JPWO2018179095A1 - Transfer type photosensitive film, method of forming cured film pattern, cured film, and touch panel - Google Patents

Abstract

The transfer type photosensitive film according to the present invention includes a support film and a first resin layer provided on the support film, and the first resin layer has a tricyclodecane skeleton or a tricyclodecene skeleton. It contains a photopolymerizable compound and an acylphosphine oxide-based photopolymerization initiator.

Description

  The present invention relates to a transfer type photosensitive film, a method for forming a cured film pattern, a cured film, 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, and display devices such as OA (Office Automation) and FA (Factory Automation) devices. 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, 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 a 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 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 that covers 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, a color difference is increased due to a difference in optical reflection characteristics between a portion where a transparent electrode pattern is formed and a portion where the transparent electrode pattern is not formed, and when a module is formed, a transparent portion is 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 base material 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 substrate 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.

  Further, 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 and a high refractive index adjusted to a specific refractive index range 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

  The present inventors have developed a photosensitive resin composition containing a di (meth) acrylate compound having a dicyclopentanyl structure (hereinafter, referred to as a tricyclodecane skeleton) or a dicyclopentenyl structure (hereinafter, referred to as a tricyclodecene skeleton). A transfer-type photosensitive film using a was studied. In examining the improvement of low moisture permeability and adhesion of the cured film pattern formed by this transfer type photosensitive film, when the cured film was formed on the transparent electrode pattern, It has been found that the electrode pattern may look more prominent (pattern appearance occurs) even when the electrode pattern is provided.

  The present inventors further examined the causes of the pattern appearance, and found that dents (also referred to as steps) were generated on the surface of the cured film provided on the ITO electrode pattern, and that this could be visually recognized as the pattern appearance. I found it.

  The present invention relates to a transfer type photosensitive film capable of favorably forming a cured film pattern having a sufficiently low moisture permeability while suppressing a step on an electrode pattern, a method of forming a cured film pattern using the same, and a touch panel. The purpose is to provide.

  In order to solve the above-mentioned problems, the present inventors have studied the factors of the occurrence of the step. When the cured film was formed on the ITO electrode and the IM layer under the same conditions, the photosensitive layer provided on the IM layer was removed. It was confirmed that the reaction rate of the resin layer was smaller than that on the ITO electrode. Based on this, the cause of the dents was as follows: 1) In the exposure step, the portion of the photosensitive resin layer from the lower reaction rate to the higher 2) In the annealing step of heating the photosensitive resin layer after exposure and development, the unreacted photopolymerizable compound is volatilized, and the high and low reaction rates It is assumed that there is a difference in heat shrinkage. From the viewpoint of suppressing the above-mentioned events 1) and 2), the inventors of the present invention used a step evaluation test having an exposure step with an exposure difference and an annealing step to determine the composition of the photosensitive resin layer. As a result of studying, it has been found that by using a specific photopolymerizable compound and a specific photopolymerization initiator in combination, it is possible to suppress the difference in the reaction rate and to reduce the level difference, and to complete the present invention. Reached. In addition, if only the method of increasing the amount of the photopolymerization initiator to reduce the amount of the unreacted photopolymerizable compound is used, a development residue may be generated, and it is difficult to form a cured film pattern satisfactorily.

  The present invention includes a support film and a first resin layer provided on the support film, wherein the first resin layer has a photopolymerizable compound having a tricyclodecane skeleton or a tricyclodecene skeleton, Provided is a transfer-type photosensitive film containing an acylphosphine oxide-based photopolymerization initiator.

  According to the transfer type photosensitive film of the present invention, by having the above configuration, a cured film pattern can be favorably formed on a transparent electrode pattern while suppressing a step. The cured film pattern can function as a rust prevention film for the electrode pattern.

  The reason for obtaining the above-mentioned effects is that the use of the acylphosphine oxide-based photopolymerization initiator allows a sufficient polymerization reaction rate to be obtained even with a photopolymerizable compound having a large molecular weight. It is considered that the events 2) and 3) could be suppressed.

  Increasing the blending amount of the photopolymerizable compound having a tricyclodecane skeleton or a tricyclodecene skeleton is effective for reducing moisture permeability and improving adhesion of a cured film pattern, while curing the cured film pattern provided on a transparent electrode pattern. The step generated in the film pattern tends to increase. According to the present invention, by combining a photopolymerizable compound having a tricyclodecane skeleton or a tricyclodecene skeleton with an acylphosphine oxide-based photopolymerization initiator, while suppressing a step, a high level of low moisture permeability and A cured film pattern having high adhesion can be formed.

  The acylphosphine oxide-based photopolymerization initiator may include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. In this case, it is possible to form a cured film pattern having low moisture permeability and excellent in color tone (particularly, low in yellowish color and close to neutral color tone).

  The first resin layer may further include an oxime ester-based photopolymerization initiator. By using an acylphosphine oxide-based photopolymerization initiator and an oxime ester-based photopolymerization initiator in combination, the moisture permeability of the formed cured film pattern can be further reduced.

  The transfer type photosensitive film according to the present invention may further include a second resin layer containing metal oxide particles provided on the first resin layer.

  According to the above-mentioned transfer type photosensitive film, a cured film pattern capable of suppressing a bone appearance phenomenon can be favorably formed on an electrode pattern while suppressing a step.

  The present invention also provides, on a substrate having an electrode pattern, the first resin layer of the transfer type photosensitive film according to the present invention, the first resin layer and the side on which the electrode pattern of the substrate is provided. Laminating so that they adhere to each other, and exposing a predetermined portion of the first resin layer on the base material, removing portions other than the predetermined portion, and forming a cured film covering part or all of the electrode pattern. And a first method for forming a cured film pattern.

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

  According to the first and second methods of forming a cured film pattern according to the present invention, a cured film pattern can be favorably formed on an electrode pattern while suppressing steps. Further, according to the second method of forming a cured film pattern according to the present invention, the cured film pattern can have a function of adjusting the refractive index.

  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 also comprises the first resin layer of the transfer type photosensitive film according to the present invention having the second resin layer alone or by curing both the first resin layer and 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. And a touch panel provided with a cured film pattern composed of a cured product of the first resin layer and a cured product of the first resin layer.

  According to the present invention, it is possible to provide a transfer type photosensitive film capable of favorably forming a cured film pattern while suppressing a step on an electrode pattern, a method of forming a cured film pattern using the same, and a touch panel. it can.

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 showing a laminate including a cured film pattern formed using a transfer type photosensitive film according to one 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. It is a schematic cross section for explaining the step evaluation method concerning 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 either one of A and B, and may include both.

  Further, in this specification, the term “layer” includes, when observed as a plan view, a structure partially formed in addition to a structure formed over the entire surface. 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, 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.

  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 quantity. The exemplified materials may be used alone or in combination of two or more unless otherwise specified.

  In addition, in the numerical ranges described in stages 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. Further, in the numerical ranges described in this specification, the upper limit or the lower limit of the numerical ranges may be replaced with the values shown in the embodiments.

<Transfer type photosensitive film>
The transfer type photosensitive film of the present embodiment includes a support film and a first resin layer provided on the support film. The transfer type photosensitive film of the present embodiment may be a transfer type photosensitive film further provided with a second resin layer containing metal oxide particles provided on the photosensitive resin layer. These transfer photosensitive films may further include a protective film provided on the photosensitive resin layer or on the second resin layer.

  FIG. 1 is a schematic sectional view showing a transfer type photosensitive film according to one embodiment of the present invention. The transfer 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 20. 30 and a protective film 40 provided on the second resin layer 30.

  By using the transfer type photosensitive film, for example, a cured film that satisfies both the function of protecting the metal wiring in the frame of the touch panel or the transparent electrode of the touch panel and the function of making the transparent electrode pattern invisible or improving the visibility of the touch screen. Patterns can be formed collectively.

(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, polyether sulfone, 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, and particularly preferably 15 to 35 μm.

(First resin layer)
The first resin 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 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 preferred. The above-mentioned copolymer may contain, in its constitutional unit, another monomer copolymerizable with the above-mentioned (meth) acrylic acid or alkyl (meth) acrylate. Specific examples of the 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.

  Among these, from the viewpoints of alkali developability (particularly developability with an aqueous inorganic alkali solution), patterning properties, and transparency, (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, cyclohexyl maleimi And a binder polymer having a structural unit derived from at least one compound selected from the group consisting of hydroxyethyl (meth) acrylate and hydroxybutyl (meth) acrylate, and (meth) acrylic acid, glycidyl (meth) acrylate Benzyl (meth) acrylate, styrene, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and (meth) acrylic acid Binder polymers having a structural unit derived from at least one compound selected from the group consisting of cyclohexyl esters are more preferable, and (meth) acrylic acid, alkyl (meth) acrylate, and glycidyl (meth) acrylate 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.

  Specific examples of 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, (meth) acrylic T-butyl acid, i-amyl (meth) acrylate, t-amyl (meth) acrylate, sec-iso-amyl (meth) acrylate, 2-octyl (meth) acrylate, 3- (meth) acrylate Octyl, t-octyl (meth) acrylate, and the like. Among these, i-propyl (meth) acrylate, i-butyl (meth) acrylate, and t-butyl methacrylate are preferred, and i-propyl methacrylate and t-butyl methacrylate are more preferred.

  Specific examples of the monomer containing a group having an alicyclic structure in the side chain include, for example, (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-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, 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 the side chain, it is possible to obtain good adhesion to a substrate, particularly 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 reaction product of a monomer having a hydroxyl group with a cyclic acid anhydride, ω-carboxy-polycaprolactone mono (meta A) acrylate and the like. These may be appropriately manufactured or commercially available ones.

  When the component (A) contains a group having an acidic group in a 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 repeating unit 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 the 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%, 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 proportion of the monomer, the patterning property by alkali development, the laminating 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 weight average molecular weight of the component (A) is preferably from 10,000 to 200,000, more preferably from 15,000 to 150,000, more preferably from 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. In addition, the weight average molecular weight can be measured by the gel permeation chromatography method described in 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. In addition, from the viewpoint of achieving both easy control 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 is preferably 75 to 150 mgKOH / g. More preferably, it is more preferably 75 to 120 mgKOH / g. Incidentally, the acid value can be measured by the method described in the examples of the present specification.

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

<Photopolymerizable compound>
Examples of the component (B) include compounds having a tricyclodecane skeleton or a tricyclodecene skeleton. From the viewpoint of suppressing corrosion of the metal wiring and the transparent electrode pattern, it is preferable to include a di (meth) acrylate compound represented by the following general formula (B-1) as a compound having a tricyclodecane skeleton or a tricyclodecene skeleton. .

［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 trivalent group having a tricyclodecane skeleton or a tricyclodecene skeleton; 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. 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, “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 100 parts by mass in terms of the total amount of the photopolymerizable compound contained in the photosensitive resin composition from the viewpoint of reducing the moisture permeability and the level difference. 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.

  As the photopolymerizable compound as the component (B), a photopolymerizable compound having an ethylenically unsaturated group, which is different from a compound having a tricyclodecane skeleton or a tricyclodecene skeleton, can be used. As the photopolymerizable compound having an ethylenically unsaturated group, for example, a monofunctional vinyl monomer having one polymerizable ethylenically unsaturated group in a molecule, and having two polymerizable ethylenically unsaturated groups in a molecule Examples include bifunctional vinyl monomers or polyfunctional vinyl monomers having at least three polymerizable ethylenically unsaturated groups in the molecule.

  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 reducing the moisture permeability of the cured film pattern and improving the adhesion, the compound having a tricyclodecane skeleton or a 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. In the present embodiment, the step having a tricyclodecane skeleton or a compound having a tricyclodecene skeleton blended in the above ratio is combined with an acylphosphine oxide-based photopolymerization initiator described later as a photopolymerization initiator to reduce the level difference. It is possible to form a cured film pattern having a high level of low moisture permeability and high adhesion while controlling.

<Photopolymerization initiator>
As the component (C), an acylphosphine oxide-based photopolymerization initiator is used. As the component (C), a conventionally known photopolymerization initiator other than the acylphosphine oxide-based photopolymerization initiator can be used in combination.

  Examples of the acylphosphine oxide-based photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 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 an acylphosphine oxide-based photopolymerization initiator, a sufficient polymerization reaction rate can be obtained in the photosensitive resin layer, and the pattern appearance can be suppressed.

  Photopolymerization initiators other than acylphosphine oxide-based photopolymerization initiators include oxime ester-based photopolymerization initiators. By using an acylphosphine oxide-based photopolymerization initiator and an oxime ester-based photopolymerization initiator in combination, the moisture permeability of the formed cured film pattern can be further reduced.

  The oxime ester-based photopolymerization initiator 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). .

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; An alkyl group, a cycloalkyl group having 4 to 6 carbon atoms, a phenyl group or a tolyl group is preferable, and an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms, a phenyl group or a tolyl group is preferable. More preferably, it is 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 ) ₂ OH, preferably —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 Daito Chemmix, Inc., product name).

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

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

  In the component (C), the proportion of the acylphosphine oxide-based photopolymerization initiator is preferably at least 1 part by mass in the total amount of 100 parts by mass of the photopolymerization initiator contained in the photosensitive resin composition from the viewpoint of exposure sensitivity. Is preferably 3 parts by mass or more, more preferably 5 parts by mass or more.

  When an acylphosphine oxide-based photopolymerization initiator and an oxime ester compound are used in combination, the acylphosphine oxide-based photopolymerization initiator and the oxime ester compound are used in view of pattern appearance, reliability, color, and curability. Is preferably from 8: 1 to 0.5: 1, and more preferably from 4: 1 to 2: 1.

  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.).

  As the triazole compound having the amino group, for example, benzotriazole, 1H-benzotriazole-1-acetonitrile, benzotriazole-5-carboxylic acid, 1H-benzotriazole-1-methanol, carboxybenzotriazole and the like are substituted with an amino group. 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, 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 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 resin layer according to the present embodiment, as other additives, if necessary, adhesion of a phosphoric acid ester having an ethylenically unsaturated group, a silane coupling agent, etc. The components (A) and (B) include a property imparting 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, and a polymerization inhibitor. Each component can be contained in an amount of about 0.01 to 20 parts by mass based on 100 parts by mass of the total amount of the components. These can be used alone or in combination of two or more.

  The thickness of the first resin layer may be 1 to 15 μm, preferably 2 to 10 μm, more preferably 3 to 8 μm, still more preferably 4 to 6 μm, and 5 to 6 μm. It is particularly preferred that there is. When the thickness is 1 to 15 μm, defects during coating are small, and a film having excellent transparency can be formed. 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.

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

  When the refractive index at 633 nm of the second resin layer 30 is within the above range, when a cured film pattern is provided on a transparent electrode pattern such as ITO, various members used on the cured film pattern (for example, a module) Between the cover glass used to form the transparent electrode pattern and the cover electrode used to form the transparent electrode pattern, and the optical index between the portion where the transparent electrode pattern such as ITO is formed and the portion where the transparent electrode pattern is not formed. The color difference due to reflection can be reduced, and the bone appearance phenomenon can be prevented. In addition, it is possible to reduce the intensity of reflected light on the entire screen, and 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, even more preferably from 1.48 to 1.51. .

  The second resin layer 30 has a minimum light transmittance of preferably at least 80%, more preferably at least 85%, even more preferably at least 90% in a wavelength range of 450 to 650 nm. 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 resin layer 30 can contain the above components (A), (B) and (C), and can further contain the above component (D) as needed. The second resin layer 30 does not necessarily need to contain a photopolymerization component such as the component (B) and the component (C). The layers can also be photocured.

  The second resin 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 resin 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 adsorption to the base material.

  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, particles of zirconium oxide or titanium oxide 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 the 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 resin 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 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 also be used. Thereby, the refractive index at a wavelength of 633 nm can be improved.

  The thickness of the second resin layer 30 may be 0.01 to 1 μm, preferably 0.03 to 0.5 μm, more preferably 0.04 to 0.3 μm, It is more preferably from 0.07 to 0.25 μm, and 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 resin layer after curing is also preferably within the above range.

When the second resin layer is a single layer and the film thickness is uniform in the film thickness direction, the refractive index of the second resin layer 30 is determined as follows using ETA-TCM (AudioDevGmbH Co., Ltd., product name). Can be sought. 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 is dried by a hot air drier at 100 ° C. After drying for 3 minutes to remove the solvent, a second resin layer is formed.
(2) Then, 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 resin layer.
(3) Next, the refractive index of the obtained refractive index measurement sample is measured at a wavelength of 633 nm by ETA-TCM (product name, manufactured by AudioDevGmbH).

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

(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 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 is preferably 70 μm or less, more preferably 60 μm or less, and more preferably 50 μm or less, from the viewpoint of winding and storing the transfer photosensitive film 1 in a roll shape. Is more preferable, and particularly preferably 40 μm or less.

  The entire cured film portion (excluding the support film 10 and the protective film 40) of the transfer-type photosensitive film 1 obtained by curing the first resin layer 20 and the second resin layer 30 in the visible light region having a wavelength of 400 to 700 nm. 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 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), image display in the sensing area is performed. It is possible to sufficiently suppress a decrease in quality, hue, and luminance.

  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 liquid and a second resin layer-forming coating liquid. They can be formed by coating and drying on the support film 10 and the protective film 40, respectively. Then, the transfer type photosensitive film 1 is formed by combining the support film 10 on which the first resin layer 20 is formed and the protective film 40 on which the second resin layer 30 is formed with the first resin layer 20 and the second resin layer 20. Can be formed by bonding together in a state where the resin layer 30 faces the resin layer. Further, the transfer type photosensitive film 1 is applied with a coating solution containing the first resin layer forming coating solution on the support film 10, dried, and then, on the first resin layer 20, the second resin It can also be formed by applying a coating liquid for formation, drying and applying a protective film 40.

  The coating liquid can be obtained by uniformly dissolving or dispersing the photosensitive resin composition according to the present embodiment and the respective components constituting the second resin 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.

[Method of forming cured film pattern]
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 cured film including the cured first resin layer 22 and the cured second resin 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 having 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 resin layer 30, the first resin layer 20, and the support film 10 are placed on the surface of the substrate 50 with the transparent electrode pattern by the second resin layer. Lamination (transfer) is performed by pressure bonding from the 30 side. A pressing roll may be used as the pressing means. The pressure roll may be provided with a heating means so as to be able to heat and pressure.

  The heating temperature in the case of thermocompression bonding is based on the viewpoint of the adhesion between the second resin layer 30 and the substrate 50 with the transparent electrode pattern, and the fact that the components of the first resin layer 20 or the second resin layer 30 are hot. In light of hardening or thermal decomposition, the temperature is preferably 10 to 160 ° C, more preferably 20 to 150 ° C, and still more preferably 30 to 150 ° C.

From the viewpoint of suppressing deformation of the substrate 50 with a transparent electrode pattern, the pressure for the compression bonding at the time of heat compression bonding is sufficiently secured while ensuring sufficient adhesion between the second resin layer 30 and the substrate 50 with a 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 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 always necessary, but the adhesion between the second resin layer 30 and the substrate 50 with the transparent electrode pattern is not required. In order to further improve the performance, the base material 50 with the transparent electrode pattern may be pre-heat treated. 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).

(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). Further, 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 the same composition as the second resin layer 30 described above.

-Exposure process-
Next, a predetermined portion of the first resin layer and the second resin layer after the transfer is irradiated with an actinic ray in a pattern via a photomask. When irradiating with actinic light, if the support film 10 on the first resin layer and the second resin layer is transparent, it can be irradiated with actinic light as it is. Irradiate light rays. A known active light source can be used as a light source for the active light. In this 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 the actinic ray is 1 × 10 ² J / m ² or more, the photocuring of the first resin layer and the second resin layer can be sufficiently advanced, and 1 × 10 ⁴ J / m ^2. / M ² or less, there is a tendency that discoloration of the first resin layer and the second resin layer can be suppressed.

  Subsequently, 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 the whole of the transparent electrode is formed. To form After the irradiation with the actinic ray, if the support film 10 is laminated on the first resin layer and the second resin 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 alkaline aqueous solution, an aqueous developing solution, or an organic solvent. Among them, 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.

  In the present embodiment, the cured film pattern is formed using the transfer type photosensitive film, but the cured film pattern is formed by the same method when using the transfer type photosensitive film not having the second resin layer. be able to.

(Cured film)
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 type photosensitive film of the present embodiment. In addition, 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 a case where 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.

  When the transfer type photosensitive film does not have the second resin layer, the cured film according to the present invention may be a cured film obtained by curing the first resin layer.

  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 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 an electronic paper.

  For example, the touch sensor can include the stack 100 shown 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 surface 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 resin layer and a cured second resin layer. When a transfer type photosensitive film having no second resin layer is used, the cured film pattern 123 is made of the cured first resin 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 bone of the sensing area (touch screen) 102 formed from the transparent electrode pattern The appearance phenomenon preventing function can be simultaneously performed. Further, by using the transfer type photosensitive film of the present embodiment, the cured film pattern 123 can have a sufficiently small surface step.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Preparation of binder polymer solution]
(Synthesis example A1)
85.7 parts by mass of 1-methoxy-2-propanol (manufactured by Daicel Chemical Industries, Ltd.) was previously added to the reaction vessel, and the temperature was raised to 80 ° C. On the other hand, 46 parts by mass of cyclohexyl methacrylate, 2 parts by mass of methyl methacrylate, 52 parts by mass of methacrylic acid, and 10 parts by mass of an azo-based polymerization initiator (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) were mixed, and the mixed solution was mixed. Obtained. This mixed solution was dropped into the above reaction vessel at 80 ° C. over 2 hours under a nitrogen gas atmosphere. After the dropwise addition, the mixture was reacted for 4 hours to obtain an acrylic 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 acrylic resin solution, 32 parts by mass of glycidyl methacrylate was added dropwise over 2 hours. After dropping, the mixture was reacted at 80 ° C. for 4 hours while blowing air, and 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 A1. The amounts of cyclohexyl methacrylate, methyl methacrylate, methacrylic acid, and glycidyl methacrylate were adjusted so that x: l: y: z = 46 mol%: 2 mol%: 20 mol%: 32 mol%.

(Synthesis example A2)
A flask equipped with a stirrer, a reflux condenser, an inert gas inlet, and a thermometer was charged with 62 parts by mass of propylene glycol monomethyl ether and 62 parts by mass of toluene, and heated to 80 ° C. under a nitrogen gas atmosphere. While maintaining the temperature at 80 ° C. ± 2 ° C., the compounds shown in Table 1 and 1.5 parts by mass of 2,2′-azobis (isobutyronitrile) were uniformly added dropwise over 4 hours. After dropping, stirring was continued at 80 ° C. ± 2 ° C. for 6 hours to obtain a binder polymer solution A2 (solid content: 45% by mass) having a weight average molecular weight of 30,000 and an acid value of 156.6 mgKOH / g.

(Examples 1 to 13 and Comparative Examples 1 to 11)
[Preparation of coating liquid for forming first resin layer]
The components shown in Tables 2 and 3 were blended in the blending amounts (unit: parts by mass) shown in the tables and mixed for 15 minutes using a stirrer to prepare a first resin layer forming coating solution. In Tables 2 and 3, the amount of the component (A) indicates the amount of the solid content. The coating liquid was adjusted to a solid content of 20 to 30% by mass using methyl ethyl ketone as a solvent.

[Preparation of second resin layer forming coating liquid]
The components shown in Table 3 were blended in the blending amounts (unit: parts by mass) shown in the same table, and mixed for 15 minutes using a stirrer to prepare a second resin layer forming coating solution. In Table 3, the amount of the component (A) indicates the amount of the solid content.

The symbols of the components in Tables 2 to 5 have the following meanings.
[(A) component]
A1: Binder polymer solution prepared by the method described above A2: Binder polymer solution prepared by the method described above

[(B) component]
A-DCP: Tricyclodecane dimethanol diacrylate (product name, manufactured by Shin-Nakamura Chemical Co., Ltd.)
DPHA: dipentaerythritol hexaacrylate (Shin-Nakamura Chemical, product name "A-DPH")

[(C) component]
TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (product name “IRGACURE TPO” manufactured by BASF Corporation)
819: bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, (product name “IRGACURE 819” manufactured by BASF Corporation)
OXE01: 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)] (product name “IRGACURE OXE01” manufactured by BASF Corporation)
OXE02: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime) (manufactured by BASF Corporation, product name "IRGACURE OXE 02"")
184: 1-hydroxy-cyclohexyl-phenyl-ketone (product name “IRGACURE 184” manufactured by BASF Corporation)
651: 2,2-dimethoxy-1,2-diphenylethan-1-one (product name “IRGACURE 651” manufactured by BASF Corporation)
754: Mixture of oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid, 2- (2-hydroxyethoxy) ethyl ester (product name “IRGACURE 754” manufactured by BASF Corporation) )

[(E) component]
E1: Zirconium oxide nanoparticle dispersion (Nissan Chemical Industries, Ltd., product name "OZ-S30K")

[Preparation of transfer type photosensitive film]
(In the case with the second resin layer)
Using a 30 μm-thick polypropylene film (manufactured by Oji F-Tex Co., Ltd., product name: ES-201) as the protective film, the above-prepared coating liquid for forming the second resin layer was formed on the protective film using a die coater. The solution was uniformly applied and dried for 3 minutes in a hot air 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.

  Using a polyethylene terephthalate film having a thickness of 16 μm (manufactured by Toray Industries, Inc., product name: FB40) as the support film, the above-prepared coating liquid for forming the first resin layer is uniformly applied on the support film using a comma coater. Then, the resultant was dried with a hot air convection dryer at 110 ° C. for 3 minutes to remove the solvent, thereby forming a first resin layer having a thickness of 8 μm.

  Next, the protective film having the second resin layer and the support film having the first resin layer are bonded at 23 ° C. using a laminator (manufactured by Hitachi Chemical Co., Ltd., product name: HLM-3000 type). Thus, a transfer photosensitive film in which a protective film, a second resin layer, a first resin layer, and a support film were laminated in this order was produced.

(When not having the second resin layer)
Using a polyethylene terephthalate film having a thickness of 16 μm (manufactured by Toray Industries, Inc., product name: FB40) as the support film, the above-prepared coating liquid for forming the first resin layer is uniformly applied on the support film using a comma coater. Then, the resultant was dried with a hot air convection dryer at 110 ° C. for 3 minutes to remove the solvent, thereby forming a first resin layer having a thickness of 8 μm.

  Next, the obtained support film having the first resin layer and a polypropylene film having a thickness of 30 μm (manufactured by Oji F-Tex Co., Ltd., product name: ES-201) as a protective film are bonded at 23 ° C. to form a protective film. Then, a transfer type photosensitive film in which the first resin layer and the support film were laminated in this order was produced.

[Step evaluation test]
First, a test for evaluating a depression (step) on the surface of a cured film formed by a transfer type photosensitive film will be described with reference to FIG. In addition, in FIG. 4, although the case where the transfer type photosensitive film having no second resin layer is evaluated is shown, when the transfer type photosensitive film having the second resin layer is evaluated, The same applies except that the first resin layer 20 has a laminated structure of the first resin layer and the second resin layer.

  A substrate 52 (ITO substrate) for evaluation was prepared. On this base material 52, the first resin layer 20 or the transfer type photosensitive film has a second resin layer while peeling off the protective film of the transfer type photosensitive film obtained in the example and the comparative example. In this case, the second resin layer 30 was opposed to the base material, and was laminated at 100 ° C., 0.6 m / min, and 0.4 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 10 side (manufactured by Oak Manufacturing Co., Ltd., trade name: EXM-1201). Light was irradiated at an exposure amount L1 of 50 mJ / cm ² through a mask 70 having a predetermined pattern (see FIG. 4A).

Next, the mask 70 was removed, and light irradiation was performed at an exposure amount L2 of 10 mJ / cm ² (see FIG. 4B).

Next, the support film 10 was removed and irradiated with light at an exposure amount L3 of 375 mJ / cm ² (see FIG. 4C).

Next, after annealing by heating at 140 ° C. 30 min, and the surface S1 of the high reaction rate that the total amount of the exposure amount is 435mJ / cm ^2, a low reaction rate the total exposure amount is 385mJ / cm ² The step G (nm) between the portion and the surface S2 was measured (see FIG. 4D). The step G (nm) was measured with a laser microscope (manufactured by Lasertec).

  When the step is 120 nm or less, the pattern appearance can be sufficiently suppressed. When the laminate 100 shown in FIG. 2 is formed, the following effects can be obtained if the recessed step on the surface of the cured film is 120 nm or less. When a module such as a touch panel is formed using the laminate 100, OCA is used to adhere the cover glass to the laminate 100. By the way, OCA is required to have high adhesion reliability to the adhered cured film under high temperature and high humidity. However, if there is a fine step on the surface of the cured film, the OCA may float (peel off) due to the step. There is. When the step on the surface of the cured film is 120 nm or less, the occurrence of the above problem can be suppressed, and the adhesion reliability of OCA under high temperature and high humidity can be improved.

[Evaluation of pattern appearance]
The annealed sample obtained in the step difference evaluation test was fixed on a black board, irradiated with light obliquely, visually observed, and evaluated according to the following criteria.
：: The pattern is not visible or difficult to see.
X: The pattern is visible.

[Moisture permeability of cured film]
Five transfer type photosensitive films were prepared. First, the protective film of the first transfer type photosensitive film was peeled off, and this was placed on a filter paper (Advantech, No. 5C, φ90 mm circle, thickness 130 μm), roll temperature 100 ° C., substrate feed rate 0. Lamination was performed under the conditions of 6 m / min and a compression pressure (cylinder pressure) of 0.5 MPa. Next, the support film was peeled off, and a second transfer type photosensitive film was laminated on the first resin layer laminated on the filter paper by peeling off the protective film. By repeating this operation, a laminated body in which a first resin layer (that is, five first resin layers) having a thickness of 40 μm and a support film were laminated on filter paper was produced.

  In the case where the transfer type photosensitive film has the second resin layer, the same procedure as above is used to form five layers of the first resin layer and the second resin layer having a thickness of about 40 μm and the support film on the filter paper. A laminated body was produced.

The laminated body was irradiated with ultraviolet rays at an exposure of 0.6 J / m ² from above the supporting film surface using a parallel light exposure machine (EXM1201 manufactured by Oak Manufacturing Co., Ltd.).

Subsequently, the support film of the laminated body irradiated with the ultraviolet rays was peeled off and removed, and the laminated body was further irradiated with ultraviolet rays from above vertically at an exposure amount of 1 × 10 ⁴ J / m ² . Thus, a moisture permeability measurement sample having a cured film formed on the filter paper was obtained.

Next, the moisture permeability was measured with reference to JIS standard (Z0208, cup method). First, a hygroscopic material (20 g of calcium chloride (anhydrous)) was placed in a measuring cup (φ60 mm, depth 15 mm, Murai Moto Seisakusho). Next, the measuring cup was covered with a circular sample piece cut out from the above-mentioned sample for moisture permeability measurement with scissors having a diameter of 70 mm. It was left in a constant temperature and humidity chamber at 40 ° C. and 90% RH for 24 hours. The moisture permeability was calculated from the change in the total mass of the measuring cup, the hygroscopic agent and the circular sample piece before and after standing. If moisture permeability 200g ^/ m 2 · 24h or less, corrosion resistance is good.

DESCRIPTION OF SYMBOLS 1 ... Transfer type photosensitive film, 10 ... Support film, 20 ... First resin layer, 22 ... Hardened first resin layer, 30 ... Second resin layer, 32 ... Hardened second resin layer, 40 ... Protective film, 50 ... Substrate with transparent electrode pattern, 50a ... Transparent electrode pattern, 60 ... Curing film, 100 ... Laminate, 101 ... Transparent substrate, 102 ... Sensing area, 103,104 ... Transparent electrode, 105 ... Drawing Wiring, 106: connection electrode, 107: connection terminal, 123: cured film pattern.

Claims (14)

Support film, comprising a first resin layer provided on the support film,
A transfer type photosensitive film, wherein the first resin layer contains a photopolymerizable compound having a tricyclodecane skeleton or a tricyclodecene skeleton, and an acylphosphine oxide-based photopolymerization initiator.   The transfer type photosensitive film according to claim 1, wherein the acylphosphine oxide-based photopolymerization initiator includes 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.   The transfer type photosensitive film according to claim 1, wherein the first resin layer further includes an oxime ester-based photopolymerization initiator.   A binder polymer in which the first resin layer contains a group having a branched structure and / or an alicyclic structure in a side chain, a group having an acidic group in a side chain, and a group having an ethylenically unsaturated group in a side chain. The transfer type photosensitive film according to claim 1, comprising:   The transfer type photosensitive film according to any one of claims 1 to 4, further comprising a second resin layer containing metal oxide particles provided on the first resin layer.   The transfer type photosensitive film according to claim 5, wherein the second resin layer contains a photopolymerizable compound having a tricyclodecane skeleton or a tricyclodecene skeleton.   The transfer photosensitive film according to any one of claims 1 to 6, which is used for forming a cured film on a substrate having an ITO electrode pattern and an index matching layer. On a substrate having an electrode pattern, the first resin layer of the transfer type photosensitive film according to any one of claims 1 to 4, the side of the substrate on which the electrode pattern is provided. Laminating so that the first resin layer is in close contact with,
After exposing a predetermined portion of the first resin layer on the base material, removing a portion other than the predetermined portion, and forming a cured film pattern covering a part or all of the electrode pattern,
A method for forming a cured film pattern, comprising: The second resin layer and the first resin layer of the transfer type photosensitive film according to claim 5 or 6, on the substrate having an electrode pattern, the electrode pattern of the substrate is provided. Laminating so that the side and the second resin layer are in close contact,
After exposing a predetermined portion of the second resin layer and the first resin layer on the base material, removing portions other than the predetermined portion to form a cured film pattern covering a part or all of the electrode pattern. Process and
A method for forming a cured film pattern, comprising:   A cured film obtained by curing the first resin layer in the transfer photosensitive film according to claim 1.   A cured film formed by curing only the first resin layer or both the first resin layer and the second resin layer of the transfer photosensitive film according to claim 5. A substrate having an electrode pattern, and a resin cured film provided on the electrode pattern, a laminate having:
The resin cured film has a step on the side opposite to the electrode pattern,
The laminate in which the step is 120 nm or less.   The laminate according to claim 12, wherein the resin cured film includes a compound having a tricyclodecane skeleton or a tricyclodecene skeleton.   A cured film of the first resin layer in the transfer photosensitive film according to any one of claims 1 to 4, or the second resin of the transfer photosensitive film according to claim 5 or 6. A touch panel comprising a cured film pattern including a cured film of a layer and a cured film of the first resin layer.

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