film 1 for 100 turns from the core 50 measured by unwinding the photosensitive film roll 100 to the diameter D1 of the core. This is a method in which winding is performed in a winding step so that (L1 / D1) is 250 to 320. Note that the photosensitive film 1 may be a photosensitive refractive index adjusting film 2.
　感光性フィルム１の巻き取り方向（長尺方向）の長さは特に限定されないが、巻芯５０に１００周以上巻き取ることができる長さであることが必要であり、巻芯５０に２００周以上巻き取ることができる長さであることが好ましく、巻芯５０に５００～１０００周巻き取ることができる長さであることがより好ましい。感光性フィルム１の具体的な巻き取り方向の長さは、例えば、１００～１０００ｍであり、好ましくは２００～８００ｍであり、より好ましくは３００～５００ｍである。感光性フィルム１の巻き取り方向の長さが上記範囲内である場合、打痕及び巻きズレの発生を抑制する効果がより有効に奏される。 The length of the photosensitive film 1 in the winding direction (long direction) is not particularly limited, but it is necessary that the photosensitive film 1 can be wound 100 times or more around the winding core 50. The length is preferably such that it can be wound, and more preferably the length that can be wound 500 to 1000 times around the winding core 50. The specific length in the winding direction of the photosensitive film 1 is, for example, 100 to 1000 m, preferably 200 to 800 m, and more preferably 300 to 500 m. When the length of the photosensitive film 1 in the winding direction is within the above range, the effect of suppressing the occurrence of dents and winding deviation is more effectively achieved.
　感光性フィルム１の幅（巻き取り方向に垂直な方向の長さ）は特に限定されないが、通常、１０～１５００ｃｍであり、好ましくは２０～５００ｃｍであり、より好ましくは３０～１００ｃｍである。感光性フィルム１の幅が上記範囲内である場合、打痕及び巻きズレの発生を抑制する効果がより有効に奏される。 幅 The width of the photosensitive film 1 (the length in the direction perpendicular to the winding direction) is not particularly limited, but is usually 10 to 1500 cm, preferably 20 to 500 cm, and more preferably 30 to 100 cm. When the width of the photosensitive film 1 is in the above range, the effect of suppressing the occurrence of dents and winding deviation is more effectively exhibited.
　感光性フィルム１を全て巻き取った状態の感光性フィルムロール１００の直径は特に限定されないが、通常、５～１００ｃｍであり、好ましくは１０～５０ｃｍであり、より好ましくは１５～３０ｃｍである。感光性フィルムロール１００の直径が上記範囲内である場合、打痕及び巻きズレの発生を抑制する効果がより有効に奏される。 直径 The diameter of the photosensitive film roll 100 in a state where the photosensitive film 1 is completely wound up is not particularly limited, but is usually 5 to 100 cm, preferably 10 to 50 cm, more preferably 15 to 30 cm. When the diameter of the photosensitive film roll 100 is within the above range, the effect of suppressing the occurrence of dents and winding deviation is more effectively achieved.
　巻芯５０は、円筒状の巻芯である。巻芯５０の材質としては、例えば、紙管、木管、プラスチック管又は金属管等が挙げられるが、巻き取り時の加圧に耐え得る観点から金属管が好ましい。上記巻芯の材質がプラスチックの場合、該プラスチックとしては、例えば、ポリエチレン樹脂、ポリプロピレン樹脂、ポリスチレン樹脂、ポリ塩化ビニル樹脂、ＡＢＳ樹脂（アクリロニトリル－ブタジエン－スチレン共重合体）等が挙げられる。 The core 50 is a cylindrical core. Examples of the material of the core 50 include a paper tube, a wooden tube, a plastic tube, and a metal tube, but a metal tube is preferable from the viewpoint of being able to withstand the pressure during winding. When the material of the core is plastic, examples of the plastic include polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer).
　巻芯５０の直径Ｄ１は特に限定されないが、通常、１～５０ｃｍであり、好ましくは３～３０ｃｍであり、より好ましくは５～１０ｃｍである。巻芯５０の直径Ｄ１が上記範囲内である場合、打痕及び巻きズレの発生を抑制する効果がより有効に奏される。 直径 The diameter D1 of the core 50 is not particularly limited, but is usually 1 to 50 cm, preferably 3 to 30 cm, and more preferably 5 to 10 cm. When the diameter D1 of the core 50 is within the above range, the effect of suppressing the occurrence of dents and winding deviation is more effectively achieved.
　巻取工程では、比（Ｌ１／Ｄ１）が２５０～３２０となるように巻き取りを行う。比（Ｌ１／Ｄ１）に関して詳しくは、上記感光性フィルムロール１００の説明において述べた通りであり、その好ましい範囲も先に述べた通りである。 In the winding step, winding is performed so that the ratio (L1 / D1) becomes 250 to 320. Details of the ratio (L1 / D1) are as described in the description of the photosensitive film roll 100, and the preferable range is also as described above.
　また、巻取工程は、感光性フィルムロール１００を巻き出して測定される感光性フィルムロール１００の外側１００周分の感光性フィルム１の長さＬ２と、感光性フィルムロール１００の外側から１００周目の位置の直径Ｄ２との比（Ｌ２／Ｄ２）が２５０～３５０となるように、巻き取りを行うことが好ましい。比（Ｌ２／Ｄ２）に関して詳しくは、上記感光性フィルムロール１００の説明において述べた通りであり、その好ましい範囲も先に述べた通りである。 In addition, the winding step is performed by unwinding the photosensitive film roll 100 and measuring the length L2 of the photosensitive film 1 for 100 turns outside the photosensitive film roll 100 and 100 turns from the outside of the photosensitive film roll 100. Winding is preferably performed so that the ratio (L2 / D2) of the eye position to the diameter D2 is 250 to 350. The details of the ratio (L2 / D2) are as described in the description of the photosensitive film roll 100, and the preferable range is also as described above.
　比（Ｌ１／Ｄ１）及び比（Ｌ２／Ｄ２）の値は、例えば、巻き取り時の巻き取り張力を調整する方法、及び、感光性フィルム１の厚さ及び材質等を調整する方法などにより、所望の範囲とすることができる。 The values of the ratio (L1 / D1) and the ratio (L2 / D2) are determined by, for example, a method of adjusting the winding tension at the time of winding and a method of adjusting the thickness and the material of the photosensitive film 1 or the like. It can be in a desired range.
　巻き取り張力は、比（Ｌ１／Ｄ１）及び比（Ｌ２／Ｄ２）の値を上述した好ましい範囲内とする観点から、１２０～２２０Ｎ／ｍとすることが好ましく、１４０～２００Ｎ／ｍとすることがより好ましく、１６０～１８０Ｎ／ｍとすることが更に好ましい。 The winding tension is preferably from 120 to 220 N / m, and more preferably from 140 to 200 N / m, from the viewpoint of setting the values of the ratio (L1 / D1) and the ratio (L2 / D2) within the above-described preferable ranges. Is more preferable, and it is still more preferable to be 160 to 180 N / m.
　巻き取り張力は、巻き始めから巻き終わりまでの感光性フィルム１に対する張力が一定に保たれるように巻き径に応じて制御されていることが好ましいが、巻き取りの途中で張力を変化させてもよい。巻き取りの途中で張力を変化させる場合において、変化前後の巻き取り張力はいずれも上述した好ましい範囲内とすることが好ましい。 The winding tension is preferably controlled in accordance with the winding diameter so that the tension on the photosensitive film 1 from the start to the end of the winding is kept constant. However, the tension is changed during the winding. Is also good. When the tension is changed during winding, it is preferable that the winding tension before and after the change both fall within the above-described preferable range.
　感光性フィルム１を巻芯５０に巻き取る際、支持フィルム１０が外側になり、保護フィルム４０が巻芯５０側になるように巻き取ることが好ましい。 (4) When winding the photosensitive film 1 around the core 50, it is preferable that the support film 10 be on the outside and the protective film 40 be wound on the core 50 side.
　巻取工程後、感光性フィルムロール１００の端面には、端面保護の見地から端面セパレータを設置してもよい。端面セパレータとしては、耐エッジフュージョンの見地から防湿端面セパレータを用いることが好ましい。 After the winding step, an end face separator may be provided on the end face of the photosensitive film roll 100 from the viewpoint of end face protection. As the end face separator, it is preferable to use a moisture-proof end face separator from the viewpoint of edge fusion resistance.
　また、得られた感光性フィルムロール１００は、透湿性の小さいブラックシートに包んで包装し、保管することが好ましい。 Further, it is preferable that the obtained photosensitive film roll 100 is wrapped and stored in a black sheet having low moisture permeability.
　本実施形態に係る感光性フィルムロール１００は、タッチパネル等のセンシングデバイス用として用いられるものであり、例えば、センシングデバイスの透明電極及び金属配線等を保護するための保護膜の形成に用いられる。これらのセンシングデバイスにおいては、タッチ画面の高い視認性が求められるが、本実施形態に係る感光性フィルムロール１００は感光性樹脂層２０への打痕の発生が抑制されているため、打痕に起因した視認性の低下を抑制することができる。 The photosensitive film roll 100 according to the present embodiment is used for a sensing device such as a touch panel, and is used, for example, for forming a protective film for protecting a transparent electrode and a metal wiring of the sensing device. In these sensing devices, high visibility of the touch screen is required. However, since the photosensitive film roll 100 according to the present embodiment suppresses the occurrence of dents on the photosensitive resin layer 20, It is possible to suppress a decrease in visibility due to the above.
　図４は、本実施形態に係る感光性フィルムロール１００を用いて保護膜が形成されたタッチパネルの一実施形態を示す模式上面図である。図４には、静電容量式のタッチパネルの一例を示す。図４に示されるタッチパネルは、透明基材１０１の片面にタッチ位置座標を検出するためのタッチ画面１０２があり、この領域の静電容量変化を検出するための透明電極１０３及び透明電極１０４が透明基材１０１上に設けられている。 FIG. 4 is a schematic top view showing one embodiment of a touch panel on which a protective film is formed using the photosensitive film roll 100 according to the present embodiment. FIG. 4 illustrates an example of a capacitive touch panel. The touch panel shown in FIG. 4 has a touch screen 102 for detecting touch position coordinates on one surface of a transparent substrate 101, and a transparent electrode 103 and a transparent electrode 104 for detecting a change in capacitance in this area are transparent. It is provided on a substrate 101.
　透明電極１０３及び透明電極１０４はそれぞれタッチ位置のＸ位置座標及びＹ位置座標を検出する。 (4) The transparent electrode 103 and the transparent electrode 104 detect the X position coordinate and the Y position coordinate of the touch position, respectively.
　透明基材１０１上には、透明電極１０３及び透明電極１０４からタッチ位置の検出信号を外部回路に伝えるための引き出し配線１０５が設けられている。また、引き出し配線１０５と、透明電極１０３及び透明電極１０４とは、透明電極１０３及び透明電極１０４上に設けられた接続電極１０６により接続されている。また、引き出し配線１０５の透明電極１０３及び透明電極１０４との接続部と反対側の端部には、外部回路との接続端子１０７が設けられている。 (4) On the transparent base material 101, a lead wiring 105 for transmitting a detection signal of a touch position from the transparent electrode 103 and the transparent electrode 104 to an external circuit is provided. In addition, the lead wiring 105 is connected to the transparent electrode 103 and the transparent electrode 104 by a connection electrode 106 provided on the transparent electrode 103 and the transparent electrode 104. Further, a connection terminal 107 for connecting to an external circuit is provided at an end of the lead-out wiring 105 opposite to a connection portion with the transparent electrode 103 and the transparent electrode 104.
　透明基材１０１としては、例えばタッチパネル（タッチセンサー）に用いられる、ガラス板、プラスチック板、セラミック板等の基材が挙げられる。 As the transparent substrate 101, for example, a substrate such as a glass plate, a plastic plate, and a ceramic plate used for a touch panel (touch sensor) is exemplified.
　透明電極１０３，１０４は、例えばＩＴＯ及びＩＺＯ（Ｉｎｄｉｕｍ　Ｚｉｎｃ　Ｏｘｉｄｅ、酸化インジウム－酸化亜鉛）等の導電性金属酸化膜を用いて、形成することができる。また透明電極は、銀繊維及びカーボンナノチューブ等の導電性繊維を用いた光硬化性樹脂層を有する感光性フィルムを用いて、形成することもできる。 The transparent electrodes 103 and 104 can be formed using a conductive metal oxide film such as ITO and IZO (Indium Zinc Oxide, indium oxide-zinc oxide). Further, the transparent electrode can be formed using a photosensitive film having a photocurable resin layer using conductive fibers such as silver fibers and carbon nanotubes.
　引き出し配線１０５、接続電極１０６及び接続端子１０７としては、金属配線（金属端子）が用いられる。金属配線は、例えば、Ａｕ、Ａｇ、Ｃｕ、Ａｌ、Ｍｏ、Ｃ等の導電性材料を用いて、スクリーン印刷、蒸着等の方法により形成することができる。 金属 A metal wiring (metal terminal) is used as the lead wiring 105, the connection electrode 106, and the connection terminal 107. The metal wiring can be formed by using a conductive material such as Au, Ag, Cu, Al, Mo, or C by screen printing, vapor deposition, or the like.
　また、透明基材１０１上には、基材と電極との間に絶縁層又はインデックスマッチング層が設けられていてもよい。インデックスマッチング層は、上述した第二の樹脂層３０と同様の組成を有していてもよい。 In addition, an insulating layer or an index matching layer may be provided on the transparent base material 101 between the base material and the electrode. The index matching layer may have a composition similar to that of the second resin layer 30 described above.
　図４に示すように、本実施形態に係るタッチパネルにおいては、本実施形態に係る感光性フィルムロール１００から引き出された感光性フィルム１又は感光性屈折率調整フィルム２を用いて、透明電極パターンが形成された部分と、形成されていない部分にまたがって硬化膜パターン１２３が形成されている。硬化膜パターン１２３は、硬化した感光性樹脂層からなる硬化膜、又は、硬化した感光性樹脂層及び硬化した第二の樹脂層からなる硬化膜である。この硬化膜パターン１２３は、透明電極１０３、透明電極１０４、引き出し配線１０５、接続電極１０６及び接続端子１０７を保護する機能を有する。硬化膜パターン１２３が硬化した感光性樹脂層及び硬化した第二の樹脂層からなる硬化膜である場合、上述した保護機能と、透明電極パターンから形成されるセンシング領域（タッチ画面）１０２の骨見え現象防止機能とを同時に奏することができる。また、本実施形態に係る感光性フィルムロール１００を用いることで、打痕の発生が抑制された硬化膜を形成することができるため、タッチ画面の視認性を良好なものとすることができる。 As shown in FIG. 4, in the touch panel according to the present embodiment, the transparent electrode pattern is formed using the photosensitive film 1 or the photosensitive refractive index adjusting film 2 drawn from the photosensitive film roll 100 according to the present embodiment. A cured film pattern 123 is formed over the formed portion and the unformed portion. The cured film pattern 123 is a cured film composed of a cured photosensitive resin layer, or a cured film composed of a cured photosensitive resin layer and a cured second resin layer. The cured film pattern 123 has a function of protecting the transparent electrode 103, the transparent electrode 104, the lead wiring 105, the connection electrode 106, and the connection terminal 107. When the cured film pattern 123 is a cured film composed of the cured photosensitive resin layer and the cured second resin layer, the above-described protection function and the bone appearance of the sensing area (touch screen) 102 formed from the transparent electrode pattern are provided. The phenomenon prevention function can be performed at the same time. Further, by using the photosensitive film roll 100 according to the present embodiment, a cured film in which the occurrence of dents is suppressed can be formed, so that the visibility of the touch screen can be improved.
　以下、実施例を挙げて本発明についてより具体的に説明する。ただし、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
＜感光性樹脂組成物の作製＞
　表１に示す成分を、同表に示す配合量（単位：質量部）で配合し、攪拌機を用いて１５分間混合して感光性樹脂組成物を作製した。なお、感光性樹脂組成物は、メチルエチルケトンを適宜加えて、固形分が３５質量％となるように調製した。また、表１中、バインダーポリマーの配合量は固形分の配合量を示す。 <Preparation of photosensitive resin composition>
The components shown in Table 1 were blended in the blending amounts (unit: parts by mass) shown in the table, and mixed for 15 minutes using a stirrer to prepare a photosensitive resin composition. The photosensitive resin composition was prepared by appropriately adding methyl ethyl ketone so that the solid content was 35% by mass. In Table 1, the compounding amount of the binder polymer indicates the compounding amount of the solid content.
　表１中の各成分の詳細は以下の通りである。
〔（Ａ）成分〕
　バインダーポリマー：モノマー配合比（メタクリル酸／メタクリル酸メチル／アクリル酸メチル＝１２／５８／３０（質量比））である共重合体のプロピレングリコールモノメチルエーテル／トルエン溶液、重量平均分子量６５０００、酸価７８ｍｇＫＯＨ／ｇ
〔（Ｂ）成分〕
　光重合性化合物：ペンタエリスリトールテトラアクリレート（新中村化学工業株式会社製、製品名：Ａ－ＴＭＭＴ）
〔（Ｃ）成分〕
　光重合開始剤：１，２－オクタンジオン，１－［４－（フェニルチオ）フェニル－，２－（Ｏ－ベンゾイルオキシム）］（ＢＡＳＦ株式会社製、製品名：ＩＲＧＡＣＵＲＥ　ＯＸＥ　０１）
〔（Ｄ）成分〕
　防錆剤：５－アミノ－１Ｈ－テトラゾール（千代田ケミカル株式会社製、製品名：Ｂ－６０３０）
〔（Ｅ）成分〕
　密着助剤：エチレン性不飽和結合を含むリン酸エステル（日本化薬株式会社製、製品名：ＰＭ－２１）
〔その他の成分〕
　重合禁止剤：２，２’－メチレン－ビス（４－エチル－６－ｔｅｒｔ－ブチルフェノール）（川口化学工業株式会社製、製品名：ＡＷ５００）
　レベリング剤：オクタメチルシクロテトラシロキサン（東レ・ダウコーニング株式会社製、製品名：ＡＤＤＩＴＩＶＥ８０３２） Details of each component in Table 1 are as follows.
[(A) component]
Binder polymer: a propylene glycol monomethyl ether / toluene solution of a copolymer having a monomer mixing ratio (methacrylic acid / methyl methacrylate / methyl acrylate = 12/58/30 (mass ratio)), a weight average molecular weight of 65,000, and an acid value of 78 mg KOH / G
[(B) component]
Photopolymerizable compound: pentaerythritol tetraacrylate (Shin-Nakamura Chemical Co., Ltd., product name: A-TMMT)
[(C) component]
Photopolymerization initiator: 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)] (BASF Corporation, product name: IRGACURE OXE 01)
[(D) component]
Rust inhibitor: 5-amino-1H-tetrazole (product name: B-6030, manufactured by Chiyoda Chemical Co., Ltd.)
[(E) component]
Adhesion aid: phosphate ester containing ethylenically unsaturated bond (Nippon Kayaku Co., Ltd., product name: PM-21)
[Other components]
Polymerization inhibitor: 2,2'-methylene-bis (4-ethyl-6-tert-butylphenol) (manufactured by Kawaguchi Chemical Co., Ltd., product name: AW500)
Leveling agent: Octamethylcyclotetrasiloxane (manufactured by Dow Corning Toray Co., Ltd., product name: ADDITIVE8032)
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
（実施例１）
　コンマコーターを用いて、厚さ１６μｍのＰＥＴフィルム（支持フィルム、東レ株式会社製、製品名：ＦＢ４０）に感光性樹脂組成物を均一に塗布した後、熱風対流式乾燥機を用いて１００℃で３分間乾燥させて溶剤を除去することにより感光性樹脂層を形成した。感光性樹脂層の乾燥後の厚さは８μｍであった。次いで、厚さ３０μｍのポリプロピレンフィルム（保護フィルム、王子エフテックス株式会社製、製品名：Ｅ－２０１Ｆ）を感光性樹脂層に貼り付けることにより、支持フィルム、感光性樹脂層及び保護フィルムがこの順で積層された長尺の転写型感光性フィルム（全長３００ｍ、幅５３ｃｍ）を得た。この感光性フィルムを、巻き取り機（株式会社ゴードーキコー製、製品名：ＧＤＳＬＩＴＴＥＲ５３７Ａ）を用いて巻き取り張力１８０Ｎ／ｍで巻芯（ＡＢＳコア、東都積水株式会社製、外径８．４ｃｍ）に巻き取ることにより、感光性フィルムロールを得た。 (Example 1)
Using a comma coater, the photosensitive resin composition was uniformly applied to a 16 μm-thick PET film (support film, product name: FB40, manufactured by Toray Industries, Inc.) and then heated at 100 ° C. using a hot air convection dryer. After drying for 3 minutes to remove the solvent, a photosensitive resin layer was formed. The thickness of the photosensitive resin layer after drying was 8 μm. Then, a 30 μm-thick polypropylene film (protective film, manufactured by Oji F-Tex Co., Ltd., product name: E-201F) is attached to the photosensitive resin layer, so that the support film, the photosensitive resin layer, and the protective film are in this order. To obtain a long transfer type photosensitive film (total length 300 m, width 53 cm) laminated. This photosensitive film is wound around a winding core (ABS core, manufactured by Toto Sekisui Co., outer diameter 8.4 cm) with a winding tension of 180 N / m using a winding machine (manufactured by Gordoki Co., Ltd., product name: GDSLITTER537A). This was taken to obtain a photosensitive film roll.
（実施例２）
　保護フィルムを厚さ１６μｍのＰＥＴフィルム（東レ株式会社製、製品名：ＦＢ４０）に変更したこと以外は実施例１と同様にして長尺の転写型感光性フィルムを得た。この感光性フィルムを実施例１と同じ条件で巻芯に巻き取ることにより、感光性フィルムロールを得た。 (Example 2)
A long transfer type photosensitive film was obtained in the same manner as in Example 1 except that the protective film was changed to a PET film having a thickness of 16 μm (manufactured by Toray Industries, Inc., product name: FB40). The photosensitive film was wound around a core under the same conditions as in Example 1 to obtain a photosensitive film roll.
（実施例３）
　保護フィルムを厚さ２０μｍのポリエチレンフィルム（タマポリ株式会社製、製品名：ＮＦ－１５）に変更したこと以外は実施例１と同様にして長尺の転写型感光性フィルムを得た。この感光性フィルムを実施例１と同じ条件で巻芯に巻き取ることにより、感光性フィルムロールを得た。 (Example 3)
A long transfer type photosensitive film was obtained in the same manner as in Example 1 except that the protective film was changed to a polyethylene film having a thickness of 20 μm (manufactured by Tamapoly Corporation, product name: NF-15). The photosensitive film was wound around a core under the same conditions as in Example 1 to obtain a photosensitive film roll.
（実施例４）
　感光性樹脂層の乾燥後の厚さを１５μｍとしたこと以外は実施例１と同様にして長尺の転写型感光性フィルムを得た。この感光性フィルムを実施例１と同じ条件で巻芯に巻き取ることにより、感光性フィルムロールを得た。 (Example 4)
A long transfer photosensitive film was obtained in the same manner as in Example 1 except that the thickness of the photosensitive resin layer after drying was 15 μm. The photosensitive film was wound around a core under the same conditions as in Example 1 to obtain a photosensitive film roll.
（比較例１）
　実施例１と同様にして長尺の転写型感光性フィルムを得た。この感光性フィルムを、巻き取り機（株式会社ゴードーキコー製、製品名：ＧＤＳＬＩＴＴＥＲ５３７Ａ）を用いて巻き取り張力２２０Ｎ／ｍで巻芯（ＡＢＳコア、東都積水株式会社製、外径８．４ｃｍ）に巻き取ることにより、感光性フィルムロールを得た。 (Comparative Example 1)
In the same manner as in Example 1, a long transfer type photosensitive film was obtained. This photosensitive film is wound around a winding core (ABS core, manufactured by Toto Sekisui Co., outer diameter 8.4 cm) with a winding tension of 220 N / m using a winding machine (manufactured by Gordoki Co., Ltd., product name: GDSLITTER537A). This was taken to obtain a photosensitive film roll.
（比較例２）
　実施例１と同様にして長尺の転写型感光性フィルムを得た。この感光性フィルムを、巻き取り機（株式会社ゴードーキコー製、製品名：ＧＤＳＬＩＴＴＥＲ５３７Ａ）を用いて巻き取り張力１４０Ｎ／ｍで巻芯（ＡＢＳコア、東都積水株式会社製、外径８．４ｃｍ）に巻き取ることにより、感光性フィルムロールを得た。 (Comparative Example 2)
In the same manner as in Example 1, a long transfer type photosensitive film was obtained. This photosensitive film is wound around a winding core (ABS core, manufactured by Toto Sekisui Co., Ltd., outer diameter 8.4 cm) at a winding tension of 140 N / m using a winding machine (manufactured by Gordoki Co., Ltd., product name: GDSLITTER537A). This was taken to obtain a photosensitive film roll.
（比較例３）
　支持フィルムを厚さ５０μｍのＰＥＴフィルム（東洋紡株式会社製、製品名：Ａ４１００）に変更し、保護フィルムを厚さ５０μｍのＰＥＴフィルム（東洋紡株式会社製、製品名：Ａ４１００）に変更し、感光性フィルムの全長を２００ｍに変更したこと以外は実施例１と同様にして長尺の転写型感光性フィルムを得た。この感光性フィルムを実施例１と同じ条件で巻芯に巻き取ることにより、感光性フィルムロールを得た。 (Comparative Example 3)
The support film was changed to a 50 μm-thick PET film (manufactured by Toyobo Co., Ltd., product name: A4100), and the protective film was changed to a 50 μm-thick PET film (manufactured by Toyobo Co., product name: A4100). A long transfer type photosensitive film was obtained in the same manner as in Example 1 except that the total length of the film was changed to 200 m. The photosensitive film was wound around a core under the same conditions as in Example 1 to obtain a photosensitive film roll.
（比較例４）
　実施例１と同様にして長尺の転写型感光性フィルムを得た。この感光性フィルムを、巻き取り機（株式会社ゴードーキコー製、製品名：ＧＤＳＬＩＴＴＥＲ５３７Ａ）を用いて巻芯（ＡＢＳコア、東都積水株式会社製、外径８．４ｃｍ）に、巻き取り張力１２０Ｎ／ｍで１５０ｍ巻き取り、その後、巻き取り張力１３０Ｎ／ｍで１５０ｍ巻き取ることにより、感光性フィルムロールを得た。 (Comparative Example 4)
In the same manner as in Example 1, a long transfer type photosensitive film was obtained. This photosensitive film was wound on a winding core (ABS core, manufactured by Toto Sekisui Co., Ltd., outer diameter 8.4 cm) with a winding tension of 120 N / m using a winding machine (product name: GDSLITTER537A, manufactured by Gordoki Co., Ltd.). The photosensitive film roll was obtained by winding 150 m and then winding 150 m at a winding tension of 130 N / m.
＜巻きズレの評価＞
　実施例及び比較例で得られた感光性フィルムロールについて、金尺を用いて、一方のロール端面における最も出っ張っている部分から最も引っ込んでいる部分までのロール端面に垂直な方向の幅を、ズレ幅として測定した。測定したズレ幅を用いて、下記の評価基準に基づき、巻きズレを評価した。結果を表２に示す。
Ａ：ズレ幅が５ｍｍ未満
Ｂ：ズレ幅が５ｍｍ以上１０ｍｍ以下
Ｃ：ズレ幅が１０ｍｍ超 <Evaluation of winding deviation>
For the photosensitive film rolls obtained in the examples and the comparative examples, the width in the direction perpendicular to the roll end surface from the most protruding portion to the most retracted portion on one roll end surface is shifted using a gold scale. Measured as width. Using the measured deviation width, winding deviation was evaluated based on the following evaluation criteria. Table 2 shows the results.
A: The deviation width is less than 5 mm B: The deviation width is 5 mm or more and 10 mm or less C: The deviation width is more than 10 mm
＜打痕の評価＞
　異物が混入した状況を意図的に作り出すために、感光性フィルムを５０ｍ巻き取った時に３００μｍ角、厚さ３０μｍのＰＥＴ樹脂片を混入させたこと以外は各実施例及び比較例と同様にして、打痕評価用の感光性フィルムロールを作製した。混入させた樹脂片に接している上下２枚の感光性フィルムを感光性フィルムロールから切り取った。切り取った感光性フィルムをＰＥＴフィルム上に、保護フィルムを剥離して感光性樹脂層側がＰＥＴフィルムに接するようにラミネートした。その後、感光性樹脂層に対して支持フィルムを介して、平行光露光機（オーク製作所製、製品名：ＥＸＭ－１２０１）を用いて露光量８０Ｊ／ｍ２で紫外線を照射した。その後、支持フィルムを剥離し、レーザー顕微鏡（レーザーテック株式会社製、製品名：ハイブリッドレーザーマイクロスコープ　ＯＰＴＥＬＩＣＳ）にて感光性樹脂層表面における打痕の凹凸の深さを測定した。測定した凹凸の深さの最大値を用いて、下記の評価基準に基づき、打痕の評価を行った。結果を表２に示す。また、図５に、比較例１の感光性樹脂層に生じた打痕の観察結果を示す。図５の（ａ）は打痕のレーザー顕微鏡写真であり、図５の（ｂ）は打痕の凹凸の高さ（深さ）及び幅を示すグラフである。図５の（ａ）中の点ａ，ｂ，ｃと、図５の（ｂ）中の点ａ，ｂ，ｃとは、それぞれ同じ地点を示す。
Ａ：凹凸深さが０．５μｍ以下
Ｂ：凹凸深さが０．５μｍ超 <Evaluation of dents>
In order to intentionally create a situation in which foreign matter was mixed, a 300 μm square, 30 μm thick PET resin piece was mixed when the photosensitive film was wound 50 m, in the same manner as in each Example and Comparative Example, A photosensitive film roll for dent evaluation was prepared. Two upper and lower photosensitive films in contact with the mixed resin piece were cut from the photosensitive film roll. The cut photosensitive film was laminated on a PET film so that the protective film was peeled off and the photosensitive resin layer side was in contact with the PET film. Thereafter, the photosensitive resin layer was irradiated with ultraviolet rays through a supporting film using a parallel light exposure machine (manufactured by Oak Manufacturing Co., Ltd., product name: EXM-1201) at an exposure amount of 80 J / m 2 . Thereafter, the support film was peeled off, and the depth of the unevenness of the dent on the surface of the photosensitive resin layer was measured with a laser microscope (manufactured by Lasertec Corporation, product name: Hybrid Laser Microscope OPTELICS). Using the measured maximum value of the depth of the unevenness, the dents were evaluated based on the following evaluation criteria. Table 2 shows the results. FIG. 5 shows the results of observation of dents formed in the photosensitive resin layer of Comparative Example 1. FIG. 5A is a laser microscope photograph of the dent, and FIG. 5B is a graph showing the height (depth) and width of the dent and projection. Points a, b, and c in FIG. 5A and points a, b, and c in FIG. 5B respectively indicate the same point.
A: The unevenness depth is 0.5 μm or less B: The unevenness depth is more than 0.5 μm
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
１…感光性フィルム、２…感光性屈折率調整フィルム、１０…支持フィルム、２０…感光性樹脂層、３０…第二の樹脂層、４０…保護フィルム、５０…巻芯、１００…感光性フィルムロール、１０１…透明基材、１０２…センシング領域、１０３，１０４…透明電極、１０５…引き出し配線、１０６…接続電極、１０７…接続端子、１２３…硬化膜パターン（硬化膜）。
  DESCRIPTION OF SYMBOLS 1 ... photosensitive film, 2 ... photosensitive refractive index adjustment film, 10 ... support film, 20 ... photosensitive resin layer, 30 ... second resin layer, 40 ... protective film, 50 ... core, 100 ... photosensitive film Roll, 101: Transparent substrate, 102: Sensing area, 103, 104: Transparent electrode, 105: Lead wiring, 106: Connection electrode, 107: Connection terminal, 123: Cured film pattern (cured film).

Claims (8)

  1. 　支持フィルムと、前記支持フィルム上に配置された感光性樹脂層と、前記感光性樹脂層上に配置された保護フィルムと、を備える長尺の感光性フィルムをロール状に巻き取った、センシングデバイス用感光性フィルムロールの製造方法であって、
    　前記感光性フィルムを巻芯に巻き取って感光性フィルムロールを得る巻取工程を有し、
    　前記支持フィルム及び前記保護フィルムの合計の厚さが１００μｍ未満であり、
    　前記感光性フィルムロールを巻き出して測定される前記巻芯から１００周分の感光性フィルムの長さＬ１と、前記巻芯の直径Ｄ１との比（Ｌ１／Ｄ１）が２５０～３２０となるように、前記巻取工程における巻き取りを行う、感光性フィルムロールの製造方法。     A sensing device in which a long photosensitive film including a support film, a photosensitive resin layer disposed on the support film, and a protective film disposed on the photosensitive resin layer is wound up in a roll shape. A method for producing a photosensitive film roll for
    A winding step of winding the photosensitive film around a core to obtain a photosensitive film roll,
    The total thickness of the support film and the protective film is less than 100 μm,
    The ratio (L1 / D1) of the length L1 of the photosensitive film for 100 turns from the core measured by unwinding the photosensitive film roll to the diameter D1 of the core is 250 to 320. And a winding method in the winding step.
  2. 　前記感光性フィルムロールを巻き出して測定される前記感光性フィルムロールの外側１００周分の感光性フィルムの長さＬ２と、前記感光性フィルムロールの外側から１００周目の位置の直径Ｄ２との比（Ｌ２／Ｄ２）が２５０～３５０となるように、前記巻取工程における巻き取りを行う、請求項１に記載の感光性フィルムロールの製造方法。 The length L2 of the photosensitive film for 100 turns outside the photosensitive film roll measured by unwinding the photosensitive film roll, and the diameter D2 at the position of the 100th turn from the outside of the photosensitive film roll. The method for producing a photosensitive film roll according to claim 1, wherein the winding in the winding step is performed so that the ratio (L2 / D2) is 250 to 350.
  3. 　前記感光性フィルムロールの巻き数が５００～１０００周である、請求項１又は２に記載の感光性フィルムロールの製造方法。 3. The method for producing a photosensitive film roll according to claim 1, wherein the number of turns of the photosensitive film roll is 500 to 1000 turns.
  4. 　前記感光性フィルムが、前記感光性樹脂層と前記保護フィルムとの間に配置された金属酸化物粒子を含有する第二の樹脂層を更に備える、請求項１～３のいずれか一項に記載の感光性フィルムロールの製造方法。 4. The photosensitive film according to claim 1, wherein the photosensitive film further includes a second resin layer containing metal oxide particles disposed between the photosensitive resin layer and the protective film. Of producing a photosensitive film roll.
  5. 　支持フィルムと、前記支持フィルム上に配置された感光性樹脂層と、前記感光性樹脂層上に配置された保護フィルムと、を備える長尺の感光性フィルムを巻芯にロール状に巻き取った、センシングデバイス用感光性フィルムロールであって、
    　前記支持フィルム及び前記保護フィルムの合計の厚さが１００μｍ未満であり、
    　前記感光性フィルムロールを巻き出して測定される前記巻芯から１００周分の感光性フィルムの長さＬ１と、前記巻芯の直径Ｄ１との比（Ｌ１／Ｄ１）が２５０～３２０である、感光性フィルムロール。     A long photosensitive film including a support film, a photosensitive resin layer disposed on the support film, and a protective film disposed on the photosensitive resin layer was wound into a roll around a core. , A photosensitive film roll for a sensing device,
    The total thickness of the support film and the protective film is less than 100 μm,
    The ratio (L1 / D1) of the length L1 of the photosensitive film for 100 turns from the core measured by unwinding the photosensitive film roll to the diameter D1 of the core is 250 to 320. Photosensitive film roll.
  6. 　前記感光性フィルムロールを巻き出して測定される前記感光性フィルムロールの外側１００周分の感光性フィルムの長さＬ２と、前記感光性フィルムロールの外側から１００周目の位置の直径Ｄ２との比（Ｌ２／Ｄ２）が２５０～３５０である、請求項５に記載の感光性フィルムロール。 The length L2 of the photosensitive film for 100 turns outside the photosensitive film roll measured by unwinding the photosensitive film roll, and the diameter D2 at the position of the 100th turn from the outside of the photosensitive film roll. The photosensitive film roll according to claim 5, wherein the ratio (L2 / D2) is from 250 to 350.
  7. 　前記感光性フィルムロールの巻き数が５００～１０００周である、請求項５又は６に記載の感光性フィルムロール。 The photosensitive film roll according to claim 5, wherein the number of turns of the photosensitive film roll is 500 to 1000 turns.
  8. 　前記感光性フィルムが、前記感光性樹脂層と前記保護フィルムとの間に配置された金属酸化物粒子を含有する第二の樹脂層を更に備える、請求項５～７のいずれか一項に記載の感光性フィルムロール。 The photosensitive resin film according to any one of claims 5 to 7, further comprising a second resin layer containing metal oxide particles disposed between the photosensitive resin layer and the protective film. Photosensitive film roll.
PCT/JP2018/026575 2018-07-13 2018-07-13 Method for manufacturing photosensitive film roll for sensing device, and photosensitive film roll for sensing device WO2020012651A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022264275A1 (en) * 2021-06-15 2022-12-22 昭和電工マテリアルズ株式会社 Photosensitive element and method for producing photosensitive element

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006011548A1 (en) * 2004-07-30 2006-02-02 Hitachi Chemical Company, Ltd. Photosensitive film, photosensitive film laminate and photosensitive film roll
JP2018506450A (en) * 2014-12-30 2018-03-08 スリーエム イノベイティブ プロパティズ カンパニー Web winding roll having microsphere-treated edge and method for producing the same
JP2018045126A (en) * 2016-09-15 2018-03-22 日立化成株式会社 Photosensitive film for vacuum lamination, transfer type photosensitive refractive index adjusting film, and method for forming cured resin pattern
JP6299940B1 (en) * 2017-03-31 2018-03-28 日立化成株式会社 Photosensitive element and photosensitive element roll

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006011548A1 (en) * 2004-07-30 2006-02-02 Hitachi Chemical Company, Ltd. Photosensitive film, photosensitive film laminate and photosensitive film roll
JP2018506450A (en) * 2014-12-30 2018-03-08 スリーエム イノベイティブ プロパティズ カンパニー Web winding roll having microsphere-treated edge and method for producing the same
JP2018045126A (en) * 2016-09-15 2018-03-22 日立化成株式会社 Photosensitive film for vacuum lamination, transfer type photosensitive refractive index adjusting film, and method for forming cured resin pattern
JP6299940B1 (en) * 2017-03-31 2018-03-28 日立化成株式会社 Photosensitive element and photosensitive element roll

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022264275A1 (en) * 2021-06-15 2022-12-22 昭和電工マテリアルズ株式会社 Photosensitive element and method for producing photosensitive element

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