JP2019215395A - Transfer type photosensitive film, method for forming cured film pattern, laminate and touch panel - Google Patents

Abstract

To provide a transfer type photosensitive film capable of forming a cured film pattern which can sufficiently reduce pattern visibility of a transparent electrode pattern while sufficiently suppressing occurrence of a development residue; and to provide a method for forming a cured film pattern, a laminate and a touch panel using the same.SOLUTION: A transfer type photosensitive film 1 has a temporary support 10, a first layer 20 which is provided on the temporary support and is formed of a photosensitive resin composition and a second layer 30 containing metal oxide particles in this order, in which the metal oxide particles contain first metal oxide particles having a particle size of 15-30 nm and second metal oxide particles having a particle size of 3.3-6.6 nm, and a content of the metal oxide particles in the second layer is 25-50 vol.%.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a transfer type photosensitive film, a method for forming a cured film pattern, a laminate, and a touch panel.

  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.

  Various types of touch panels have been put into practical use, but in recent years, the use of a projected capacitive touch panel has been advanced. Generally, 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 by the X axis and the Y axis. Has formed. As a material for these electrodes, ITO (Indium-Tin-Oxide, indium tin oxide) is mainly used.

  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. In a touch panel, when it comes into contact with a fingertip, a corrosive component such as moisture or salt may enter the sensing area into 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.

  In order to prevent corrosion of the metal wiring, a photosensitive resin composition layer containing a di (meth) acrylate compound having a dicyclopentanyl structure or a dicyclopentenyl structure is provided on a substrate for a touch panel. After curing a predetermined portion of the material layer by irradiation with actinic rays, a method of removing a portion other than the predetermined portion and forming a cured film of a photosensitive resin assembly covering a part or the whole of the substrate has been proposed. (See Patent Document 1 below). According to this method, a cured film having a sufficiently low moisture permeability can be formed on the touch panel substrate.

  On the other hand, in a projected capacitive touch panel, the color difference increases due to the difference in the optical reflection characteristics between the part where the transparent electrode pattern is formed and the part where the transparent electrode pattern is not formed. There is a problem of the so-called "bone appearance phenomenon" in which the electrode pattern is reflected on the screen. In addition, reflection between a transparent electrode pattern and a visibility improving film (OCA: Optical Clear Adhesive) for bonding a cover glass and a transparent electrode pattern to be used for modularization between a substrate and a transparent electrode. There is also a problem that the light intensity increases and the transmittance of the screen decreases.

  In contrast, for example, in Patent Document 2 below, a transparent electrode pattern is formed by providing an index matching layer (optical adjustment layer) (hereinafter, referred to as an “IM layer”) between a base material and a transparent electrode pattern. There is disclosed a transparent conductive resin substrate that reduces a color difference between a curved portion and a non-formed portion to prevent a bone appearance phenomenon and a decrease in transmittance of a screen.

  In addition, for example, in Patent Document 3 below, as a technique for preventing the transparent electrode pattern from being visually recognized, a first curable transparent resin layer having a low refractive index adjusted to a specific refractive index range and a high curable transparent resin layer having a high refractive index are used. A transfer film having a second curable transparent resin layer adjacent thereto is disclosed.

JP 2015-121929 A JP-A-8-240800 WO 2014/084112 pamphlet

  When a protective film is provided on a copper wiring in a frame area of a touch panel, for example, a protective film may not be formed on a part of an external connection terminal portion. When a cured film is provided at a necessary place using a photosensitive resin composition, patterning is usually performed by a process including exposure and development. As the developing means at this time, an aqueous alkaline developer is preferably used from the viewpoint of the safety of the working environment.

  Then, the present inventors studied formation of a cured film pattern using a transferable photosensitive film in which a developable photosensitive resin composition layer and a high refractive index layer were laminated. In this study, it was found that when a high refractive index layer containing a large amount of metal oxide particles was provided in order to sufficiently reduce the bone appearance phenomenon, development residues were likely to occur.

  The present invention is directed to a transfer type photosensitive film capable of forming a cured film pattern capable of sufficiently reducing a bone appearance phenomenon of a transparent electrode pattern while sufficiently suppressing generation of a development residue, and a cured film using the same. It is an object to provide a method for forming a pattern, a laminate, and a touch panel.

  The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, combined two types of metal oxide particles having different particle diameter ranges into a layer laminated on the photosensitive resin composition layer, It has been found that by adjusting the volume ratio of the metal oxide particles in the above, it is possible to achieve both the effect of reducing the bone appearance phenomenon and the developability, and have completed the present invention.

  The present invention provides a temporary support, provided on the temporary support, a first layer made of a photosensitive resin composition, and a second layer containing metal oxide particles, in this order, metal The oxide particles include a first metal oxide particle having a particle size of 15 to 30 nm and a second metal oxide particle having a particle size of 3.3 to 6.6 nm. A transfer type photosensitive film having a content of metal oxide particles of 25 to 50% by volume is provided.

  According to the transfer type photosensitive film of the present invention, by having the above-described configuration, a cured film pattern capable of sufficiently reducing the bone appearance phenomenon of the transparent electrode pattern can be formed while sufficiently suppressing generation of development residues. Can be.

  The present inventors consider the reason why the above effects are exhibited by the present invention as follows. First, when a cured film pattern is formed using a transferable photosensitive film having a photosensitive resin layer and a high refractive index layer on a substrate on which a transparent electrode pattern is provided, the base is formed by laminating from the high refractive index layer side. A laminated structure of material / high refractive index layer / photosensitive resin layer is formed, and the laminated structure is exposed and developed from the photosensitive resin layer side. Here, the reason why development residue is likely to occur when metal oxide particles are highly blended in the high refractive index layer is that most of the photosensitive resin contained in the high refractive index layer exists in the gap between the metal oxide particles. It is considered that the dissolution of the photosensitive resin by the developing solution is hindered. On the other hand, in the transfer type photosensitive film of the present invention, in the second layer, the first metal oxide particles having the specific particle size and the specific metal oxide particles having a particle size smaller than the first metal oxide particles have the specific particle size. By mixing with the second metal oxide particles having a particle size of, the particle filling structure in which the second metal oxide particles are present between the first metal oxide particles in the second layer. It is easy to form. Since the second layer has such a particle filling structure, even when the metal oxide particles are filled to a level that can sufficiently reduce the bone appearance phenomenon, the metal oxide particles have a high density. The present inventors speculate that the packing reduces the gap between the particles, increases the proportion of the photosensitive resin present on the surface side of the second layer, and improves the developability.

In the transfer type photosensitive film of the present invention, from the viewpoint of further improving developability, the ratio M ₂ of the average particle diameter M ₂ of the second metal oxide particles to the average particle diameter M ₁ of the _first metal oxide particles. / M ₁ is preferably from 0.10 to 0.44.

  In the transfer type photosensitive film of the present invention, the second layer may contain a photosensitive resin composition.

  In the transfer type photosensitive film of the present invention, the content of the first metal oxide particles in the second layer is from 15 to 40% by volume from the viewpoint of suppressing the bone appearance phenomenon while further improving the developability. The content of the second metal oxide particles in the second layer is preferably 2 to 10% by volume.

  The present invention also provides, on a substrate having an electrode pattern, the first layer and the second layer of the transfer type photosensitive film according to the present invention, the side of the substrate on which the electrode pattern is provided and the second layer. The step of laminating so that the layers are in close contact with each other, and after exposing a predetermined portion of the first layer and the second layer on the substrate, removing portions other than the predetermined portion, and covering a part or all of the electrode pattern. Forming a cured film pattern.

  According to the method of forming a cured film pattern of the present invention, by using the transfer type photosensitive film according to the present invention, when the electrode is a transparent electrode, the cured film pattern can sufficiently reduce the bone appearance phenomenon. Can be formed while sufficiently suppressing generation of a development residue.

  The present invention is also a laminate comprising a substrate having an electrode pattern and a cured film provided on the electrode pattern, wherein the cured film has a region containing metal oxide particles on the substrate side. And wherein the metal oxide particles include a first metal oxide particle having a particle size of 15 to 30 nm and a second metal oxide particle having a particle size of 3.3 to 6.6 nm; In which the content of the metal oxide particles is 25 to 50% by volume.

  The laminate of the present invention has a cured film capable of sufficiently reducing the bone appearance phenomenon when the electrode is a transparent electrode. Further, in the laminate of the present invention, since the cured film can be formed by the transfer type photosensitive film according to the present invention, a problem caused by a development residue can hardly occur.

In the laminate of the present invention, the average ratio _M 2 / _{M 1} of the particle diameter _{M 2} of the second metal oxide particles to the average particle diameter _{M 1} of the first metal oxide particles, 0.10 to 0.44 It may be.

  Further, the content of the first metal oxide particles in the region may be 15 to 40% by volume, and the content of the second metal oxide particles in the region may be 2 to 10% by volume. .

  The present invention also provides a touch panel including the laminate according to the present invention, wherein the substrate is a substrate for a touch panel. Since the touch panel of the present invention includes the laminate according to the present invention, the phenomenon of visible bones of the transparent electrode pattern can be sufficiently suppressed, and the touch panel can be excellent in visibility. Further, in the touch panel of the present invention, since the cured film can be formed by the transfer type photosensitive film according to the present invention, problems caused by development residues such as poor connection at external connection terminals are less likely to occur. obtain.

  According to the present invention, a transfer type photosensitive film capable of forming a cured film pattern capable of sufficiently reducing a bone appearance phenomenon of a transparent electrode pattern while sufficiently suppressing generation of a development residue, and using the same. A method for forming a cured film pattern, a laminate, and a touch panel can be provided.

FIG. 1 is a schematic sectional view showing a transfer type photosensitive film according to one embodiment of the present invention. FIG. 1 is a schematic cross-sectional view illustrating a laminate including a cured film pattern formed using a transfer-type photosensitive film according to an embodiment of the present invention on a substrate with a transparent electrode pattern. 1 is a schematic top view showing a touch panel according to one embodiment of the present invention.

  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.

  Further, in this specification, the term “layer” includes, when observed in a plan view, a structure having a partly formed shape in addition to a structure having a partly formed whole surface. 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. Further, a numerical range indicated by using “to” indicates a range including numerical values described before and after “to” as a minimum value and a maximum value, respectively.

  Further, in the present specification, the content of each component in the composition, if 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 the amount. Unless otherwise specified, the exemplified materials may be used alone or in combination of two or more.

  In addition, in the numerical ranges described stepwise in this specification, the upper limit or the lower limit of the numerical range of a certain stage may be replaced with the upper limit or the 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.

[Transfer type photosensitive film]
The transfer type photosensitive film of the present embodiment is a temporary support, provided on the temporary support, a first layer made of a photosensitive resin composition, and a second layer containing metal oxide particles. , In this order. The transfer type photosensitive film may further include a protective film provided on the second layer.

  FIG. 1 is a schematic sectional view showing a transfer type photosensitive film according to one embodiment of the present invention. The transfer type photosensitive film 1 shown in FIG. 1 includes a support film 10 as a temporary support, a first layer 20 provided on the support film 10, and a second layer 20 provided on the first layer 20. And a protective film 40 provided on the second layer 30.

(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.

  The thickness of the support film 10 is preferably 5 to 100 μm, and more preferably 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. Is more preferably 15 to 40 μm, particularly preferably 15 to 35 μm.

(First layer)
The first layer 20 includes a binder polymer (hereinafter, also referred to as a component (A)), a photopolymerizable compound (hereinafter, also referred to as a component (B)), and a photopolymerization initiator (hereinafter, also referred to as a component (C)). ) Is preferably formed from a photosensitive resin composition containing

<Binder polymer>
As the component (A), a polymer having a carboxyl group is preferably used from the viewpoint of enabling patterning by alkali development.

  As the component (A), a copolymer containing a structural unit derived from (meth) acrylic acid and an alkyl (meth) acrylate is preferable. The above-mentioned copolymer may contain the other monomer which can be copolymerized with the above (meth) acrylic acid and the alkyl (meth) acrylate in the structural unit. Specific examples of other monomers include glycidyl (meth) acrylate, benzyl (meth) acrylate, styrene, and cyclohexyl (meth) acrylate.

  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.

  From the viewpoints of alkali developability (especially developability in an aqueous inorganic alkali solution), patterning properties, and transparency, the binder polymer is composed of (meth) acrylic acid, glycidyl (meth) acrylate, benzyl (meth) acrylate, styrene, Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Dicyclopentenyloxy (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxy (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexylma Binder polymers having a structural unit derived from at least one compound selected from the group consisting of imide, hydroxyethyl (meth) acrylate and hydroxybutyl (meth) acrylate are preferable, and (meth) acrylic acid, glycidyl (meth) acrylate Ester, benzyl (meth) acrylate, styrene, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and (meth) acryl Binder polymers having structural units derived from at least one compound selected from the group consisting of acid cyclohexyl esters are more preferable, and (meth) acrylic acid, alkyl (meth) acrylate, and (meth) acrylic acid Succinimidyl ester and (meth) binder polymer having a structural unit derived from acrylic acid cyclohexyl ester are particularly preferred. Further, the binder polymer may be a copolymer containing at least hydroxyethyl (meth) acrylate or hydroxybutyl (meth) acrylate as the above structural unit, such as hydroxyethyl (meth) acrylate or hydroxybutyl (meth) acrylate, and isocyanatoethyl (meth) acrylate. Acrylate or glycidyl (meth) acrylate may be subjected to an addition reaction.

  In the present embodiment, from the viewpoint of reducing the moisture permeability of the cured film, a group having a branched structure and / or an alicyclic structure in the side chain, a group having an acidic group in the side chain, and an ethylenically unsaturated group in the side chain A binder polymer containing a group having a group can be used. The group having a branched structure and / or an alicyclic structure in the side chain 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 having an acidic group in the side chain can be introduced by a monomer containing a group having an acidic group in the side chain.

  Examples of the monomer containing a group having a branched structure in the side chain include i-propyl (meth) acrylate, i-butyl (meth) acrylate, s-butyl (meth) acrylate, and t- (meth) acrylate. Butyl, i-amyl (meth) acrylate, t-amyl (meth) acrylate, sec-iso-amyl (meth) acrylate, 2-octyl (meth) acrylate, 3-octyl (meth) acrylate, ( (Meth) acrylic acid t-octyl and the like. Among them, 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.

  Examples of 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. As more specific examples, for example, (meth) acrylic acid (bicyclo [2.2.1] heptyl-2), (meth) acrylic acid-1-adamantyl, (meth) acrylic acid-2-adamantyl, (meth) ) -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-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, (meth) acyl Octahydro-4,7-menthanoinden-5-yl luate, octahydro-4,7-menthanoinden-1-ylmethyl (meth) acrylate, 1-menthyl (meth) acrylate, (meth) acrylic acid Dicyclopentanyl, 3-hydroxy-2,6,6-trimethyl-bicyclo [3.1.1] heptyl (meth) acrylate, -3,7,7-trimethyl-4-hydroxy (meth) acrylate -Bicyclo [4.1.0] heptyl, (nor) bornyl (meth) acrylate, isobornyl (meth) acrylate, fentyl (meth) acrylate, -2,2,5-trimethylcyclohexyl (meth) acrylate, And cyclohexyl (meth) acrylate. Among these (meth) acrylates, cyclohexyl (meth) acrylate, (nor) bornyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, and (meth) acrylic acid- 2-adamantyl, fentyl (meth) acrylate, 1-menthyl (meth) acrylate, dicyclopentanyl (meth) acrylate are preferred, cyclohexyl (meth) acrylate, (nor) bornyl (meth) acrylate, ( Isobornyl (meth) acrylate and 2-adamantyl (meth) acrylate are particularly preferred.

  When the component (A) contains a group having a branched structure and / or an alicyclic structure in a side chain, it is possible to obtain good adhesion to a substrate, particularly good adhesion to a substrate having an index matching layer. it can. Further, by having a group having an alicyclic structure in the side chain, the moisture permeability of the cured film can be reduced.

  Specific examples of the monomer containing a group having an acidic group in the side chain can be appropriately selected from known monomers, and include, for example, (meth) acrylic acid, vinylbenzoic acid, maleic acid, and monoalkyl maleate. , Fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyanocinnamic acid, acrylic acid dimer, an addition product of a monomer having a hydroxyl group and a cyclic acid anhydride, ω-carboxy-polycaprolactone mono (meta ) Acrylate and the like. These may be appropriately manufactured or commercially available products.

  When the component (A) contains a group having an acidic group in the side chain, patterning by alkali development can be performed.

  The group having an ethylenically unsaturated group in the side chain is not particularly limited, and a (meth) acryloyl group is preferable as the ethylenically unsaturated group. The link 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, and a carbamoyl group. The method for introducing an ethylenically unsaturated group into the side chain can be appropriately selected from known methods. For example, a method for adding a (meth) acrylate having an epoxy group to a group having an acidic group, a method for adding a hydroxy group, A method of adding a (meth) acrylate having an isocyanate group to a group having the same, a method of adding a (meth) acrylate having a hydroxy group to a group having an isocyanate group, and the like can be given. Among them, a method of adding a (meth) acrylate having an epoxy group to a group having an acidic group is preferred because it is the easiest to manufacture and the cost is low.

  When the component (A) contains a group having an ethylenically unsaturated group in a side chain, good adhesion to a substrate, particularly good adhesion to a substrate having an index matching layer can be obtained. Further, the moisture permeability of the cured film can be reduced.

  Based on the total amount of the monomers constituting the component (A), the proportion of the monomers constituting the group having a branched structure and / or an alicyclic structure in the side chain is preferably from 10 to 70 mol%, and preferably from 15 to 65 mol%. %, More preferably 20 to 60 mol%. Further, based on the total amount of the monomers constituting the component (A), the proportion of the monomers constituting the group having an acidic group in the side chain is preferably from 5 to 70 mol%, more preferably from 10 to 60 mol%. Is more preferable, and 20 to 50 mol% is further preferable. Further, based on the total amount of the monomers constituting the component (A), the proportion of the monomers constituting the group having an ethylenically unsaturated group in the side chain is preferably from 5 to 70 mol%, more preferably from 10 to 60 mol%. Is more preferably 20 to 50 mol%. By satisfying the ratio of the monomer, the patterning property by alkali development, the lamination property to the base material, and the good adhesion to the base material which may have the index matching layer can be improved in a well-balanced manner.

  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 75 mgKOH / g or more from the viewpoint of easily forming a cured film (cured film pattern) having a desired shape by alkali development. Further, 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) is preferably 75 to 200 mgKOH / g, and more preferably 75 to 150 mgKOH / g. More preferably, it is more preferably 75 to 120 mgKOH / g. The acid value can be measured by the method described in the examples of the present specification.

  Note that the first layer 20 may further contain a binder polymer other than the above-mentioned (A) binder polymer.

<Photopolymerizable compound>
As the photopolymerizable compound 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 a monofunctional vinyl monomer, a bifunctional vinyl monomer, and a polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups.

  As the monofunctional vinyl monomer, for example, (meth) acrylic acid, alkyl (meth) acrylate, and alkyl (meth) acrylate exemplified as monomers used in the synthesis of a copolymer which is a preferred example of the component (A) are used. Polymerizable monomers are mentioned.

  Examples of the bifunctional vinyl monomer include polyethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenol A polyoxyethylene polyoxypropylene di (meth) acrylate (2 , 2-bis (4- (meth) acryloxypolyethoxypolypropoxyphenyl) propane), bisphenol A diglycidyl ether di (meth) acrylate, a compound having a hydroxyl group and an ethylenically unsaturated group (for example, β-hydroxyethyl acrylate) , Β-hydroxyethyl methacrylate) and a polycarboxylic acid (eg, phthalic anhydride).

  The photosensitive resin composition of the present embodiment preferably contains a compound having a tricyclodecane skeleton or a tricyclodecene skeleton from the viewpoint of improving adhesion to an electrode. In addition, from the viewpoint of suppressing corrosion of the metal wiring and the transparent electrode pattern, a di (meth) acrylate compound represented by the following general formula (B-1) is included as a compound having a tricyclodecane skeleton or a tricyclodecene skeleton. Is preferred.

［一般式（Ｂ−１）中、Ｒ^１及びＲ^２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、Ｒ^３及びＲ^４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。］

[In the general formula (B-1), R ¹ and R ² 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 ³ and R ⁴ each independently represent 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 are selected. ]

In the general formula (B-1), R ³ and R ⁴ are preferably an ethylene group or a propylene group, and more preferably an ethylene group. Further, the propylene group may be any of an n-isopropylene group and an isopropylene group.

  According to the compound represented by the general formula (B-1), the divalent group having a tricyclodecane skeleton or a tricyclodecene skeleton contained in X has a bulky structure, so that a low cured film is obtained. The moisture permeability can be realized, 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).

  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.).

  In the component (B), the proportion of the compound having a tricyclodecane skeleton or a tricyclodecene skeleton is preferably from 100 parts by mass of the total amount of the photopolymerizable compound contained in the photosensitive resin composition from the viewpoint of preventing corrosion of metal wiring. Of these, the amount is preferably at least 50 parts by mass, more preferably at least 70 parts by mass, even more preferably at least 80 parts by mass.

  Examples of the polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups include a (meth) acrylate compound having a skeleton derived from pentaerythritol, a (meth) acrylate compound having a skeleton derived from dipentaerythritol, and trimethylol (Meth) acrylate compounds having a propane-derived skeleton.

  Here, “(meth) acrylate having a skeleton derived from dipentaerythritol” means an esterified product of dipentaerythritol and (meth) acrylic acid, and the esterified product is a compound modified with an alkyleneoxy group. Are also included. The esterified product preferably has 6 ester bonds in one molecule, but may contain a compound having 1 to 5 ester bonds. The (meth) acrylate compound having a skeleton derived from trimethylolpropane means an esterified product of trimethylolpropane and (meth) acrylic acid, and the esterified product is a compound modified with an alkyleneoxy group. Are also included. The above-mentioned esterified product preferably has three ester bonds in one molecule, but may contain a compound having one or two ester bonds. Further, as the (meth) acrylate compound having a skeleton derived from trimethylolpropane, a compound obtained by dimerizing a trimethylolpropane di (meth) acrylate compound may be used.

  Specifically, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Compound obtained by reacting a polyhydric alcohol such as ditrimethylolpropane tetraacrylate with an α, β-unsaturated carboxylic acid (eg, acrylic acid, methacrylic acid, etc.); trimethylolpropane triglycidyl ether tri (meth) acrylate A compound obtained by an addition reaction of a glycidyl group-containing compound such as glycidyl group and an α, β-unsaturated carboxylic acid; a compound obtained by adding a diglycerin such as diglycerin (meth) acrylate to an α, β-unsaturated carboxylic acid. Compounds And the like.

  The above compounds can be used alone or in combination of two or more.

  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.

  From the viewpoint of lowering the moisture permeability of the cured film pattern and improving the adhesion, the compound having a tricyclodecane skeleton or tricyclodecene skeleton is preferably 5 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B). It is preferably at least 10 parts by mass, more preferably at least 10 parts by mass, further preferably at least 20 parts by mass, particularly preferably at least 25 parts by mass.

<Photopolymerization initiator>
The component (C) is not particularly limited as long as it can cure the first layer by irradiation with actinic rays. From the viewpoints of transparency and corrosion prevention of metal wiring, acylphosphine oxide-based photopolymerization initiators and oxime ester-based photopolymerization initiators are preferred.

  Examples of the acylphosphine oxide-based photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and 2,4,6- Trimethylbenzoyl-phosphinate. Acylphosphine oxide-based photopolymerization initiators are available as IRGACURE TPO, IRGACURE 819, and IRGACURE TPO-L (product names, manufactured by BASF Corporation). By using the acylphosphine oxide-based photopolymerization initiator, a sufficient polymerization reaction rate can be obtained in the cured film, and the pattern appearance can be suppressed.

  Examples of the oxime ester-based photopolymerization initiator include a compound represented by the following general formula (1), a compound represented by the following general formula (2), and a compound represented by the following general formula (3).

In the formula (1), 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; It is preferably an alkyl group, a cycloalkyl group having 4 to 6 carbon atoms, a phenyl group or a tolyl group, and is 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. More preferably, it is more preferably 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)} is preferably from 2 OH, -H, -O (CH 2 ) ₂ OH or —COO (CH ₂ ) ₂ OH.

In the formula (2), each of two R ¹⁴ independently represents an alkyl group having 1 to 6 carbon atoms, and is 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.

In the formula (3), 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 of a compound represented by the following formula (3-1). 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 (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 (manufactured by DAI-TO-MIX KK, product name).

  The compound represented by the general formula (3) is available as ADEKA OPTOMER N-1919 (product name, manufactured by ADEKA Corporation).

  In the present embodiment, it is preferable to use an acylphosphine oxide-based photopolymerization initiator and an oxime ester-based photopolymerization initiator in combination. By using an acylphosphine oxide-based photopolymerization initiator and an oxime ester-based photopolymerization initiator in combination, the moisture permeability of the formed cured resin film can be further reduced.

  In this case, the mass ratio between the acylphosphine oxide-based photopolymerization initiator and the oxime ester compound is preferably from 8: 1 to 0.5: 1 from the viewpoint of reducing the bone appearance phenomenon and preventing corrosion of the metal wiring. More preferably, the ratio is from 4: 1 to 2: 1.

  The content of the component (C) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B) from the viewpoint of excellent light sensitivity and resolution. The amount is more preferably from 5 to 5 parts by mass, further preferably from 1 to 3 parts by mass, and particularly preferably from 1 to 2 parts by mass.

<Rust inhibitor>
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.).

  Examples of the triazole compound having an amino group include, for example, benzotriazole, 1H-benzotriazole-1-acetonitrile, benzotriazole-5-carboxylic acid, 1H-benzotriazole-1-methanol, carboxybenzotriazole, and the like, in which the amino group is substituted. Examples of the compound include compounds in which a triazole compound containing a mercapto group such as 3-mercaptotriazole and 5-mercaptotriazole is substituted with an amino group.

  Examples of the tetrazole compound having an amino group include 5-amino-1H-tetrazole (manufactured by Chiyoda Chemical Co., Ltd., product name: B6030), 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 thereof include alkali metal salts of 1-methyl-5-amino-tetrazole such as sodium, potassium and lithium.

  When the photosensitive resin composition contains the component (D), the content 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 parts by mass is more preferable, and 0.3 to 0.8 parts by mass is particularly preferable.

  In the photosensitive resin composition forming the first layer according to the present embodiment, as other additives, if necessary, adhesion properties of a phosphoric acid ester having an ethylenically unsaturated group, a silane coupling agent, etc. Additives, rust inhibitors, leveling agents, plasticizers, fillers, defoamers, flame retardants, stabilizers, antioxidants, fragrances, thermal crosslinking agents, polymerization inhibitors, etc., as components (A) and (B) Can be contained in an amount of about 0.01 to 20 parts by mass with respect to 100 parts by mass in total. These can be used alone or in combination of two or more.

  The thickness of the first layer may be 1 to 15 μm, preferably 2 to 10 μm, more preferably 3 to 8 μm, further preferably 4 to 6 μm, and more preferably 5 to 6 μm. Is particularly preferred. When the thickness is 1 to 15 μm, a defect at the time of coating is small, and a film having excellent transparency can be formed. Further, the thickness of the first layer after curing is preferably within the above range.

(Second layer)
The second layer 30 is a layer containing metal oxide particles. The second layer 30 can have a relatively higher refractive index than the first layer 20 by containing metal oxide particles. The second layer 30 preferably has a refractive index at 633 nm in the range of 1.40 to 1.90, more preferably 1.50 to 1.90, and more preferably 1.53 to 1.85. More preferably, it is particularly preferably 1.55 to 1.75. When the second layer contains a curable component, the refractive index of the second layer after curing at 633 nm is preferably within the above range.

  When the refractive index at 633 nm of the second layer 30 is within the above range, when the cured film pattern is provided on a transparent electrode pattern such as ITO, various members used on the cured film pattern (for example, modularization) The optical reflection between the portion where the transparent electrode pattern such as ITO is formed and the portion where the transparent electrode pattern such as ITO is not formed is the intermediate value of the refractive index of the cover glass used when bonding and the transparent electrode pattern. Can reduce the color difference, and can prevent the bone appearance phenomenon. 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.

  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, further preferably from 1.48 to 1.51. .

  The second 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 range of 450 to 650 nm is preferably within the above range.

  The second layer 30 can contain the above components (A), (B) and (C), and can further contain the above component (D) as needed. The second layer 30 does not necessarily need to contain a photopolymerization component such as the component (B) and the component (C), and uses the photopolymerization component that migrates from an adjacent resin layer due to layer formation to form the second layer 30. Light curing can also be used.

  The second layer 30 contains metal oxide particles (hereinafter, also referred to as component (E)). 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 layer and the refractive index at a wavelength of 633 nm when a transfer type photosensitive film is prepared. Further, the developability can be improved while suppressing the adsorption to the substrate.

  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.

  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.

  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.).

  The second layer 30 may contain titanium oxide nanoparticles as the component (E). Further, among the titanium oxide nanoparticles, the particle size distribution Dmax is preferably 50 nm or less, and more preferably 10 to 50 nm.

  As the component (E), besides the above metal oxide particles, for example, oxide particles or sulfide particles containing atoms such as Mg, Al, Si, Ca, Cr, Cu, Zn, and Ba can also be used. These can be used alone or in combination of two or more.

  In the present embodiment, a first metal oxide particle having a particle diameter of 15 to 30 nm (hereinafter, also referred to as a component (E-1)) and a second metal oxide particle having a particle diameter of 3.3 to 6.6 nm. It is preferable to include metal oxide particles (hereinafter, also referred to as component (E-2)). Since the (E-1) component and the (E-2) component are blended in the second layer, the particle diameter is small between the (E-1) components having a large particle diameter in the second layer. A particle-filled structure in which the component (E-2) exists is easily formed.

  The particle diameter of the metal oxide particles can be measured by a laser diffraction type particle size distribution meter or the like.

In the present embodiment, from the viewpoint of further improving the developability, the average ratio M _{2 /} M ₁ of the particle diameter M ₂ of the second metal oxide particles to the average particle diameter M ₁ of the first metal oxide particles, It is preferably 0.10 to 0.44, more preferably 0.15 to 0.40, and even more preferably 0.20 to 0.35.

  The average particle size of the particles can be measured by a particle size distribution measuring device such as a laser diffraction type particle size distribution meter.

  In the present embodiment, the content of the metal oxide particles in the second layer is preferably from 25 to 50% by volume, and more preferably from 30 to 50% by volume, from the viewpoint of achieving a balance between the reduction of the bone appearance phenomenon and the developability. %, More preferably 35 to 50% by volume.

The volume% of the metal oxide particles in the second layer can be determined as follows. For example, when the metal oxide particles contained in the second layer are only one kind of composition (for example, only zirconium oxide), components other than the metal oxide particles in the second layer (for example, organic components such as resin). mass and density and M _o and D _o, respectively, when M ₁ and D _1, respectively by weight and density of the metal oxide particles, the volume percent of metal oxide particles is determined from the following equation.
Volume percent of metal oxide particles _{= (M 1 / D 1)} × 100 / [(M o / D o) + (M 1 / D 1)]
The density of the metal oxide particles can be determined by using physical properties such as a chronological table.
Further, the metal oxide particles contained in the second layer are only the component (E-1) and the component (E-2), and the metal oxide particles having different components (E-1) and (E-2). In this case, the volume% of the metal oxide particles in the second layer can be determined as follows.
Volume _percent of metal oxide particles _{= [(M 1 / D 1} ) + (M 2 / D 2)] × 100 / [(M o / D o) + (M 1 / D 1) + (M 2 / D ₂ )]
In the formula, M ₁ and D ₁ indicate the mass and density of a component (eg, an organic component such as a resin) other than the metal oxide particles in the second layer, and M ₁ and D ₁ are (E-1) shows the mass and density of the components, _{M 2} and _{D 2} shows the mass and density of the (E-2) component.

  From the viewpoint of improving developability, the content of the component (E-1) in the second layer is preferably from 15 to 40% by volume, more preferably from 16 to 39% by volume, and from 17 to 39% by volume. More preferably, it is 38% by volume.

  From the viewpoint of improving the developability, the content of the component (E-2) in the second layer is preferably 2 to 10% by volume, more preferably 2 to 8% by volume, and 2 to 8% by volume. More preferably, it is 6% by volume.

  From the viewpoint of suppressing the bone appearance phenomenon while further improving the developability, the volume ratio of the component (E-2) to the component (E-1) in the second layer [(E-2) / (E-1) )] Is preferably 0.05 to 0.40, more preferably 0.10 to 0.40, and even more preferably 0.10 to 0.30.

  For the second layer, in addition to the metal oxide particles, for example, 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 can be used. Thereby, the refractive index at a wavelength of 633 nm can be improved.

  The thickness of the second layer 30 may be 0.01 to 1 μm, preferably 0.03 to 0.5 μm, more preferably 0.04 to 0.3 μm, and 0.1 to 0.3 μm. It is more preferably from 07 to 0.25 μm, particularly preferably from 0.05 to 0.2 μm. When the thickness is 0.01 to 1 μm, the above-described reflected light intensity of the entire screen can be further reduced. Further, the thickness of the second layer after curing is preferably within the above range.

When the second layer is a single layer and the film thickness is uniform in the film thickness direction, the refractive index of the second layer 30 is obtained as follows using ETA-TCM (manufactured by AudioDev Corporation, product name). be able to. The following measurement is performed under the condition of 25 ° C.
(1) A coating solution for forming the second 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 is coated with a hot air convection dryer at 100 ° C. Dry for a minute to remove the solvent and form a second layer.
(2) Next, the sample is allowed to stand in a box 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 layer.
(3) Next, the obtained refractive index measurement sample is measured for its refractive index at a wavelength of 633 nm by ETA-TCM (product name, manufactured by AudioDev Co., Ltd.).

  The refractive index of the single-layer first layer can be measured in the same manner. In the case of the transfer type photosensitive film, since it is difficult to measure the refractive index of the second layer single layer, the value is set to the value of the outermost layer on the protective film side of the second layer.

(Other layers)
The transfer type photosensitive film of the present invention may be provided with another layer appropriately selected within a range where the effects of the present invention can be obtained. The other layer is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include a cushion layer, an oxygen shielding layer, a release layer, and an adhesive layer. The transfer type photosensitive 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.

(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.

  The thickness of the protective film 40 is preferably 5 to 100 μm, but from the viewpoint of storing the transferable photosensitive film 1 in a roll form, it is preferably 70 μm or less, more preferably 60 μm or less, and more preferably 50 μm or less. Is more preferable, and particularly preferably 40 μm or less.

  Total light transmission of a cured film portion (excluding the support film 10 and the protection film 40) of the transfer type photosensitive film 1 obtained by curing the first layer 20 and the second layer 30 in a visible light region having a wavelength of 400 to 700 nm. The minimum value of the rate (Tt) is preferably 90.00% or more, more preferably 90.50% or more, and even more preferably 90.70% or more. 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.

  The first layer 20 and the second layer 30 of the transfer type photosensitive film 1 are prepared, for example, by preparing a first layer forming coating solution and a second layer forming coating solution, respectively, It can be formed by coating and drying on the protective film 40. The transfer-type photosensitive film 1 includes the support film 10 on which the first layer 20 is formed and the protective film 40 on which the second layer 30 is formed by combining the first layer 20 and the second layer 30. Can be formed by sticking together in a state where they face each other. In addition, the transfer type photosensitive film 1 is applied with a coating solution containing the first layer forming coating solution on the support film 10, dried, and then, on the first layer 20, the second forming coating solution is coated. It can also be formed by applying a liquid, drying, and attaching a protective film 40.

  The coating liquid can be obtained by uniformly dissolving or dispersing the above-described components of the photosensitive resin composition according to the present embodiment and the second layer in a solvent.

  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.

  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 transfer type photosensitive film according to the present embodiment can be applied to formation of a protective film in various electronic components. The electronic component according to the present embodiment has 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 an electronic paper.

[Method of forming cured film pattern]
The method of forming a cured film pattern according to the present embodiment includes, on a substrate having an electrode pattern, the first layer and the second layer of the above-described transfer type photosensitive film of the present embodiment, A step of laminating so that the provided side and the second layer are in close contact with each other, and after exposing a predetermined portion of the first layer and the second layer on the substrate, removing portions other than the predetermined portion to form an electrode pattern. Forming a cured film pattern covering part or all of the above.

  FIG. 2 is a schematic cross-sectional view showing a laminate having a cured film formed using the transfer photosensitive film according to one embodiment of the present invention on a substrate with a transparent electrode pattern. The laminate 100 shown in FIG. 2 includes a substrate 50 with a transparent electrode pattern having a transparent electrode pattern 50a, and a cured film 60 provided on the transparent electrode pattern 50a of the substrate 50 with a transparent electrode pattern. The cured film 60 is a resin cured film including the cured first layer 22 and the cured second layer 32, and is formed using the transfer photosensitive film 1 of the present embodiment. The cured film 60 satisfies both the function of protecting the transparent electrode pattern 50a and the function of making the transparent electrode pattern 50a invisible or improving the visibility of the touch screen. Hereinafter, an embodiment of a method for manufacturing a laminate in which a cured film is formed on a substrate with a transparent electrode pattern will be described.

-Lamination process-
First, after removing the protective film 40 of the transfer type photosensitive film 1, the second layer 30, the first layer 20, and the support film 10 are placed on the surface of the substrate 50 with the transparent electrode pattern from the second layer 30 side. Lamination (transfer) is performed by pressing. As the pressing means, a pressing roll may be used. The pressure roll may be provided with a heating means so as to be capable of thermocompression bonding.

  The heating temperature in the case of thermocompression bonding is based on the viewpoint of the adhesion between the second layer 30 and the substrate 50 with a transparent electrode pattern, and the fact that the components of the first layer 20 or the second layer 30 are thermoset or thermoset. From the viewpoint of making it difficult to decompose, the temperature is preferably from 10 to 160 ° C, more preferably from 20 to 150 ° C, even more preferably from 30 to 150 ° C.

In addition, the pressing pressure at the time of heating and pressing is set to a linear pressure from the viewpoint of suppressing deformation of the base material with a transparent electrode pattern 50 while ensuring sufficient adhesion between the second layer 30 and the base material with a transparent electrode pattern 50. Is preferably 50 to 1 × 10 ⁵ N / m, more preferably 2.5 × 10 ^{2 to} 5 × 10 ⁴ N / m, and more preferably 5 × 10 ² to 4 × 10 ⁴ N / m. More preferably,

  If the transfer type photosensitive film 1 is heat-pressed as described above, the pre-heat treatment of the substrate 50 with the transparent electrode pattern is not necessarily required, but the adhesion between the second layer 30 and the substrate 50 with the transparent electrode pattern is not required. In order to further improve the temperature, the base material 50 with a transparent electrode pattern may be pre-heated. The processing temperature at this time is preferably 30 to 150 ° C.

(Base material)
Examples of the base material constituting the base material 50 with a transparent electrode pattern include a base material such as a glass plate, a plastic plate, and a ceramic plate used for a touch panel (touch sensor). As the substrate of the substrate having the electrode pattern of the present embodiment, a substrate for a touch panel made of the above material can be used.

(Transparent electrode and metal wiring)
The transparent electrode can be formed using a conductive metal oxide film such as ITO and IZO (Indium Zinc Oxide, indium oxide-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 using a conductive material such as Au, Ag, Cu, Al, Mo, or C by a method such as screen printing or vapor deposition. Further, an insulating layer or an index matching layer may be provided between the substrate and the electrode on the substrate. The index matching layer may have a composition similar to that of the second layer 30 described above.

-Exposure process-
Next, a predetermined portion of the first layer and the second layer after the transfer is irradiated with actinic rays in a pattern via a photomask. When irradiating with an actinic ray, if the support film 10 on the first layer and the second layer is transparent, the actinic ray can be irradiated as it is. Irradiate. A known active light source can be used as a light source for the active light. In the present specification, the pattern is not limited to the shape of fine wiring forming a circuit, but also includes a shape in which only a connection portion with another substrate is removed in a rectangular shape and a shape in which only a frame portion of the substrate is removed. It is.

The irradiation amount of the actinic ray is 1 × 10 ² to 1 × 10 ⁴ J / m ² , and the irradiation may be accompanied by heating. When the irradiation amount of this actinic ray is 1 × 10 ² J / m ² or more, the photocuring of the first layer and the second layer can be sufficiently advanced, and 1 × 10 ⁴ J / m 2. If it is ² or less, discoloration of the first layer and the second layer tends to be suppressed.

  Subsequently, the unexposed portions of the first layer and the second layer after irradiation with actinic rays are removed with a developer to form a cured film (refractive index adjustment pattern) 60 covering a part or the whole of the transparent electrode. I do. After the actinic ray irradiation, if the support film 10 is laminated on the first layer and the second layer, the support film 10 is removed, and then the developing step is performed.

  The development step can be performed by a known method such as spraying, showering, rocking immersion, brushing, and scrubbing using a known developing solution such as an aqueous alkali solution, an aqueous developing solution, or an organic solvent. Especially, it is preferable to carry out spray development using an alkaline aqueous solution from the viewpoint of environment and safety. The development temperature and time can be adjusted in a conventionally known range.

[Laminate]
The laminate of the present embodiment is a laminate having a substrate having an electrode pattern and a cured film provided on the electrode pattern, wherein the cured film is a region containing metal oxide particles on the substrate side. Wherein the metal oxide particles include a first metal oxide particle having a particle size of 15 to 30 nm and a second metal oxide particle having a particle size of 3.3 to 6.6 nm, The content of the metal oxide particles in the above region may be 25 to 50% by volume.

  The above-mentioned laminate can be obtained by the above-described method for producing a laminate using the transfer type photosensitive film of the present embodiment. The region containing the metal oxide particles can be formed, for example, by the cured second layer 32 shown in FIG.

In the laminate of the present embodiment, the average ratio M _{2 /} M ₁ of the particle diameter M ₂ of the second metal oxide particles to the average particle diameter M ₁ of the first metal oxide particles, 0.10 to 0. 44, 0.15 to 0.40, or 0.20 to 0.35.

  Further, the content of the metal oxide particles in the region containing the metal oxide particles may be 25 to 50% by volume, 30 to 50% by volume, or 35 to 50% by volume. Is also good.

  The content of the component (E-1) in the region containing the metal oxide particles may be 15 to 40% by volume, 16 to 39% by volume, or 17 to 38% by volume. May be.

  The content of the component (E-2) in the region containing the metal oxide particles may be 2 to 10% by volume, 2 to 8% by volume, or 2 to 6% by volume. May be.

  The volume ratio [(E-2) / (E-1)] of the component (E-2) to the component (E-1) in the region containing the metal oxide particles is 0.05 to 0.40. May be present, may be 0.10 to 0.40, or may be 0.10 to 0.30.

[Touch panel]
The touch panel of the present embodiment includes a laminate obtained by using the transfer type photosensitive film of the present embodiment or the laminate according to the present embodiment described above, and the substrate is a substrate for a touch panel. The touch panel according to the present embodiment can include, for example, a touch sensor having the stacked body 100 illustrated in FIG. When the touch sensor is used as a module such as a touch panel, OCA for bonding the cover glass and the laminate 100 can be used.

  FIG. 3 is a schematic top view showing a touch panel according to one embodiment of the present invention. FIG. 3 illustrates an example of a capacitive touch panel. The touch panel shown in FIG. 3 has a touch screen 102 for detecting touch position coordinates on one side of a transparent base material 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 electrode 103 and the transparent electrode 104 detect the X position coordinate and the Y position coordinate of the touch position, respectively.

  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.

  As shown in FIG. 3, in the touch panel according to the present embodiment, a cured film pattern is formed by using the transfer type photosensitive film of the present embodiment over a portion where the transparent electrode pattern is formed and a portion where the transparent electrode pattern is not formed. 123 are formed. The cured film pattern 123 includes a cured first layer and a cured second layer. According to the cured film pattern 123, the function of protecting the transparent electrode 103, the transparent electrode 104, the lead wiring 105, the connection electrode 106 and the connection terminal 107, and the function of the bone of the sensing area (touch screen) 102 formed by the transparent electrode pattern The appearance phenomenon preventing function can be performed at the same time. In the touch panel according to the present embodiment, by using the transfer type photosensitive film of the present embodiment, development residue is sufficiently reduced on the connection terminal 107, and problems such as poor connection at the connection terminal occur. It can be difficult.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

<Preparation of binder polymer solution>
(Binder polymer A)
85.7 parts by mass of 1-methoxy-2-propanol (manufactured by Daicel Chemical Industries, Ltd.) was added to the reaction vessel, and the temperature was raised to 80 ° C. Separately, 17.5 parts by mass of methacrylic acid, 50.5 parts by mass of ethyl methacrylate, 32.0 parts by mass of ethyl acrylate and an azo-based polymerization initiator (trade name: V-601, manufactured by Wako Pure Chemical Industries, Ltd.) ) 0.6 parts by mass were mixed to obtain a mixed solution. This mixed solution was dropped into the reaction vessel at 80 ° C. over 2 hours under a nitrogen gas atmosphere. After the dropping, the mixture was reacted for 4 hours to obtain a resin solution.

  Next, after adding 2.5 parts by mass of hydroquinone monomethyl ether and 8.4 parts by mass of tetraethylammonium bromide to the resin solution obtained above, the mixture was reacted at 80 ° C. for 4 hours while blowing air. Then, propylene glycol monomethyl ether acetate was added as a solvent so that the solid content concentration became 45% by mass, to obtain a binder polymer solution containing binder polymer A. The weight average molecular weight and the acid value of the binder polymer A were determined by the following methods. As a result, the weight average molecular weight was 64000, and the acid value was 117 mgKOH.

[Method of measuring weight average molecular weight]
The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC), and was derived by conversion using a calibration curve of standard polystyrene. The measurement conditions for GPC are shown below.
<< GPC measurement conditions >>
Pump: Hitachi L-6000 type (trade name, manufactured by Hitachi, Ltd.)
Column: Gelpack GL-R420, Gelpack GL-R430, Gelpack GL-R440 (these are the product names of Hitachi Chemical Co., Ltd.)
Eluent: tetrahydrofuran Measurement temperature: 40 ° C
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 RI (trade name, manufactured by Hitachi, Ltd.)

[Method of measuring acid value]
The acid value was measured by a neutralization titration method based on JIS K0070 as described below. First, a solid content (non-volatile content) was obtained by heating the binder polymer solution at 130 ° C. for 1 hour to remove volatile components. After 1 g of the solid binder polymer was precisely weighed, 30 g of acetone was added to the binder polymer and uniformly dissolved to obtain a resin solution. Next, after adding an appropriate amount of phenolphthalein as an indicator to the resin solution, neutralization titration was performed using a 0.1 mol / L aqueous solution of potassium hydroxide. Then, the acid value was calculated by the following equation.
Acid value = 0.1 × V × f ₁ × 56.1 / (Wp × I / 100)
[Wherein V represents the titer (mL) of the 0.1 mol / L aqueous potassium hydroxide solution used for the titration, and f ₁ represents the factor (concentration conversion coefficient) of the 0.1 mol / L aqueous potassium hydroxide solution. Wp represents the mass (g) of the resin solution, and I represents the ratio (mass%) of the solid content in the resin solution. ]

<Preparation of First Layer Forming Coating Solution>
After mixing the solvent and each component of Table 1 (unit of the blending amount: parts by mass), the mixture was mixed for 15 minutes using a stirrer to prepare a first layer forming coating solution. As the solvent, 100 parts by mass of methyl ethyl ketone was used based on 100 parts by mass of the total of the binder polymer and the photopolymerizable compound.

<Preparation of Second Layer Forming Coating Solution>
After the solvent and the components shown in Table 1 (units of the blending amount: parts by mass) were mixed, they were mixed for 15 minutes using a stirrer to prepare a second coating liquid for forming a layer. The solvent used was 200 parts by mass of propylene glycol monomethyl ether based on a total of 120 parts by mass of the metal oxide particles.

  The symbols of the components in Table 1 have the following meanings.

[(A) component: binder polymer]
Binder polymer A: Binder polymer A produced by the above method

[(B) component: photopolymerizable compound]
A-DCP: Tricyclodecane dimethanol diacrylate (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[Component (C): Photopolymerization initiator]
OXE-01: 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)] (trade name "IRGACURE OXE-01" manufactured by BASF Corporation)
Irg-TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (trade name “IRGACURE TPO” manufactured by BASF Corporation)

[(D) component: rust inhibitor]
B6030: 5-amino-1H-tetrazole (trade name, manufactured by Chiyoda Chemical Co., Ltd.)

[Component (E): metal oxide particles]
(E-1) Component ZrO ₂ -1: zirconium oxide particles (average particle size: 18 nm), content of particles having a particle size of 15 to 30 nm: 98 (% by mass)
TiO ₂ -1: titanium oxide particles (average particle size 19 nm), content of particles having a particle size of 15 to 30 nm: 98 (% by mass)
(E-2) component _ZrO 2 -2: zirconium oxide particles (average particle diameter 3.8 nm), particle content having a particle size 3.3~6.6nm: 86 (wt%)
TiO ₂ -2: titanium oxide particles (average particle size: 4.4 nm), particle content of 3.3 to 6.6 nm: 89 (% by mass)

[Other ingredients]
(Adhesion aid)
PM-21: Phosphate ester having an ethylenically unsaturated group (trade name, manufactured by Nippon Kayaku Co., Ltd.)
(Leveling agent) ADDITIVE8032: Octamethylcyclotetrasiloxane (trade name, manufactured by Dow Corning Toray Co., Ltd.)
(Polymerization inhibitor) AW500: 2,2'-methylene-bis (4-ethyl-6-tert-butylphenol) (trade name, manufactured by Kawaguchi Chemical Co., Ltd.)

<Preparation of transfer type photosensitive film>
A 16 μm-thick polyethylene terephthalate film (trade name: FB40, manufactured by Toray Industries, Inc.) was prepared as a support film. After uniformly applying the first layer-forming coating solution on the support film using a comma coater, and drying it for 3 minutes with a hot air convection dryer at 100 ° C. to remove the solvent, a 8 μm-thick first layer was formed. A laminate 1 having one layer was obtained.

  A 30-μm-thick polypropylene film (trade name: ES-201, manufactured by Oji F-Tex Corporation) was prepared as a protective film. The coating liquid for forming the second layer is uniformly applied on the protective film using a die coater, and then dried for 3 minutes with a hot air convection dryer at 110 ° C. to remove the solvent, thereby obtaining a thickness of 0.1 μm. To obtain a laminate 2 including the second layer.

  Next, the first layer of the laminate 1 and the second layer of the laminate 2 were bonded together at 23 ° C. using a laminator (trade name: HLM-3000 type, manufactured by Hitachi Chemical Co., Ltd.), and a support film was formed. , A first layer, a second layer, and a protective film were laminated in this order to produce a transfer type photosensitive film.

<Characteristics of second layer>
The volume of each component contained in the second layer was calculated based on the information on the blending amount and density of each component.

Specifically, the following values were used for the density of the metal oxide particles.
Zirconium oxide: 5.68
Titanium oxide: 4.23
Further, the density of the organic component except for the solvent contained in the second layer was measured by Archimedes' method, and the density was 1.1. Using the density value Do and the density of the metal oxide particles, the mass Mo of the organic component contained in the second layer and the mass Mm of the metal oxide particles contained in the second layer are determined by volume (volume). Parts). From these values, the volume ratio (%) of the metal oxide particles contained in the second layer was calculated.

<Evaluation of development residue>
The transfer-type photosensitive films obtained in Examples and Comparative Examples were vacuum-laminated on a Cu sputtered PET film (manufactured by Oike Industry Co., Ltd.), and then sprayed with 1% Na ₂ CO ₃ at 30 ° C. for 40 seconds. Then, development was performed.

Next, the presence or absence of discoloration on the substrate surface due to the development residue was visually evaluated according to the following five grades. Table 2 shows the observation results.
5: No discoloration is observed.
4: Partially discolored part 3: Partly discolored part 2: Undeveloped part, 20% or less of the whole 1: Undeveloped part, 20% or more of the whole

<Evaluation of bone appearance phenomenon>
A base material for evaluation (ITO base material) was prepared. While peeling off the protective film of the transfer type photosensitive film obtained in each of Examples and Comparative Examples on this substrate, the second layer was opposed to the substrate. Lamination was performed under the conditions of 4 MPa.

After lamination, 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 100 mJ / cm ² . Next, annealing was performed by removing the support film and heating at 140 ° C. for 30 minutes.

The annealed sample obtained above was fixed on a black board, irradiated with light obliquely, visually observed, and evaluated according to the following criteria.
A: The pattern is not visible or difficult to see.
F: The pattern is visible.

DESCRIPTION OF SYMBOLS 1 ... Transfer type photosensitive film, 10 ... Support film (temporary support), 20 ... First layer, 22 ... Hardened first layer, 30 ... Second layer, 32 ... Hardened second layer, Reference numeral 40: protective film, 50: substrate with a transparent electrode pattern, 50a: transparent electrode pattern, 60: cured film, 100: laminated body, 101: transparent substrate, 102: sensing area, 103, 104: transparent electrode, 105: Lead-out wiring, 106 connection electrode, 107 connection terminal, 123 cured film pattern.

Claims (9)

Temporary support, provided on the temporary support, a first layer made of a photosensitive resin composition, and a second layer containing metal oxide particles, in this order,
The metal oxide particles include: first metal oxide particles having a particle size of 15 to 30 nm; and second metal oxide particles having a particle size of 3.3 to 6.6 nm.
The transfer type photosensitive film, wherein the content of the metal oxide particles in the second layer is 25 to 50% by volume. Wherein the first metal oxide average ratio _M 2 / _{M 1} of an average of said second metal oxide particles to the particle diameter _{M 1} particle diameter _{M 2} particles is from 0.10 to 0.44, claim 2. The transfer type photosensitive film according to 1.   The transfer type photosensitive film according to claim 1, wherein the second layer includes a photosensitive resin composition. The content of the first metal oxide particles in the second layer is 15 to 40% by volume,
The transfer type photosensitive film according to any one of claims 1 to 3, wherein the content of the second metal oxide particles in the second layer is 2 to 10% by volume. On a substrate having an electrode pattern, the first layer and the second layer of the transfer type photosensitive film according to any one of claims 1 to 4, the electrode pattern of the substrate is provided Laminating so that the side that has been and the second layer are in close contact,
After exposing a predetermined portion of the first layer and the second layer on the base material, removing a portion other than the predetermined portion, forming a cured film pattern covering a part or all of the electrode pattern. ,
A method for forming a cured film pattern, comprising: A substrate having an electrode pattern, and a cured film provided on the electrode pattern, a laminate having:
The cured film has a region containing metal oxide particles on the substrate side,
The metal oxide particles include: first metal oxide particles having a particle size of 15 to 30 nm; and second metal oxide particles having a particle size of 3.3 to 6.6 nm.
The laminate, wherein the content of the metal oxide particles in the region is 25% to 50% by volume. Wherein the first metal oxide average ratio _M 2 / _{M 1} of an average of said second metal oxide particles to the particle diameter _{M 1} particle diameter _{M 2} particles is from 0.10 to 0.44, claim 7. The laminate according to 6. The content of the first metal oxide particles in the region is 15 to 40% by volume,
The laminate according to claim 6, wherein the content of the second metal oxide particles in the region is 2% to 10% by volume. A laminate comprising the laminate according to any one of claims 6 to 8,
A touch panel, wherein the substrate is a substrate for a touch panel.

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