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WO2018179096A1 - Film photosensible de type transfert, procédé de formation d'un motif de film durci, et panneau tactile - Google Patents

Film photosensible de type transfert, procédé de formation d'un motif de film durci, et panneau tactile Download PDF

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Publication number
WO2018179096A1
WO2018179096A1 PCT/JP2017/012680 JP2017012680W WO2018179096A1 WO 2018179096 A1 WO2018179096 A1 WO 2018179096A1 JP 2017012680 W JP2017012680 W JP 2017012680W WO 2018179096 A1 WO2018179096 A1 WO 2018179096A1
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WO
WIPO (PCT)
Prior art keywords
resin layer
group
type photosensitive
meth
transfer type
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2017/012680
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English (en)
Japanese (ja)
Inventor
和仁 渡部
匠 渡邊
向　郁夫
攻治 安部
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Corp
Original Assignee
Hitachi Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Priority to JP2019508391A priority Critical patent/JP6943279B2/ja
Priority to KR1020197028867A priority patent/KR102401215B1/ko
Priority to CN201780089039.7A priority patent/CN110462559A/zh
Priority to PCT/JP2017/012680 priority patent/WO2018179096A1/fr
Publication of WO2018179096A1 publication Critical patent/WO2018179096A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2012—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image using liquid photohardening compositions, e.g. for the production of reliefs such as flexographic plates or stamps
    • G—PHYSICS
    • G06—COMPUTING OR CALCULATING; COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means

Definitions

  • the present invention relates to a transfer type photosensitive film, a method for forming a cured film pattern, and a touch panel.
  • a projected capacitive touch panel In general, in a projected capacitive touch panel, a plurality of X electrodes and a plurality of Y electrodes orthogonal to the X electrodes have a two-layer structure in order to express two-dimensional coordinates based on the X and Y axes. Forming. As a material for these electrodes, ITO (Indium-Tin-Oxide) is the mainstream.
  • a metal wiring such as copper is formed in the frame region in order to transmit a touch position detection signal.
  • a corrosive component such as moisture or salt may enter the sensing region from the inside when touching the fingertip.
  • the metal wiring corrodes, and there is a risk of an increase in electrical resistance between the electrode and the driving circuit, or disconnection.
  • a photosensitive resin composition layer containing a di (meth) acrylate compound having a dicyclopentanyl structure or a dicyclopentenyl structure is provided on a touch panel substrate, and this photosensitive resin composition
  • touch panels in which electrodes are provided on a flexible substrate may be used.
  • This touch panel is subjected to processing such as punching or cutting with a flat plate punching machine or a rotary cutter in order to improve productivity.
  • the cured film pattern provided on the touch panel is required to have crack resistance that does not easily cause cracks even after the above-described steps.
  • An object of the present invention is to provide a transfer type photosensitive film capable of forming a cured film pattern having both low moisture permeability and crack resistance, a cured film pattern forming method using the same, and a touch panel. .
  • the present inventors have intensively studied, and in the photosensitive resin layer containing a binder polymer, a photopolymerizable compound, and a photopolymerization initiator, as a copolymerization component, branched and / or alicyclic rings. It has been found that a cured film pattern having low moisture permeability can be formed by using a binder polymer containing a monomer having a structure and a monomer having an acidic group. On the other hand, the present inventors have also obtained the knowledge that the above-mentioned cured film pattern tends to decrease the crack resistance.
  • the compound having the functional group capable of reacting with the acidic group and the ethylenically unsaturated group is converted into an ethylenically unsaturated group equivalent of the binder polymer. It has been found that a cured film pattern that achieves both low moisture permeability and crack resistance can be formed by further reacting in such a way as to satisfy a specific range, and the present invention has been completed.
  • the present invention comprises a support film and a first resin layer provided on the support film, and the first resin layer contains a binder polymer, a photopolymerizable compound, and a photopolymerization initiator.
  • the binder polymer contains a group having a branched and / or alicyclic structure in the side chain, a group having an acidic group in the side chain, and a group having an ethylenically unsaturated group in the side chain;
  • a transfer type photosensitive film having an ethylenically unsaturated group equivalent of 50 to 3.00 (mmol / g).
  • a cured film pattern having both low moisture permeability and crack resistance can be formed by having the above configuration.
  • the cured film pattern formed on the metal wiring can function as a protective film for rust prevention of the metal wiring.
  • the reason why the above effect is obtained is that by adding a group having a branched and / or alicyclic structure in the side chain of the binder polymer, a bulky structure is added to reduce the moisture permeability of the cured film. It is considered that forming such a low moisture-permeable cured film pattern on the metal wiring makes it difficult for the moisture that causes corrosion to come into contact with the metal wiring.
  • a group having an ethylenically unsaturated group in the side chain of the binder polymer and adjusting the ethylenically unsaturated group equivalent of the binder polymer to a specific range the distance between cross-linking points in the cured film becomes longer. It is considered that flexibility was improved and crack resistance was compatible.
  • the binder polymer may further contain a group having a phenyl group in the side chain.
  • the first resin layer may further contain a phosphoric ester having an ethylenically unsaturated group.
  • a protective film capable of highly suppressing corrosion of metal wiring for example, rust of copper wiring
  • metal wiring for example, rust of copper wiring
  • the photopolymerization initiator may contain an oxime ester compound.
  • the transfer type photosensitive film has high sensitivity, and the moisture permeability of the formed cured film pattern can be further reduced.
  • the transfer type photosensitive film according to the present invention can further include a second resin layer containing metal oxide particles provided on the first resin layer.
  • the projected capacitive touch panel has a two-layer structure on a substrate by a plurality of X electrodes using a transparent electrode material and a plurality of Y electrodes using a transparent electrode material orthogonal to the X electrodes. It has a structure in which a transparent electrode pattern is formed.
  • a color difference becomes large due to a difference in optical reflection characteristics between a portion where the transparent electrode pattern is formed and a portion where the transparent electrode pattern is not formed.
  • OCA Optical Clear Adhesive
  • the transfer type photosensitive film having the second resin layer according to the present invention According to the transfer type photosensitive film having the second resin layer according to the present invention, the above problem can be suppressed.
  • the first resin layer of the transfer type photosensitive film according to the present invention is adhered to the substrate having electrodes, and the side on which the electrodes of the substrate are provided and the first resin layer are in close contact with each other. And a step of laminating the first resin layer on the substrate so as to remove a portion other than the predetermined portion and forming a cured film covering a part or all of the electrode.
  • a first method for forming a cured film pattern is provided.
  • the second resin layer and the first resin layer of the transfer type photosensitive film according to the present invention having the second resin layer are provided on the substrate having the electrode. Laminating the second side and the second resin layer in close contact with each other, and exposing the second resin layer and the predetermined portion of the first resin layer on the base material, then removing other than the predetermined portion, Forming a cured film pattern that covers a part or all of the electrode, and a second method for forming a cured film pattern.
  • the first and second methods for forming a cured film pattern according to the present invention it is possible to form a cured film pattern having both low moisture permeability and crack resistance on the electrode.
  • the cured film pattern can have a function of adjusting the refractive index, and suppress the above-described problems of bone appearance phenomenon and screen transmittance decrease. be able to.
  • the present invention also provides a cured film obtained by curing the first resin layer in the transfer type photosensitive film according to the present invention.
  • the present invention is also obtained by curing only the first resin layer or both the first resin layer and the second resin layer of the transfer type photosensitive film according to the present invention having the second resin layer. Provide a cured film.
  • the present invention also provides a cured product of the first resin layer in the transfer type photosensitive film according to the present invention or a second resin layer of the transfer type photosensitive film according to the present invention having a second resin layer.
  • a touch panel provided with a cured film pattern comprising a cured product of the above and a cured product of a first resin layer is provided.
  • the transfer type photosensitive film which can form the cured film pattern which makes low moisture permeability and crack tolerance compatible, the formation method of a cured film pattern using the same, and a touch panel can be provided. .
  • (meth) acrylic acid means acrylic acid or methacrylic acid
  • (meth) acrylate means acrylate or a corresponding methacrylate.
  • a or B only needs to include one of A and B, or may include both.
  • the term “layer” includes a structure formed in a part in addition to a structure formed in the entire surface when observed as a plan view.
  • the term “process” is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term “process” is used as long as the intended action of the process is achieved. included.
  • the numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • each component in the composition is the sum of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means quantity.
  • the exemplary materials may be used alone or in combination of two or more unless otherwise specified.
  • the upper limit value or lower limit value of a numerical range of a certain step may be replaced with the upper limit value or lower limit value of the numerical range of another step.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
  • the transfer type photosensitive film of the present embodiment comprises a support film and a first resin layer provided on the support film.
  • the transfer type photosensitive film of the present embodiment may further include a second resin layer containing metal oxide particles provided on the first resin layer.
  • These transfer type photosensitive films may further include a protective film provided on the first resin layer or the second resin layer.
  • FIG. 1 is a schematic sectional view showing a transfer type photosensitive film according to an embodiment of the present invention.
  • the transfer type photosensitive film 1 shown in FIG. 1 includes a support film 10, a first resin layer 20 provided on the support film 10, and a second resin layer provided on the first resin layer. 30 and a protective film 40 provided on the second resin layer 30.
  • the transfer-type photosensitive film for example, a cured film satisfying both functions of protecting the metal wiring on the frame of the touch panel or the transparent electrode of the touch panel, and making the transparent electrode pattern invisible or improving the visibility of the touch screen. Patterns can be formed in a batch.
  • a polymer film As the support film 10, a polymer film can be used.
  • the material for the polymer film include polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, polyethersulfone, and cycloolefin polymer.
  • the thickness of the support film 10 is preferably 5 to 100 ⁇ m, preferably 10 to 70 ⁇ m, from the viewpoint of ensuring coverage and suppressing the reduction in resolution when irradiated with actinic rays through the support film 10. Is more preferably 15 to 40 ⁇ m, and particularly preferably 15 to 35 ⁇ m.
  • the first resin layer 20 includes a binder polymer (hereinafter also referred to as (A) component), a photopolymerizable compound (hereinafter also referred to as (B) component), and a photopolymerization initiator (hereinafter referred to as (C) component). It is preferably formed from a photosensitive resin composition containing
  • the component (A) includes a group having a branched structure and / or an alicyclic structure in the side chain (hereinafter also referred to as (i) group), and a group having an acidic group in the side chain (hereinafter referred to as (ii) And a binder polymer (hereinafter also referred to as component (A-1)) containing a group having an ethylenically unsaturated group in the side chain (hereinafter also referred to as (iii) group).
  • the group can be introduced by a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain.
  • the group can be introduced by a monomer containing a group having an acidic group in the side chain.
  • the monomer containing a group having a branched structure in the side chain include, for example, i-propyl (meth) acrylate, i-butyl (meth) acrylate, s-butyl (meth) acrylate, and (meth) acrylic.
  • acrylic acid 3- examples include octyl and (meth) acrylic acid t-octyl.
  • i-propyl (meth) acrylate, i-butyl (meth) acrylate, and t-butyl methacrylate are preferable, and i-propyl methacrylate and t-butyl methacrylate are more preferable.
  • the monomer containing a group having an alicyclic structure in the side chain include (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. More specific examples include, for example, (meth) acrylic acid (bicyclo [2.2.1] heptyl-2), (meth) acrylic acid-1-adamantyl, (meth) acrylic acid-2-adamantyl, ) -3-methyl-1-adamantyl acrylate, 3,5-dimethyl-1-adamantyl (meth) acrylate, 3-ethyladamantyl (meth) acrylate, 3-methyl-5 (meth) acrylate -Ethyl-1-adamantyl, (meth) acrylic acid-3,5,8-triethyl-1-adamantyl, (meth) acrylic acid-3,5-dimethyl-8-ethyl-1-adamantyl, (meth) acrylic acid 2-methyl-2-adamantyl, 2-ethyl
  • cyclohexyl (meth) acrylic acid, (nor) bornyl (meth) acrylic acid, isobornyl (meth) acrylic acid, (meth) acrylic acid-1-adamantyl, (meth) acrylic acid- 2-adamantyl, phentyl (meth) acrylate, 1-menthyl (meth) acrylate, and tricyclodecane (meth) acrylate are preferred, cyclohexyl (meth) acrylate, (nor) bornyl (meth) acrylate, (meth) ) Isobornyl acrylate, 2-adamantyl (meth) acrylate, and tricyclodecane (meth) acrylate are particularly preferred.
  • the moisture permeability of the formed cured film pattern can be sufficiently reduced.
  • the monomer containing a group having an acidic group in the side chain can be appropriately selected from known ones.
  • the component (A-1) contains a group having an acidic group in the side chain
  • patterning by alkali development can be performed. Further, introduction of a group having an ethylenically unsaturated group in the side chain and adjustment of the ethylenically unsaturated group equivalent in the binder polymer are facilitated.
  • the group having an ethylenically unsaturated group in the side chain is not particularly limited, and a (meth) acryloyl group is preferable.
  • the connection between the ethylenically unsaturated group and the monomer is not particularly limited as long as it is a divalent linking group such as an ester group, an amide group, or a carbamoyl group.
  • the method of introducing an ethylenically unsaturated group into the side chain can be appropriately selected from known methods.
  • a method of adding a (meth) acrylate having an epoxy group to a group having an acidic group, a hydroxy group It can be introduced into the component (A-1) by a method of adding a (meth) acrylate having an isocyanate group to a group having a group, a method of adding a (meth) acrylate having a hydroxy group to a group having an isocyanate group, or the like.
  • the method of adding a (meth) acrylate having an epoxy group to a repeating unit having an acidic group is preferred because it is the easiest to produce and is low in cost.
  • the crack resistance of the formed cured film pattern can be sufficiently improved.
  • the ratio of the monomers constituting the group having a branched structure and / or alicyclic structure in the side chain is preferably 10 to 70 mol%, It is more preferably 65 mol%, particularly preferably 20 to 60 mol%.
  • the ratio of the monomer constituting the group having an acidic group in the side chain based on the total amount of the monomer constituting the component (A-1) is preferably 5 to 70 mol%, and 10 to 60 mol%. More preferred is 20 to 50 mol%.
  • the ratio of the monomer constituting the group having an ethylenically unsaturated group in the side chain based on the total amount of the monomer constituting the component (A-1) is preferably 5 to 70 mol%. It is more preferably mol%, more preferably 20 to 50 mol%.
  • the ethylenically unsaturated group equivalent of the component (A-1) is 0.50 to 3.00 mmol / g from the viewpoint of achieving both low moisture permeability and crack resistance of the cured film pattern. Preferably, it is 1.00 to 3.00 mmol / g, more preferably 1.50 to 3.00 mmol / g.
  • the ethylenically unsaturated group equivalent can be measured by a titration method using the addition reaction (Michael addition) of an amine to the ethylenically unsaturated group of the (meth) acryloyl group of the binder polymer.
  • the specific measurement method is as follows.
  • the binder polymer solution is heated at 130 ° C. for 1 hour to remove volatile components to obtain a solid content.
  • About 1 g of a sample is precisely weighed and placed in an Erlenmeyer flask, and then about 10 ml of acetone is added and dissolved.
  • Ethylenically unsaturated group equivalent (mmol / g) f ⁇ (AB) / 2S
  • A is a titration (ml) of a 0.5 mol / L acetic acid / methanol titration solution required for titration of the sample
  • B is a 0.5 mol / L acetic acid / methanol titration solution required for a blank test.
  • f is a factor (concentration conversion factor) of 0.5 mol / L acetic acid / methanol titration solution
  • S is sampled amount (g) [if sample contains solvent, amount excluding solvent ( g)].
  • Component (A-1) is a group other than the group having a branched structure and / or alicyclic structure in the side chain, a group having an acidic group in the side chain, and a group having an ethylenically unsaturated group in the side chain. Structural units derived from other groups can be contained.
  • the component (A-1) is preferably a copolymer containing a structural unit derived from (meth) acrylic acid and (meth) acrylic acid alkyl ester. In this case, the copolymer is the above (meth)
  • the structural unit may contain other monomers that can be copolymerized with acrylic acid and (meth) acrylic acid alkyl ester.
  • Examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid-2-ethylhexyl ester, (meth) acrylic And acid hydroxyl ethyl ester.
  • Other monomers are preferably compounds having a phenyl group.
  • the compound having a phenyl group include phenylbenzyl (meth) acrylate, phenoxybenzyl (meth) acrylate, nonylphenoxypolyethylene glycol acrylate, ethoxylated o-phenylphenol acrylate, and benzyl (meth) acrylate.
  • benzyl (meth) acrylate From the viewpoint of reducing the moisture permeability of the cured film, it is preferable to use benzyl (meth) acrylate.
  • the binder polymer contains a group having a phenyl group in the side chain, a bulky structure is added, so that the moisture permeability of the cured film is reduced.
  • Other monomers also include (meth) acrylic acid glycidyl ester, styrene and the like.
  • the component (A-1) is a (meth) acrylic acid tricyclodecane ester or (meth) acrylic acid cyclohexyl ester as a group (i) from the viewpoint of forming a cured film pattern having both low moisture permeability and crack resistance.
  • the weight average molecular weight of the component (A-1) is preferably 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. 000 is more preferable, 30,000 to 100,000 is particularly preferable, and 40,000 to 100,000 is very preferable.
  • a weight average molecular weight can be measured by the gel permeation chromatography method described in the Example of this specification.
  • the acid value of the component (A-1) is preferably 75 mgKOH / g or more from the viewpoint of easily forming a cured film (cured film pattern) having a desired shape by alkali development. From the viewpoint of achieving both controllability of the cured film shape and rust prevention of the cured film, the acid value of the component (A-1) is preferably 75 to 200 mgKOH / g, and preferably 75 to 150 mgKOH / g. g is more preferable, and 75 to 120 mgKOH / g is further more preferable.
  • an acid value can be measured by the method described in the Example of this specification.
  • the first resin layer 20 may further contain a binder polymer other than the component (A-1) described above.
  • the content ratio of the component (A-1) in the component (A) is preferably 60 to 100% by mass, more preferably 70 to 100% by mass based on the total amount of the component (A). Preferably, it is 80 to 100% by mass.
  • a photopolymerizable compound having an ethylenically unsaturated group can be used as the component (B).
  • the photopolymerizable compound having an ethylenically unsaturated group include a monofunctional vinyl monomer having one polymerizable ethylenically unsaturated group in the molecule and two polymerizable ethylenically unsaturated groups in the molecule.
  • Bifunctional vinyl monomers or polyfunctional vinyl monomers having at least three polymerizable ethylenically unsaturated groups in the molecule can be mentioned.
  • Examples of the monofunctional vinyl monomer having one polymerizable ethylenically unsaturated group in the molecule include those exemplified as monomers used for the synthesis of a copolymer which is a preferred example of the component (A). Can be mentioned.
  • the bifunctional vinyl monomer having two polymerizable ethylenically unsaturated groups in the molecule includes a compound having a tricyclodecane skeleton or a tricyclodecene skeleton from the viewpoint of reducing the moisture permeability of the cured film. preferable. From the viewpoint of inhibiting corrosion of the metal wiring and transparent electrode pattern, it is preferable that the compound having a tricyclodecane skeleton or a tricyclodecene skeleton includes a di (meth) acrylate compound represented by the following general formula (B-1). .
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group
  • X represents a divalent group having a tricyclodecane skeleton or a tricyclodecene skeleton
  • R 3 and R 4 each independently represents an alkylene group having 1 to 4 carbon atoms
  • n and m each independently represents an integer of 0 to 2
  • p and q each independently represents an integer of 0 or more.
  • P + q 0 to 10 is selected.
  • R 3 and R 4 are preferably an ethylene group or a propylene group, and more preferably an ethylene group.
  • the propylene group may be either an n-isopropylene group or an isopropylene group.
  • the divalent group having a tricyclodecane skeleton or a tricyclodecene skeleton contained in X has a bulky structure, so that the cured film has a low viscosity. Moisture permeability can be realized, and the corrosion resistance of the metal wiring and the transparent electrode can be improved.
  • tricyclodecane skeleton and “tricyclodecene skeleton” in the present specification refer to the following structures (where each bond is an arbitrary position).
  • a 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.).
  • the proportion of the compound having a tricyclodecane skeleton or a tricyclodecene skeleton is, among the total amount of 100 parts by mass of the photopolymerizable compound contained in the photosensitive resin composition, from the viewpoint of reducing moisture permeability. , 50 parts by mass or more, preferably 70 parts by mass or more, and more preferably 80 parts by mass or more.
  • a bifunctional vinyl monomer having two polymerizable ethylenically unsaturated groups in the molecule, other than a compound having a tricyclodecane skeleton or a tricyclodecene skeleton includes polyethylene glycol di (meth) acrylate and trimethylolpropane. Examples 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 conventionally known ones can be used without particular limitation.
  • the polyfunctional vinyl monomer includes 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 the following skeleton: bones derived from dipentaerythritol such
  • the polyfunctional vinyl monomer includes a (meth) acrylate compound having a skeleton derived from pentaerythritol, a (meth) acrylate compound having a skeleton derived from dipentaerythritol, and a (meth) acrylate having a skeleton derived from trimethylolpropane. It is more preferable to include a compound, a (meth) acrylate compound having a skeleton derived from ditrimethylolpropane, or a (meth) acrylate compound having a skeleton derived from cyanuric acid. Among these, it is preferable to use a (meth) acrylate compound having a skeleton derived from ditrimethylolpropane because the crack resistance of the cured film can be improved.
  • (meth) acrylate compound having a skeleton derived from will be described by taking a (meth) acrylate compound having a skeleton derived from ditrimethylolpropane as an example.
  • (Meth) acrylate having a skeleton derived from ditrimethylolpropane means an esterified product of ditrimethylolpropane and (meth) acrylic acid, and the esterified product includes a compound modified with an alkyleneoxy group.
  • the esterified product preferably has a maximum number of 4 ester bonds in one molecule, but a compound having 1 to 3 ester bonds may be mixed.
  • the component (B) is a compound having a tricyclodecane skeleton or a tricyclodecene skeleton, ditrimethylolpropane tetra (meth) acrylate, or the like. It is preferable to include one or more of (meth) acrylate compounds having a skeleton derived from ditrimethylolpropane.
  • the content of the component (A) and the component (B) is preferably 35 to 85 parts by mass of the component (A) with respect to 100 parts by mass of the total amount 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.
  • a conventionally known photopolymerization initiator can be used without any particular limitation, but a highly transparent photopolymerization initiator is preferably used.
  • the component (C) preferably contains an oxime ester compound and / or a phosphine oxide compound in that a cured resin film pattern can be formed with sufficient resolution even on a substrate with a thickness of 10 ⁇ m or less.
  • the phosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
  • the oxime ester compound is preferably a compound represented by the following general formula (1), a compound represented by the following general formula (2), or a compound represented by the following general formula (3).
  • R 11 and R 12 each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group or a tolyl group, and having 1 to 8 carbon atoms
  • An alkyl group, a cycloalkyl group having 4 to 6 carbon atoms, a phenyl group or a tolyl group is preferable, and an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms, a phenyl group or a tolyl group is preferable.
  • R 13 represents —H, —OH, —COOH, —O (CH 2 ) OH, —O (CH 2 ) 2 OH, —COO (CH 2 ) OH or —COO (CH 2 ) 2 OH; It is preferably H, —O (CH 2 ) OH, —O (CH 2 ) 2 OH, —COO (CH 2 ) OH, or —COO (CH 2 ) 2 OH, and —H, —O (CH 2 ) 2 OH or —COO (CH 2 ) 2 OH is more preferable.
  • R 14 each independently represents an alkyl group having 1 to 6 carbon atoms, and is preferably a propyl group.
  • R 15 represents NO 2 or ArCO (wherein Ar represents an aryl group), and Ar is preferably a tolyl group.
  • R 16 and R 17 each independently represent an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group, preferably a methyl group, a phenyl group, or a tolyl group.
  • R 18 represents an alkyl group having 1 to 6 carbon atoms, and is preferably an ethyl group.
  • R 19 is an organic group having an acetal bond, and is preferably a substituent corresponding to R 19 in a compound represented by the formula (3-1) described later.
  • R 20 and R 21 each independently represents an alkyl group having 1 to 12 carbon atoms, a phenyl group or a tolyl group, preferably a methyl group, a phenyl group or a tolyl group, and more preferably a methyl group.
  • R 22 represents a hydrogen atom or an alkyl group.
  • the compound represented by the above general formula (1) is available as IRGACURE OXE 01 (product name, manufactured by BASF Corporation).
  • the compound represented by the general formula (2) is available as DFI-091 (product name, manufactured by Daito Chemix Co., Ltd.).
  • the compound represented by the general formula (3) is available as Adekaoptomer N-1919 (product name, manufactured by ADEKA Corporation).
  • the content of the component (C) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B) in terms of excellent photosensitivity and resolution. It is more preferably from 8 to 8 parts by mass, further preferably from 1 to 6 parts by mass, and particularly preferably from 1 to 4 parts by mass.
  • the photosensitive resin composition according to this 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 prevention property of the cured film. It is preferable to further contain 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 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, etc. , 3-mercaptotriazole, 5-mercaptotriazole, and other triazole compounds containing a mercapto group are substituted with amino groups.
  • tetrazole compounds having an amino group examples include 5-amino-1H-tetrazole, 1-methyl-5-amino-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, and 1-carboxymethyl-5-amino-tetrazole.
  • Etc. These tetrazole compounds may be water-soluble salts thereof. Specific examples include alkali metal salts of 1-methyl-5-amino-tetrazole such as sodium, potassium and lithium.
  • the content thereof is preferably 0.05 to 5.0 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). 0.1 to 2.0 parts by mass is more preferable, 0.2 to 1.0 part by mass is further preferable, and 0.3 to 0.8 part by mass is particularly preferable.
  • the photosensitive resin composition according to the present embodiment has adhesiveness to a transparent electrode such as a substrate and an ITO electrode that may have an index matching layer, and good developability on a metal wiring such as a copper wiring. From the viewpoint of forming a cured film that has been achieved at a high level, and from the viewpoint of preventing the occurrence of development residue, it further contains a phosphate ester containing an ethylenically unsaturated group (hereinafter also referred to as component (E)). Is preferred.
  • Unichemical Corporation has a high level of compatibility between the adhesion to the base material and the ITO electrode and the developability on the metal wiring while ensuring sufficient rust prevention of the cured film to be formed.
  • the company's Phosmer series (Phosmer-M, Phosmer-CL, Phosmer-PE, Phosmer-MH, Phosmer-PP, etc.) or KAYAMER series (PM-21, PM-2, etc.) manufactured by Nippon Kayaku Co., Ltd. are preferred. .
  • the content is the component (A) from the viewpoint of achieving both high adhesion to the base material and the ITO electrode and developability on the metal wiring.
  • an adhesion imparting agent such as a silane coupling agent, a rust inhibitor, a leveling agent, A plasticizer, a filler, an antifoaming agent, a flame retardant, a stabilizer, an antioxidant, a fragrance, a thermal crosslinking agent, a polymerization inhibitor, etc. are each added to 100 parts by mass of the total amount of the component (A) and the component (B). About 0.01 to 20 parts by mass can be contained. These can be used alone or in combination of two or more.
  • the thickness of the first resin layer may be 1 to 15 ⁇ m, preferably 2 to 10 ⁇ m, more preferably 3 to 8 ⁇ m, still more preferably 4 to 6 ⁇ m, and 5 to 6 ⁇ m. It is particularly preferred that When the thickness is 1 to 15 ⁇ m, there are few defects at the time of coating, and film formation with excellent transparency is possible.
  • the thickness of the first resin layer after curing (that is, the thickness of the cured film pattern) is also preferably within the above range.
  • the second resin layer 30 is a layer containing metal oxide particles.
  • the second resin layer 30 can have a refractive index relatively higher than that of the first resin layer 20 by containing metal oxide particles.
  • the second resin layer 30 preferably has a refractive index in the range of 1.40 to 1.90 at 633 nm, more preferably 1.50 to 1.90, and 1.53 to 1.85. More preferably, it is particularly preferably 1.55 to 1.75.
  • the refractive index in 633 nm of the 2nd resin layer after hardening is also in the said range.
  • various members used on the cured film pattern when the cured film pattern is provided on a transparent electrode pattern such as ITO. It becomes an intermediate value of the refractive index of the cover glass and the OCA that bonds the transparent electrode pattern to the transparent electrode pattern, and is optical in the portion where the transparent electrode pattern such as ITO is formed and the portion where it is not formed. It is possible to reduce the color difference due to reflection and prevent the appearance of bone. Moreover, it becomes possible to reduce the reflected light intensity of the whole screen, and to suppress the transmittance
  • the refractive index of a transparent electrode such as ITO is preferably 1.80 to 2.10, more preferably 1.85 to 2.05, and even more preferably 1.90 to 2.00.
  • the refractive index of a member such as OCA is preferably 1.45 to 1.55, more preferably 1.47 to 1.53, and further preferably 1.48 to 1.51. .
  • the second resin layer 30 preferably has a minimum light transmittance of 80% or more in a wavelength region of 450 to 650 nm, more preferably 85% or more, and further preferably 90% or more.
  • the minimum light transmittance in the wavelength region of 450 to 650 nm of the second resin layer after curing is also within the above range.
  • the 2nd resin layer 30 can contain said (A) component, (B) component, and (C) component, and said (D) component and / or said (E) component as needed. Can further be contained.
  • the second resin layer 30 does not necessarily contain a photopolymerization component such as the component (B) or the component (C), and the second resin layer is formed by utilizing a photopolymerization component that migrates from an adjacent resin layer due to layer formation. The layer 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.
  • the metal oxide particles include particles made of metal oxides such as zirconium oxide, titanium oxide, tin oxide, zinc oxide, indium tin oxide, indium oxide, aluminum oxide, and yttrium oxide. Among these, particles of zirconium oxide or titanium oxide are preferable from the viewpoint of suppressing the bone appearance phenomenon.
  • the zirconium oxide particles when the material of the transparent electrode is ITO, it is preferable to use zirconium oxide nanoparticles from the viewpoint of improving the refractive index and adhesion between the ITO and the transparent substrate.
  • the particle size distribution Dmax is preferably 40 nm or less.
  • Zirconium oxide nanoparticles are OZ-S30K (product name, manufactured by Nissan Chemical Industries, Ltd.), OZ-S40K-AC (product name, manufactured by Nissan Chemical Industries, Ltd.), SZR-K (dispersion of zirconium oxide methyl ethyl ketone, Sakai Chemical). Kogyo Co., Ltd., product name) and SZR-M (zirconium oxide methanol dispersion, Sakai Chemical Industry Co., Ltd., product name) are commercially available.
  • the second resin layer 30 may contain titanium oxide nanoparticles as the component (F).
  • the particle size distribution Dmax is preferably 50 nm or less, more preferably 10 to 50 nm.
  • oxide particles or sulfide particles containing atoms such as Mg, Al, Si, Ca, Cr, Cu, Zn, and Ba can be used. These can be used alone or in combination of two or more.
  • organic compounds such as a compound having a triazine ring, a compound having an isocyanuric acid skeleton, and a compound having a fluorene skeleton can also be used.
  • the refractive index in wavelength 633nm can be improved.
  • the thickness of the 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 from 0.07 to 0.25 ⁇ m, particularly preferably from 0.05 to 0.2 ⁇ m. When the thickness is 0.01 to 1 ⁇ m, the reflected light intensity of the entire screen can be further reduced. Moreover, it is preferable that the thickness of the 2nd resin layer after hardening is also in the said range.
  • the refractive index of the second resin layer 30 is as follows using ETA-TCM (product name, manufactured by AudioDev GmbH). Can be requested. The following measurement is performed under the condition of 25 ° C. (1) A coating solution for forming the 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 residence type dryer at 100 ° C. Dry for 3 minutes to remove the solvent and form a second resin layer. (2) Next, the sample is allowed to stand for 30 minutes in a box dryer (model number: NV50-CA, manufactured by Mitsubishi Electric Corporation) heated to 140 ° C.
  • a box dryer model number: NV50-CA, manufactured by Mitsubishi Electric Corporation
  • the refractive index in the single first resin layer can also be measured by the same method.
  • the value of the outermost surface layer on the protective film side of the second resin layer is used.
  • the transfer type photosensitive film of this embodiment may be provided with other appropriately selected layers as long as the effects of the present invention are obtained.
  • the transfer type photosensitive film may have these layers individually by 1 type, and may have 2 or more types. Moreover, you may have 2 or more of the same kind of layers.
  • Examples of the protective film 40 include polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, a polyethylene-vinyl acetate copolymer, a polyethylene-vinyl acetate copolymer film, and a laminated film of these films and polyethylene.
  • the thickness of the protective film 40 is preferably 5 to 100 ⁇ m, but from the viewpoint of storing the transfer type photosensitive film 1 in a roll shape, it is preferably 70 ⁇ m or less, more preferably 60 ⁇ m or less, and 50 ⁇ m or less. More preferably, it is particularly preferably 40 ⁇ m or less.
  • the minimum value of the light transmittance (Tt) is preferably 90.00% or more, more preferably 90.50% or more, and further preferably 90.70% or more. If the total light transmittance in a 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), image display in the sensing area It can suppress sufficiently that quality, a hue, and a brightness
  • the total light transmittance (Tt) in the visible light region can be measured by the method described in the examples of this specification.
  • the first resin layer 20 and the second resin layer 30 of the transfer type photosensitive film 1 are prepared, for example, by preparing a first resin layer forming coating solution and a second resin layer forming coating solution. It can form by apply
  • the transfer type photosensitive film 1 includes a support film 10 on which the first resin layer 20 is formed and a protective film 40 on which the second resin layer 30 is formed. It can form by pasting together in the state which opposed resin layer 30 of this.
  • the transfer type photosensitive film 1 is formed by applying and drying a first resin layer forming coating solution on the support film 10, and then forming a second resin layer forming coating solution on the first resin layer 20. Can be formed by applying, drying, and attaching the protective film 40.
  • the coating liquid can be obtained by uniformly dissolving or dispersing each component constituting the photosensitive resin composition according to the present embodiment and the second resin layer in a solvent.
  • the solvent used as the coating solution is not particularly limited, and known ones can be used. Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, methanol, ethanol, propanol, butanol, methylene glycol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether , Diethylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, chloroform, methylene chloride and the like.
  • Application methods include doctor blade coating method, Mayer bar coating method, roll coating method, screen coating method, spinner coating method, inkjet coating method, spray coating method, dip coating method, gravure coating method, curtain coating method, and die coating method. Etc.
  • the drying conditions are not particularly limited, but the drying temperature is preferably 60 to 130 ° C., and the drying time is preferably 0.5 to 30 minutes.
  • FIG. 2 is a schematic cross-sectional view showing a laminate comprising a cured film formed using a transfer type photosensitive film according to an embodiment of the present invention on a substrate with a transparent electrode pattern.
  • the laminated body 100 shown by FIG. 2 is provided with the base material 50 with the transparent electrode pattern which has the transparent electrode pattern 50a, and the cured film 60 provided on the transparent electrode pattern 50a of the base material 50 with a transparent electrode pattern.
  • the cured film 60 is a cured film composed of the cured first resin layer 22 and the cured second resin layer 32, and is formed using the transfer type photosensitive film 1 of the present embodiment.
  • the cured film 60 satisfies both the protective function of the transparent electrode pattern 50a and the function of making the transparent electrode pattern 50a invisible or improving the visibility of the touch screen.
  • an embodiment of a method for producing a laminate in which a cured film is formed on a substrate with a transparent electrode pattern will be described.
  • the pressing means include a pressing roll.
  • the pressure roll may be provided with a heating means so that it can be heat-pressure bonded.
  • the heating temperature is such that the components of the first resin layer 20 or the second resin layer 30 are heated from the viewpoint of adhesion between the second resin layer 30 and the substrate 50 with the transparent electrode pattern. From the viewpoint of making it hard to be cured or thermally decomposed, it is preferably 10 to 160 ° C, more preferably 20 to 150 ° C, and further preferably 30 to 150 ° C.
  • the pressing pressure at the time of thermocompression bonding is a line from the viewpoint of suppressing the deformation of the substrate 50 with the transparent electrode pattern while ensuring sufficient adhesion between the second resin layer 30 and the substrate 50 with the transparent electrode pattern.
  • the pressure is preferably 50 to 1 ⁇ 10 5 N / m, more preferably 2.5 ⁇ 10 2 to 5 ⁇ 10 4 N / m, and 5 ⁇ 10 2 to 4 ⁇ 10 4 N / m. More preferably.
  • the pre-heat treatment of the substrate 50 with a transparent electrode pattern is not necessarily required, but the second resin layer 30 and the substrate 50 with a transparent electrode pattern are in close contact with each other. From the point of further improving the property, the substrate 50 with a transparent electrode pattern may be preheated.
  • the treatment temperature at this time is preferably 30 to 150 ° C.
  • Base material As a base material which comprises the base material 50 with a transparent electrode pattern, base materials, such as a glass plate used for a touch panel (touch sensor), a plastic plate, a ceramic board, are mentioned, for example.
  • the transparent electrode can be formed using a conductive metal oxide film such as ITO and IZO (Indium Zinc Oxide).
  • the transparent electrode can also be formed using a photosensitive film having a photocurable resin layer using conductive fibers such as silver fibers and carbon nanotubes.
  • the metal wiring can be formed by a method such as screen printing or vapor deposition using a conductive material such as Au, Ag, Cu, Al, Mo, and C, for example.
  • an insulating layer or an index matching layer may be provided on the base material between the base material and the electrode.
  • the index matching layer may have the same composition as the second resin layer 30 described above.
  • actinic rays are irradiated in a pattern form to a predetermined portion of the first resin layer and the second resin layer after transfer via a photomask.
  • the support film 10 on the first resin layer and the second resin layer is transparent when irradiating with actinic light, it can be irradiated with actinic light as it is. Irradiate light.
  • a known active light source can be used as the active light source.
  • the pattern in this specification is not limited to the shape of the fine wiring that forms the circuit, but also includes the shape in which only the connection portion with the other base material is removed in a rectangular shape and the shape in which only the frame portion of the base material is removed. It is.
  • the irradiation amount of actinic rays is 1 ⁇ 10 2 to 1 ⁇ 10 4 J / m 2 , and heating can be accompanied during irradiation. If the irradiation amount of this actinic ray is 1 ⁇ 10 2 J / m 2 or more, it is possible to sufficiently proceed the photocuring of the first resin layer and the second resin layer, and 1 ⁇ 10 4 J If it is / m 2 or less, there is a tendency that the first resin layer and the second resin layer can be prevented from being discolored.
  • the unexposed portions of the first resin layer and the second resin layer after irradiation with actinic rays are removed with a developer, and a cured film (refractive index adjustment pattern) 60 covering a part or all of the transparent electrode is obtained.
  • a cured film (refractive index adjustment pattern) 60 covering a part or all of the transparent electrode is obtained.
  • the image development process is performed.
  • the development step can be performed by a known method such as spraying, showering, rocking dipping, brushing, or scrubbing using a known developer such as an aqueous alkaline solution, an aqueous developer, or an organic solvent.
  • spray development is preferably performed using an alkaline aqueous solution from the viewpoint of environment and safety.
  • the development temperature and time can be adjusted within a conventionally known range.
  • the cured film pattern is formed using the transfer type photosensitive film having the second resin layer.
  • the same method is used when using the transfer type photosensitive film not having the second resin layer.
  • a cured film pattern can be formed.
  • the cured film according to the present invention may be a cured film obtained by curing the first resin layer and the second resin layer of the transfer photosensitive film of the present embodiment. For example, when most of the second resin layer is covered with the first resin layer and is not exposed, the second resin layer does not necessarily need to be cured.
  • the cured film according to the present invention includes such a case that the first resin layer is cured and the second resin layer is not cured.
  • the cured film according to the present invention is preferably formed in a pattern.
  • the cured film according to the present invention may be a cured film obtained by curing the first resin layer when the transfer type photosensitive film does not have the second resin layer.
  • the transfer type photosensitive film according to this embodiment can be applied to the formation of a protective film in various electronic parts.
  • the electronic component according to this embodiment includes a cured film pattern formed using a transfer type photosensitive film. Examples of the electronic component include a touch sensor, a touch panel, a liquid crystal display, an organic electroluminescence, a solar cell module, a printed wiring board, and electronic paper.
  • the touch sensor can include the laminate 100 shown in FIG.
  • OCA that adheres the cover glass and the laminate 100 can be used.
  • FIG. 3 is a schematic top view showing a touch panel according to an embodiment of the present invention.
  • FIG. 3 shows an example of a capacitive touch panel.
  • the touch panel shown in FIG. 3 has a touch screen 102 for detecting a touch position coordinate on one side of a transparent substrate 101, and the transparent electrode 103 and the transparent electrode 104 for detecting a change in capacitance in this region are transparent. It is provided on the base material 101.
  • the transparent electrode 103 and the transparent electrode 104 detect the X position coordinate and the Y position coordinate of the touch position, respectively.
  • a lead-out wiring 105 for transmitting a touch position detection signal from the transparent electrode 103 and the transparent electrode 104 to an external circuit is provided.
  • the lead-out 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.
  • a connection terminal 107 for connecting to an external circuit is provided at the end of the lead-out wiring 105 opposite to the connection portion between the transparent electrode 103 and the transparent electrode 104.
  • a cured film pattern is formed across the portion where the transparent electrode pattern is formed and the portion where the transparent electrode pattern is not formed, using the transfer type photosensitive film of the present embodiment.
  • 123 is formed.
  • the cured film pattern 123 includes a cured first resin layer and a cured second resin layer.
  • the cured film pattern 123 consists of a hardened 1st resin layer.
  • the cured film pattern 123 the function of protecting the transparent electrode 103, the transparent electrode 104, the lead-out wiring 105, the connection electrode 106 and the connection terminal 107, and the bone of the sensing region (touch screen) 102 formed from the transparent electrode pattern A visual phenomenon prevention function can be performed at the same time.
  • the cured film pattern 123 can have a sufficiently small step on the surface.
  • Binder polymer solutions 2 to 5 and 8 (all having a solid content of 45% by mass) were obtained in the same manner as in the binder polymer solution 1 except that the blending amount was changed as shown in Table 1.
  • the weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC), and was derived by conversion using a standard polystyrene calibration curve.
  • GPC gel permeation chromatography
  • the acid value was measured by a neutralization titration method based on JIS K0070 as shown below. First, the binder polymer solution was heated at 130 ° C. for 1 hour to remove volatile matter, thereby obtaining a solid content. Then, after accurately weighing 1 g of the solid binder polymer, 30 g of acetone was added to the binder polymer, and this was uniformly dissolved to obtain a resin solution. Next, an appropriate amount of an indicator, phenolphthalein, was added to the resin solution, and neutralization titration was performed using a 0.1 mol / L potassium hydroxide aqueous solution. And the acid value was computed by following Formula.
  • Acid value 0.1 ⁇ V ⁇ f 1 ⁇ 56.1 / (Wp ⁇ I / 100)
  • V is a titration amount (mL) of 0.1 mol / L potassium hydroxide aqueous solution used for titration
  • f 1 is a factor (concentration conversion factor) of 0.1 mol / L potassium hydroxide aqueous solution
  • Wp represents the mass (g) of the measured resin solution
  • I represents the proportion (mass%) of the non-volatile content in the measured resin solution.
  • the components shown in Table 3 or 4 were blended in the blending amounts (unit: parts by mass) shown in the same table and mixed for 15 minutes using a stirrer to prepare a second coating solution for forming a resin layer.
  • the blending amount of the binder polymer solution 10 indicates the blending amount of the solid content.
  • the first resin layer-forming coating solution prepared above is uniformly applied on the support film using a comma coater.
  • the solvent was removed by drying with a hot air convection dryer at 100 ° C. for 3 minutes to form a first resin layer having a thickness of 8 ⁇ m.
  • the second coating solution for forming a resin layer prepared above was used on the protective film using a die coater.
  • the solution was uniformly applied and dried for 3 minutes with a hot air retention drier at 110 ° C. to remove the solvent, thereby forming a second resin layer having a thickness of 60 nm and a refractive index of 1.4.
  • the support film having the first resin layer and the protective film having the second resin layer are bonded at 23 ° C. using a laminator (manufactured by Hitachi Chemical Co., Ltd., product name: HLM-3000 type). Then, a transfer type photosensitive film in which the support film, the first resin layer, the second resin layer, and the protective film were laminated in this order was produced.
  • a laminator manufactured by Hitachi Chemical Co., Ltd., product name: HLM-3000 type
  • A-DCP Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name)
  • T-1420 Ditrimethylolpropane tetraacrylate (Nippon Kayaku Co., Ltd., product name)
  • ADDITIVE 8032 Octamethylcyclotetrasiloxane (product name, manufactured by Toray Dow Corning Co., Ltd.)
  • AW500 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (product name, manufactured by Kawaguchi Chemical Co., Ltd.)
  • B6030 5-1H-aminotetrazole (product name, manufactured by Chiyoda Chemical Co., Ltd.)
  • OZ-S30K Zirconium oxide nanoparticle dispersion (product name, manufactured by Nissan Chemical Industries, Ltd.)
  • the exposure amount is 5 ⁇ 10 2 J / m 2 (i-line) from vertically above the support film surface. (Measured value at a wavelength of 365 nm) and ultraviolet rays were irradiated imagewise.
  • stacked on the 1st resin layer is removed, and also with the exposure amount of 1 * 10 ⁇ 4 > J / m ⁇ 2 > from the upper side of the 1st resin layer side (measurement value in i line (wavelength 365nm)) Ultraviolet rays were irradiated to obtain a moisture permeability measurement sample in which a cured film made of the cured product of the second resin layer and the cured product of the first resin layer was formed.
  • a cup method was performed as a moisture permeability measurement.
  • About 20 g of dried calcium chloride is put in the measuring cup, and the lid is covered with a circular sample cut out with scissors to a size of about ⁇ 70 mm from the above test sample, and 60 ° C. and 90% RH in a constant temperature and humidity chamber. The condition was left for 24 hours.
  • the moisture permeability [g / m 2 ⁇ 24 h] was calculated from the weight change before and after being left standing. In addition, if the moisture permeability of a cured film is 250 or less, sufficient rust prevention effect will be acquired.
  • a photomask is placed on the support film, and an exposure amount of 5 is applied from above the photomask surface vertically using a parallel light exposure machine (EXM1201 manufactured by Oak Manufacturing Co., Ltd.).
  • EXM1201 manufactured by Oak Manufacturing Co., Ltd.
  • 10 J / m 2 measured value at i-line (wavelength 365 nm)
  • ultraviolet rays were imagewise irradiated.
  • stacked on the 1st resin layer is removed, and also with the exposure amount of 1 * 10 ⁇ 4 > J / m ⁇ 2 > from the upper side of the 1st resin layer side (measurement value in i line (wavelength 365nm))
  • a mandrel test was performed with reference to the JIS standard (K5400).
  • the test sample was cut with scissors to a size of 1.5 cm ⁇ 4.0 cm and set in a cylindrical mandrel bending tester (manufactured by BYK Gardner).
  • One side of the sample is fixed, a weight of 100 g is attached to one side, the protective film side is bent to 180 degrees around the cylinder with the protective film side as the upper surface, and the cured film side is observed with a microscope.
  • Crack resistance was evaluated.
  • ⁇ 0.5 Uses a cylinder of ⁇ 0.5mm, and there is no crack in the protective film.
  • ⁇ 1 A cylinder of ⁇ 1.0mm is used, and there is no crack in the protective film.
  • ⁇ 2 Uses a cylinder with a diameter of ⁇ 2.0mm, and there is no crack in the protective film.
  • ⁇ 3 Uses a cylinder with a diameter of ⁇ 3.0mm, and there is no crack in the protective film.
  • IM layer index matching layer
  • substrate with ITO were prepared. While peeling the protective film of the transfer type photosensitive film obtained in Examples and Comparative Examples on the ITO of the base material, the second resin layer is opposed to the base material, and the roll temperature is 100 ° C., the substrate feed speed. Lamination was performed under the conditions of 0.4 m / min and pressure bonding pressure (cylinder pressure) of 4 ⁇ 10 5 Pa.
  • the substrate was cooled, and when the temperature of the substrate reached 23 ° C., using an exposure machine having a high-pressure mercury lamp from the support film side (manufactured by Oak Manufacturing Co., Ltd., trade name: EXM-1201), Light irradiation was performed at an exposure amount of 80 mJ / cm 2 .
  • a sample for cross-cut adhesion test composed of a cured film of the first resin layer having a thickness of 8.0 ⁇ m and a cured product of the second resin layer was obtained.
  • a cross-cut test was performed based on ASTM D3359 for the adhesion of the cured film to the index matching layer (IM layer) and the substrate with ITO, and the ratio of the peeled portion was measured. Based on this measurement result, a case where adhesion was the best (no peeling at all) was “5”, and a case where it was the worst (all peeling) was “0”. .
  • the substrate was cooled, and when the temperature of the substrate reached 23 ° C., using an exposure machine having a high-pressure mercury lamp from the support film side (manufactured by Oak Manufacturing Co., Ltd., trade name: EXM-1201), Light irradiation was performed at an exposure amount of 80 mJ / cm 2 .
  • the support film was removed and irradiated with light at an exposure amount of 400 mJ / cm 2 .
  • sintering was performed at 140 ° C. for 30 minutes to obtain a sample for reliability test including a cured film of the first resin layer having a thickness of 8.0 ⁇ m and a cured product of the second resin layer.
  • the obtained sample was left in a high-temperature and high-humidity tank at 85 ° C. and 85% RH, and the time until the copper substrate was corroded with the naked eye was evaluated.
  • SYMBOLS 1 Transfer type photosensitive film, 10 ... Support film, 20 ... 1st resin layer, 22 ... Cured 1st resin layer, 30 ... 2nd resin layer, 32 ... 2nd cured resin layer, 40 DESCRIPTION OF SYMBOLS ... Protective film, 50 ... Base material with transparent electrode pattern, 50a ... Transparent electrode pattern, 60 ... Cured film, 100 ... Laminated body, 101 ... Transparent base material, 102 ... Sensing region, 103, 104 ... Transparent electrode, 105 ... Drawer Wiring, 106... Connection electrode, 107... Connection terminal, 123.

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  • Polymers & Plastics (AREA)
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Abstract

L'invention concerne un film photosensible de type transfert qui est pourvu d'un film de support et d'une première couche de résine qui est disposée sur le film de support. La première couche de résine contient un polymère liant, un composé photopolymérisable et un initiateur de photopolymérisation ; et le polymère liant contient un groupe qui a une structure ramifiée et/ou alicyclique dans une chaîne latérale, un groupe qui a un groupe acide dans une chaîne latérale, et un groupe qui a un groupe à insaturation éthylénique dans une chaîne latérale, tout en ayant un équivalent de groupe à insaturation éthylénique de 0,50 à 3,00 mmol/g.
PCT/JP2017/012680 2017-03-28 2017-03-28 Film photosensible de type transfert, procédé de formation d'un motif de film durci, et panneau tactile Ceased WO2018179096A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2019508391A JP6943279B2 (ja) 2017-03-28 2017-03-28 転写型感光性フィルム、硬化膜パターンの形成方法及びタッチパネル
KR1020197028867A KR102401215B1 (ko) 2017-03-28 2017-03-28 전사형 감광성 필름, 경화막 패턴의 형성 방법 및 터치 패널
CN201780089039.7A CN110462559A (zh) 2017-03-28 2017-03-28 转印型感光性膜、固化膜图案的形成方法及触摸面板
PCT/JP2017/012680 WO2018179096A1 (fr) 2017-03-28 2017-03-28 Film photosensible de type transfert, procédé de formation d'un motif de film durci, et panneau tactile

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PCT/JP2017/012680 WO2018179096A1 (fr) 2017-03-28 2017-03-28 Film photosensible de type transfert, procédé de formation d'un motif de film durci, et panneau tactile

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022037025A (ja) * 2018-10-18 2022-03-08 富士フイルム株式会社 転写フィルム、硬化膜の製造方法、積層体の製造方法、及び、タッチパネルの製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012078528A (ja) * 2010-09-30 2012-04-19 Fujifilm Corp 感光性組成物、感光性樹脂転写フィルム、樹脂パターン及び樹脂パターンの製造方法、並びに液晶表示装置用基板及び液晶表示装置
JP2014108541A (ja) * 2012-11-30 2014-06-12 Fujifilm Corp 転写フィルムおよび透明積層体、それらの製造方法、静電容量型入力装置ならびに画像表示装置
JP2015121929A (ja) * 2013-12-24 2015-07-02 日立化成株式会社 硬化膜付きタッチパネル用基材の製造方法、それに用いる感光性樹脂組成物、感光性エレメント及びタッチパネル

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4994136B2 (ja) * 2006-07-26 2012-08-08 富士フイルム株式会社 感光性組成物、感光性樹脂転写フイルム及びフォトスペーサーの製造方法並びに液晶表示装置用基板、及び液晶表示装置
JP2012073589A (ja) * 2010-08-31 2012-04-12 Fujifilm Corp 感光性組成物、感光性フィルム、感光性積層体、永久パターン形成方法、及びプリント基板
WO2013084283A1 (fr) * 2011-12-05 2013-06-13 日立化成株式会社 Procédé de formation d'un film protecteur pour électrodes de panneau tactile, composition de résine photosensible, et élément photosensible
JP5914392B2 (ja) * 2012-03-15 2016-05-11 富士フイルム株式会社 感光性フィルム、静電容量型入力装置の製造方法および静電容量型入力装置、並びに、これを備えた画像表示装置
WO2016063962A1 (fr) * 2014-10-24 2016-04-28 富士フイルム株式会社 Film de transfert et son procédé de fabrication, procédé de fabrication d'un stratifié, procédé de fabrication d'un dispositif d'entrée capacitif, et procédé de fabrication d'un dispositif d'affichage d'image

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012078528A (ja) * 2010-09-30 2012-04-19 Fujifilm Corp 感光性組成物、感光性樹脂転写フィルム、樹脂パターン及び樹脂パターンの製造方法、並びに液晶表示装置用基板及び液晶表示装置
JP2014108541A (ja) * 2012-11-30 2014-06-12 Fujifilm Corp 転写フィルムおよび透明積層体、それらの製造方法、静電容量型入力装置ならびに画像表示装置
JP2015121929A (ja) * 2013-12-24 2015-07-02 日立化成株式会社 硬化膜付きタッチパネル用基材の製造方法、それに用いる感光性樹脂組成物、感光性エレメント及びタッチパネル

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022037025A (ja) * 2018-10-18 2022-03-08 富士フイルム株式会社 転写フィルム、硬化膜の製造方法、積層体の製造方法、及び、タッチパネルの製造方法

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KR20190128187A (ko) 2019-11-15
CN110462559A (zh) 2019-11-15
JPWO2018179096A1 (ja) 2020-01-30
JP6943279B2 (ja) 2021-09-29

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