JP2018165788A - Transfer photosensitive film, curable resin patterning method, and touch panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transfer photosensitive film that can form a cured film that protects a transparent electrode pattern and has sufficiently low moisture permeability.SOLUTION: A transfer photosensitive film has a support film 10, and a photosensitive resin layer 20 provided on the support film 10. In the photosensitive resin layer 20, the total concentration of hydrophilic groups selected from -O-, -C-CO-, -OH, -N-CO- and -COOH is 0.020 mol/g or less.SELECTED DRAWING: Figure 1

Description

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

  Liquid crystal display elements or touch panels (touch sensors) are used in large electronic devices such as personal computers and televisions, small electronic devices such as car navigation systems, mobile phones, and electronic dictionaries, and display devices such as OA / FA devices. These liquid crystal display elements or touch panels are provided with electrodes made of a transparent electrode material. As the transparent electrode material, ITO (Indium-Tin-Oxide), indium oxide, and tin oxide are mainly used because of high visible light transmittance.

  Various types of touch panels have already been put into practical use. Since the projected capacitive touch panel can detect multiple fingertips, it has good operability such that a complicated instruction can be given. For this reason, a projected capacitive touch panel is increasingly used as an input device on a display surface in a device having a small display device such as a mobile phone and a portable music player.

  In general, in a projected capacitive touch panel, a plurality of X electrodes and a plurality of Y electrodes orthogonal to the X electrodes have a two-layer structure in order to express two-dimensional coordinates based on the X and Y axes. Forming. In recent years, the use of conductive fibers typified by Ag nanowires and carbon nanotubes has been studied as a material for these electrodes, but ITO is still the mainstream.

  By the way, the frame area of the touch panel is an area where the touch position cannot be detected. Therefore, it is important to reduce the area of the frame region in order to improve the product value. In the frame area, it is necessary to arrange a metal wiring in order to transmit a touch position detection signal. However, in order to reduce the frame area, it is necessary to reduce the width of the metal wiring. Since the conductivity of ITO is not sufficiently high, the metal wiring is generally formed of copper.

  However, when the touch panel is brought into contact with a fingertip or the like, corrosive components such as moisture and salt may enter the inside from the sensing region. When a corrosive component enters the inside of the touch panel, the metal wiring corrodes, and there is a risk of an increase in electrical resistance or disconnection between the electrode and the driving circuit.

  A projected capacitive touch panel in which an insulating layer is formed on a metal to prevent corrosion of metal wiring is known (for example, see Patent Document 1 below). In such a touch panel, a silicon dioxide layer is formed on a metal by a plasma chemical vapor deposition method (plasma CVD method) to prevent corrosion of the metal. However, in such a method, since the plasma CVD method is used, a high temperature treatment is required, and there are problems such as a limitation of the base material and an increase in manufacturing cost.

  As a method for producing a protective film in a display device such as a touch panel, a method using a photosensitive resin composition instead of the plasma CVD method is known. For example, as a method of providing a protective film (for example, a resist film) at a required location, a method of providing a photosensitive layer containing a photosensitive resin composition on a predetermined substrate, and exposing and developing the photosensitive layer is known. (For example, refer to Patent Document 2 below). The production of the protective film with the photosensitive resin composition can be expected to reduce the cost as compared with the plasma CVD method.

JP 2011-28594 A International Publication No. 2013/084873

  A protective film in a display device such as a touch panel is required to have low moisture permeability in order to obtain excellent rust prevention. Then, this invention aims at providing the transfer type photosensitive film which can form the cured film with sufficient low moisture permeability which protects a transparent electrode pattern, the formation method of a cured resin pattern using the same, and a touch panel. And

  In order to achieve the above object, the present invention comprises a support film and a photosensitive resin layer provided on the support film, and in the photosensitive resin layer, -O-, -C-CO-, Provided is a transfer type photosensitive film in which the total concentration of hydrophilic groups selected from —OH, —N—CO—, and —COOH is 0.020 mol / g or less. According to such a transfer type photosensitive film, by controlling the concentration of the hydrophilic group in the photosensitive resin layer within the above range, a cured film with sufficiently reduced moisture permeability can be formed, and a display such as a touch panel can be formed. Corrosion of metal wiring in the apparatus can be sufficiently prevented. The photosensitive resin layer also has good adhesion to a substrate having a transparent electrode pattern.

  In the transfer type photosensitive film, the photosensitive resin layer may contain a binder polymer, a photopolymerizable compound, and a photopolymerization initiator. When the photosensitive resin layer contains the above components, it is easy to form a cured resin pattern including a cured product of the photosensitive resin layer.

  The photopolymerizable compound may include a compound having a tricyclodecane skeleton or a tricyclodecene skeleton. When a compound having a tricyclodecane skeleton or a tricyclodecene skeleton is used, it is easy to reduce the concentration of the hydrophilic group in the photosensitive resin layer, and it becomes easy to form a cured film with sufficiently reduced moisture permeability. In addition, when a compound having a tricyclodecane skeleton or a tricyclodecene skeleton is used, the adhesion between the substrate having the transparent electrode pattern and the photosensitive resin layer becomes better.

  The photopolymerization initiator may contain an oxime ester compound and / or a phosphine oxide compound. When these photopolymerization initiators are used, a cured resin pattern can be formed with sufficient resolution even with a thin film having a thickness of 10 μm or less.

  The binder polymer may have a carboxyl group. Here, the binder polymer includes (meth) acrylic acid, (meth) acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, styrene, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meta It may be a binder polymer having a structural unit derived from at least one compound selected from the group consisting of: butyl acrylate, (meth) acrylic acid 2-ethylhexyl ester, and (meth) acrylic acid tricyclodecyl ester. . When the binder polymer is used, the alkali developability, patterning property and transparency of the photosensitive resin layer can be improved.

  The photosensitive resin layer may further contain a phosphate ester containing an ethylenically unsaturated bond. When the photosensitive resin layer contains a phosphate ester containing an ethylenically unsaturated bond, the adhesion to the transparent electrode pattern can be improved, and the occurrence of development residue can be reduced.

  The transfer type photosensitive film may further include a second resin layer containing metal oxide particles provided on the photosensitive resin layer. In this case, in a display device such as a touch panel, it becomes possible to reduce a color difference due to a difference in optical reflection characteristics between a portion where the transparent electrode pattern is formed and a portion where the transparent electrode pattern is not formed. It is possible to suppress the occurrence of the so-called “bone appearance phenomenon” problem in which the electrode pattern is reflected on the screen. When the second resin layer is provided, the transfer type photosensitive film has a refractive index adjustment function.

  The second resin layer includes at least one metal oxide particle selected from the group consisting of zirconium oxide, titanium oxide, tin oxide, zinc oxide, indium tin oxide, indium oxide, aluminum oxide, and yttrium oxide. May be. In this case, it is easy to adjust the refractive index of the second resin layer at a wavelength of 633 nm to an appropriate range.

  The thickness of the second resin layer may be 10 to 1000 nm. When the thickness of the second resin layer is within the above range, the reflected light intensity of the entire touch screen on the touch panel can be further reduced.

  The present invention also includes a step of laminating the photosensitive resin layer of the transfer-type photosensitive film of the present invention on a substrate, and exposing the predetermined portion of the photosensitive resin layer on the substrate to the predetermined A method of forming a cured resin pattern, comprising: removing a portion other than the portion to form a cured resin pattern. Here, when the transfer type photosensitive film includes the second resin layer, the second resin layer and the photosensitive resin layer are formed on the base material, and the base material and the second resin layer are provided. Lamination is carried out so that the predetermined portions of the second resin layer and the photosensitive resin layer are exposed, and then the portions other than the predetermined portions are removed to form a cured resin pattern.

  The present invention further provides a touch panel provided with a cured resin pattern including a cured product of the photosensitive resin layer in the transfer type photosensitive film of the present invention. Here, when the transfer type photosensitive film includes the second resin layer, the cured resin pattern further includes a cured product of the second resin layer. When the cured product of the second resin layer is provided, the cured resin pattern has a refractive index adjustment function.

  According to the present invention, it is possible to provide a transfer type photosensitive film capable of forming a cured film having a sufficiently low moisture permeability for protecting a transparent electrode pattern, a method for forming a cured resin pattern using the same, and a touch panel. .

It is a schematic cross section which shows the transfer type photosensitive film which concerns on one Embodiment of this invention. It is a schematic cross section which shows the laminated body which equips the base material with a transparent electrode pattern with the cured film formed using the transfer type photosensitive film which concerns on one Embodiment of this invention. It is a model top view which shows the touchscreen which concerns on one Embodiment of this invention.

  Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the drawings depending on cases. However, the present invention is not limited to the following embodiments. In the present specification, “(meth) acrylic acid” means acrylic acid or methacrylic acid, and “(meth) acrylate” means acrylate or a corresponding methacrylate. The “(poly) oxyethylene chain” means an oxyethylene group or a polyoxyethylene group, and the “(poly) oxypropylene chain” means an oxypropylene group or a polyoxypropylene group. “A or B” only needs to include one of A and B, or may include both.

  In addition, in this specification, the term “layer” includes a structure formed in a part in addition to a structure formed in the entire surface when observed as a plan view. In addition, in this specification, the term “process” is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term “process” is used as long as the intended action of the process is achieved. included. Moreover, the numerical value range shown using "to" shows the range which includes the numerical value described before and behind "to" as a minimum value and a maximum value, respectively.

  Furthermore, in the present specification, the content of each component in the composition is the sum of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means quantity. In addition, the exemplary materials may be used alone or in combination of two or more unless otherwise specified.

  In addition, in the numerical ranges described stepwise in the present specification, the upper limit value or lower limit value of a numerical range of a certain step may be replaced with the upper limit value or lower limit value of the numerical range of another step. Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.

<Transfer type photosensitive film>
The transfer type photosensitive film of this embodiment comprises a support film and a photosensitive resin layer provided on the support film. The transfer type photosensitive film may further include a second resin layer provided on the photosensitive resin layer. The transfer type photosensitive film may further include a protective film provided on the photosensitive resin layer or the second resin layer.

  FIG. 1 is a schematic cross-sectional view showing a transfer type photosensitive film (transfer type photosensitive refractive index adjusting film) according to an embodiment of the present invention. A transfer type photosensitive film 1 shown in FIG. 1 includes a support film 10, a photosensitive resin layer 20 provided on the support film 10, and a second resin layer 30 provided on the photosensitive resin layer. And a protective film 40 provided on the second resin layer 30.

  By using the transfer-type photosensitive film, for example, a cured film satisfying both functions of protecting the metal wiring on the frame of the touch panel or the transparent electrode of the touch panel, and making the transparent electrode pattern invisible or improving the visibility of the touch screen. It can be formed in a lump.

(Support film)
As the support film 10, a polymer film can be used. Examples of the material for the polymer film include polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, polyethersulfone, and cycloolefin polymer.

  The thickness of the support film 10 is preferably 5 to 100 μm, preferably 10 to 70 μm, from the viewpoint of ensuring coverage and suppressing a reduction in resolution when irradiating actinic rays through the support film 10. More preferably, it is 15-40 micrometers, It is more preferable, It is especially preferable that it is 15-35 micrometers.

(Photosensitive resin layer)
The photosensitive resin layer 20 includes a binder polymer (hereinafter also referred to as (A) component), a photopolymerizable compound (hereinafter also referred to as (B) component), and a photopolymerization initiator (hereinafter also referred to as (C) component). ) And a photosensitive resin composition. In the photosensitive resin layer 20, the total concentration of hydrophilic groups selected from —O—, —C—CO—, —OH, —N—CO—, and —COOH is 0.020 mol / g or less.

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

  The component (A) is preferably a copolymer containing structural units derived from (meth) acrylic acid and (meth) acrylic acid alkyl ester. The copolymer may contain in the structural unit other monomers that can be copolymerized with the (meth) acrylic acid and the (meth) acrylic acid alkyl ester. Specific examples of the other monomer include (meth) acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, and styrene. Moreover, it is preferable to use the monomer which has tricyclo frame | skeletons, such as (meth) acrylic acid tricycloalkyl ester, from a viewpoint of reducing the water vapor transmission rate of the cured film obtained.

  Examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid Examples thereof include hydroxyl ethyl ester.

  Among these, (meth) acrylic acid, (meth) acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, styrene, from the viewpoint of alkali developability (particularly developability with respect to an inorganic alkaline aqueous solution), patternability, and transparency. (Meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid tricyclodecyl ester, dicyclopentenyl (meth) Acrylate, dicyclopentenyloxy (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxy (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexylmale Preferred is a binder polymer having a structural unit derived from at least one compound selected from the group consisting of hydrogen, hydroxyethyl (meth) acrylate and hydroxybutyl (meth) acrylate, (meth) acrylic acid, glycidyl (meth) acrylate Esters, (meth) acrylic acid benzyl ester, styrene, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester and (meth) acrylic Binder polymers having a structural unit derived from at least one compound selected from the group consisting of acid tricyclodecyl esters are more preferable, (meth) acrylic acid, (meth) acrylic acid glycidyl ester, (meth) acrylic acid benzoate. Glycol ester and (meth) binder polymer having a structural unit derived from acrylic acid tricyclodecyl ester is particularly preferred. By using a binder polymer having a structural unit derived from these compounds, the adhesion between the substrate having a transparent electrode pattern and the photosensitive resin layer can be improved, and the concentration of the hydrophilic group in the photosensitive resin layer is reduced. It is easy to form, and it becomes easy to form a cured film with sufficiently reduced moisture permeability. In addition, the binder polymer is a copolymer of at least hydroxyethyl (meth) acrylate or hydroxybutyl (meth) acrylate as the structural unit, and hydroxyethyl (meth) acrylate or hydroxybutyl (meth) acrylate. An acrylate or glycidyl (meth) acrylate may be subjected to an addition reaction.

  The weight average molecular weight of the component (A) is preferably 10,000 to 200,000, more preferably 15,000 to 150,000, and 30,000 to 150,000 from the viewpoint of resolution. More preferably, it is particularly preferably 30,000 to 100,000, and very preferably 40,000 to 100,000. In addition, a weight average molecular weight can be measured by the gel permeation chromatography method described in the Example of this specification.

  The acid value of the component (A) is preferably 75 mgKOH / g or more from the viewpoint of easily forming a cured film (protective film) 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 75 to 150 mgKOH / g. More preferably, it is 75 to 120 mgKOH / g. In addition, an acid value can be measured by the method described in the Example of this specification.

  The hydroxyl value of the component (A) is preferably 50 mgKOH / g or less, more preferably 45 mgKOH / g or less, from the viewpoint of further improving the rust prevention property of the cured film.

  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, or a polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups. Moreover, it is preferable that (B) component contains the compound which has tricyclo ring skeletons, such as (meth) acrylic acid tricycloalkyl ester, from a viewpoint of reducing the water vapor transmission rate of the cured film obtained.

  As said monofunctional vinyl monomer, what was illustrated as a monomer used for the synthesis | combination of the copolymer which is a suitable example of the said (A) component is mentioned, for example.

  The bifunctional vinyl monomer having two polymerizable ethylenically unsaturated groups in the molecule includes a compound having a tricyclodecane skeleton or a tricyclodecene skeleton from the viewpoint of reducing the moisture permeability of the cured film. preferable. From the viewpoint of inhibiting corrosion of the metal wiring and the transparent electrode pattern, the compound having a tricyclodecane skeleton or a tricyclodecene skeleton preferably includes a di (meth) acrylate compound represented by the following general formula (B-1). .

［一般式（Ｂ−１）中、Ｒ^３１及びＲ^３２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^３３及びＲ^３４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 General Formula (B-1), R ³¹ and R ³² each independently represent a hydrogen atom or a methyl group, X represents a divalent group having a tricyclodecane skeleton or a tricyclodecene skeleton, and R ³³ and R ³⁴ each independently represent an alkylene group having 1 to 4 carbon atoms, n and m each independently represent an integer of 0 to 2, and p and q each independently represents an integer of 0 or more. , P + q = 0 to 10 is selected. ]

In the general formula (B-1), R ³³ and R ³⁴ are preferably an ethylene group or a propylene group, and more preferably an ethylene group. The propylene group may be either an n-isopropylene group or 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 the cured film has a low thickness. Moisture permeability can be realized, and the corrosion resistance 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 (where each 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, among the total amount of 100 parts by mass of the photopolymerizable compound contained in the photosensitive resin composition, from the viewpoint of reducing moisture permeability. , 50 parts by mass or more, preferably 70 parts by mass or more, and more preferably 80 parts by mass or more.

  A bifunctional vinyl monomer having two polymerizable ethylenically unsaturated groups in the molecule, other than a compound having a tricyclodecane skeleton or a tricyclodecene skeleton, includes polyethylene glycol di (meth) acrylate and trimethylolpropane. Examples include di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2,2-bis (4- (meth) acryloxypolyethoxypolypropoxyphenyl) propane, and bisphenol A diglycidyl ether di (meth) acrylate.

  As the polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups, conventionally known ones can be used without particular limitation. From the viewpoint of corrosion prevention and developability of metal wiring or transparent electrode, the polyfunctional vinyl monomer includes a (meth) acrylate compound having a skeleton derived from trimethylolpropane such as trimethylolpropane tri (meth) acrylate; tetramethylolmethane (Meth) acrylate compounds having a skeleton derived from tetramethylolmethane such as tri (meth) acrylate and tetramethylolmethanetetra (meth) acrylate; derived from pentaerythritol such as pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate (Meth) acrylate compounds having the following skeleton: bones derived from dipentaerythritol such as dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate A (meth) acrylate compound having a skeleton derived from ditrimethylolpropane such as ditrimethylolpropane tetra (meth) acrylate; or a (meth) acrylate compound having a skeleton derived from diglycerin; derived from cyanuric acid It is preferable to use a (meth) acrylate compound having a skeleton.

  Among these, the polyfunctional vinyl monomer includes a (meth) acrylate compound having a skeleton derived from pentaerythritol, a (meth) acrylate compound having a skeleton derived from dipentaerythritol, and a (meth) acrylate having a skeleton derived from trimethylolpropane. It is more preferable to include a compound, a (meth) acrylate compound having a skeleton derived from ditrimethylolpropane, or a (meth) acrylate compound having a skeleton derived from cyanuric acid.

  Here, the “(meth) acrylate compound having a skeleton derived from” will be described by taking a (meth) acrylate compound having a skeleton derived from ditrimethylolpropane as an example. (Meth) acrylate having a skeleton derived from ditrimethylolpropane means an esterified product of ditrimethylolpropane and (meth) acrylic acid, and the esterified product includes a compound modified with an alkyleneoxy group. The The esterified product preferably has a maximum number of 4 ester bonds in one molecule, but a compound having 1 to 3 ester bonds may be mixed.

  When a monomer having at least three polymerizable ethylenically unsaturated groups in the molecule is used in combination with a monofunctional vinyl monomer or a bifunctional vinyl monomer, the ratio to be used is not particularly limited, but photocurability and electrode corrosion From the viewpoint of preventing the polymerization, the proportion of the monomer having at least three polymerizable ethylenically unsaturated groups in the molecule is 30 mass out of 100 mass parts of the total amount of the photopolymerizable compound contained in the photosensitive resin composition. Part or more, preferably 50 parts by weight or more, and more preferably 75 parts by weight or more.

  The content of the component (A) and the component (B) is preferably 35 to 85 parts by mass of the component (A) with respect to 100 parts by mass of the total amount of the components (A) and (B). More preferably, it is 80 mass parts, It is further more preferable that it is 50-70 mass parts, It is especially preferable that it is 55-65 mass parts. In particular, the component (A) is preferably 35 parts by mass or more with respect to 100 parts by mass of the total amount of the component (A) and the component (B) in terms of maintaining the pattern formability and transparency of the cured film. 40 parts by mass or more, more preferably 50 parts by mass or more, and particularly preferably 55 parts by mass or more.

  As the component (C), a conventionally known photopolymerization initiator can be used without any particular limitation, but a highly transparent photopolymerization initiator is preferably used. The component (C) preferably contains an oxime ester compound and / or a phosphine oxide compound in that a cured resin film pattern can be formed with sufficient resolution even on a substrate with a thickness of 10 μm or less. Examples of the phosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.

  The oxime ester compound is preferably a compound represented by the following general formula (1), a compound represented by the following general formula (2), or a compound represented by the following general formula (3).

In 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, and 1 to 8 carbon atoms. It is preferably an alkyl group, a cycloalkyl group having 4 to 6 carbon atoms, a phenyl group or a tolyl group, 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. More preferred is a methyl group, a cyclopentyl group, a phenyl group or a tolyl group. R ¹³ represents —H, —OH, —COOH, —O (CH ₂ ) OH, —O (CH ₂ ) ₂ OH, —COO (CH ₂ ) OH or —COO (CH ₂ ) ₂ OH; It is preferably H, —O (CH ₂ ) OH, —O (CH ₂ ) ₂ OH, —COO (CH ₂ ) OH, or —COO (CH ₂ ) ₂ OH, and —H, —O (CH ₂ ) ₂ OH or —COO (CH ₂ ) ₂ OH is more preferable.

In formula (2), two R < ¹⁴ > shows a C1-C6 alkyl group each independently, and it is preferable that it is a propyl group. R ¹⁵ represents NO ₂ or ArCO (wherein Ar represents an aryl group), and Ar is preferably a tolyl group. R ¹⁶ and R ¹⁷ each independently represent an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group, and is preferably a methyl group, a phenyl group, or a tolyl group.

In 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 included in the compound represented by the formula (3-1) described later. R ²⁰ and R ²¹ each independently represents an alkyl group having 1 to 12 carbon atoms, a phenyl group or a tolyl group, preferably a methyl group, a phenyl group or a tolyl group, and more preferably a methyl group. . R ²² represents a hydrogen atom or an alkyl group.

  Examples of the compound represented by the general formula (1) include a compound represented by the following formula (1-1) and a compound represented by the following formula (1-2). The compound represented by the following formula (1-1) is available as IRGACURE OXE 01 (manufactured by BASF Japan Ltd., product name).

  Examples of the compound represented by the general formula (2) include a compound represented by the following formula (2-1). The compound represented by the following formula (2-1) is available as DFI-091 (manufactured by Daito Chemix Co., Ltd., product name).

  Examples of the compound represented by the general formula (3) include a compound represented by the following formula (3-1). The compound represented by the following formula (3-1) is available as Adekaoptomer N-1919 (manufactured by ADEKA, product name).

  As another oxime ester compound, a compound represented by the following formula (4) and a compound represented by the following formula (5) can be used.

  Among the above, the compound represented by the formula (1-1) is very preferable. Whether the compound represented by the above formula (1-1) is contained in the cured film is determined by detecting heptanonitrile and benzoic acid when pyrolysis gas chromatography / mass spectrometry of the cured film is performed. Whether or not it can be judged as an index. When the cured film is not subjected to a high-temperature heating step, it can be understood that the compound represented by the above formula (1-1) was contained in the cured film by detecting heptanonitrile and benzoic acid. The detection peak area of benzoic acid in pyrolysis gas chromatograph mass spectrometry of the cured film is detected in the range of 1 to 10% with respect to the detection peak area of heptanonitrile.

  In the pyrolysis gas chromatograph mass spectrometry of the cured film, it is preferable to perform gas chromatograph mass spectrometry on the gas generated by heating the measurement sample at 140 ° C. Although the heating time of said measurement sample should just be the range for 1 to 60 minutes, it is preferable that it is 30 minutes. An example of measurement conditions for pyrolysis gas chromatograph mass spectrometry is shown below.

(Measurement conditions for pyrolysis gas chromatograph mass spectrometry)
Measuring device: GC / MS QP-2010 (manufactured by Shimadzu Corporation, product name)
Column: HP-5MS (manufactured by Agilent Technologies, product name)
Even Temp: heated at 40 ° C. for 5 minutes and then heated to 300 ° C. at a rate of 15 ° C./min. Carrier gas: helium, 1.0 mL / min
Interface temperature: 280 ° C
Ion source temperature: 250 ° C
Sample injection volume: 0.1 mL

  The content of the component (C) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B) in terms of excellent photosensitivity and resolution. More preferably, it is -5 mass parts, It is further more preferable that it is 1-3 mass parts, It is especially preferable that it is 1-2 mass parts.

  The photosensitive resin composition according to this embodiment has a triazole compound having a mercapto group, a tetrazole compound having a mercapto group, a thiadiazole compound having a mercapto group, and an amino group from the viewpoint of further improving the rust prevention property of the cured film It is preferable to further contain at least one compound selected from the group consisting of a triazole compound and a tetrazole compound having an amino group (hereinafter also referred to as component (D)). 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 benzotriazole, 1H-benzotriazole-1-acetonitrile, benzotriazole-5-carboxylic acid, 1H-benzotriazole-1-methanol, carboxybenzotriazole, etc. , 3-mercaptotriazole, 5-mercaptotriazole, and the like, and the like.

  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. Etc. These tetrazole compounds may be water-soluble salts thereof. Specific examples include alkali metal salts of 1-methyl-5-amino-tetrazole such as sodium, potassium and lithium.

  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 component (A) and the component (B). 0.1-2.0 mass parts is more preferable, 0.2-1.0 mass part is further more preferable, and 0.3-0.8 mass part is especially preferable.

  The photosensitive resin composition according to the present embodiment contains a phosphate ester containing an ethylenically unsaturated bond (hereinafter also referred to as the (E) component) from the viewpoint of preventing adhesion of the ITO electrode and generation of development residue. It is preferable to do. In addition, in this specification, the phosphate ester containing an ethylenically unsaturated bond shall be handled as (E) component instead of (B) component.

  As the phosphate ester containing an ethylenically unsaturated bond as the component (E), from the viewpoint of achieving both high adhesion and developability to the ITO electrode while ensuring sufficient rust prevention of the cured film to be formed. The Phosmer series (Phosmer-M, Phosmer-CL, Phosmer-PE, Phosmer-MH, Phosmer-PP, etc.) manufactured by Unichemical Co., Ltd., or the KAYAMER series (PM-21, PM-2 manufactured by Nippon Kayaku Co., Ltd.) Etc.) is preferred.

  The photosensitive resin layer 20 formed using the photosensitive resin composition described above has a total concentration of hydrophilic groups selected from —O—, —C—CO—, —OH, —N—CO—, and —COOH. Must be 0.020 mol / g or less. When the total concentration of the hydrophilic groups is 0.020 mol / g or less, a cured film having a sufficiently low moisture permeability can be formed. From the viewpoint of further reducing the moisture permeability of the resulting cured film, the total concentration of the hydrophilic groups is more preferably 0.019 mol / g or less, still more preferably 0.018 mol / g or less. It is particularly preferable that the amount be 0.017 mol / g or less. The total concentration of the hydrophilic groups can be within the above range by adjusting the types and blending amounts of the component (A) and the component (B) to be used. In particular, by using a component having a tricyclo ring structure as the component (A) and the component (B), the total concentration of the hydrophilic groups can be effectively reduced, and the moisture permeability and prevention of the cured film can be reduced. The rust property can be improved.

  The thickness of the photosensitive resin layer 20 is preferably 15 μm or less in terms of the thickness after drying, in order to sufficiently exhibit the effect as a protective film and sufficiently bury the step on the surface of the substrate with the transparent electrode pattern. More preferably, it is 10-10 micrometers, and it is further more preferable that it is 3-8 micrometers. Further, the thickness of the photosensitive resin layer after curing is also preferably within the above range.

(Second resin layer)
The second resin 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 1.53 to 1.85. Is more preferable, and 1.55-1.75 is particularly preferable. Moreover, when the 2nd resin layer contains a sclerosing | hardenable component, it is preferable that the refractive index in 633 nm of the 2nd resin layer after hardening is also in the said range.

  When the refractive index at 633 nm of the second resin layer 30 is within the above range, various members (for example, modules) used on the cured film pattern when the cured film pattern is provided on a transparent electrode pattern such as ITO. It becomes an intermediate value of the refractive index of the cover glass and the OCA that bonds the transparent electrode pattern to the transparent electrode pattern, and is optical in the portion where the transparent electrode pattern such as ITO is formed and the portion where it is not formed. It is possible to reduce the color difference due to reflection and prevent the appearance of bone. Moreover, it becomes possible to reduce the reflected light intensity of the whole screen, and to suppress the transmittance | permeability fall on a screen.

  The refractive index of a transparent electrode such as ITO is preferably 1.80 to 2.10, more preferably 1.85 to 2.05, and even more preferably 1.90 to 2.00. . Further, the refractive index of a member such as OCA is preferably 1.45 to 1.55, more preferably 1.47 to 1.53, and further preferably 1.48 to 1.51. .

  The second resin layer 30 preferably has a minimum light transmittance of 80% or more in a wavelength region of 450 to 650 nm, more preferably 85% or more, and further preferably 90% or more. Moreover, when the 2nd resin layer contains a sclerosing | hardenable component, it is preferable that the minimum light transmittance in the 450-650 nm wavelength range of the 2nd resin layer after hardening is also in the said range.

  The 2nd resin layer 30 can contain said (A) component, (B) component, and (C) component, and said (D) component and / or said (E) component as needed. Furthermore, it can contain. The second resin layer 30 does not necessarily contain a photopolymerization component such as the component (B) or the component (C), and the second resin layer is formed by utilizing a photopolymerization component that migrates from an adjacent resin layer due to layer formation. The layer can also be photocured.

  The second resin layer 30 contains metal oxide particles (hereinafter also referred to as component (F)). The metal oxide particles preferably contain metal oxide particles having a refractive index of 1.50 or more at a wavelength of 633 nm. Thereby, when the transfer type photosensitive refractive index adjusting film is prepared, it is possible to improve the transparency of the second resin layer and the refractive index at a wavelength of 633 nm. Moreover, developability can be improved, suppressing adsorption | suction to a 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, yttrium oxide, and glass. 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 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 (product name, manufactured by Nissan Chemical Industries, Ltd.), OZ-S40K-AC (product name, manufactured by Nissan Chemical Industries, Ltd.), SZR-K (zirconium oxide methyl ethyl ketone dispersion, Sakai Chemical Co., Ltd.). Kogyo Co., Ltd., product name) and SZR-M (zirconium oxide methanol dispersion, Sakai Chemical Industry Co., Ltd., product name) are commercially available.

  The second resin layer 30 may contain titanium oxide nanoparticles as the component (F). Moreover, 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 (F), in addition to the metal oxide particles, oxide particles or sulfide particles containing atoms such as Mg, Al, Si, Ca, Cr, Cu, Zn, and Ba can be used. These can be used alone or in combination of two or more.

  In addition to the metal oxide particles, organic compounds such as a compound having a triazine ring, a compound having an isocyanuric acid skeleton, and a compound having a fluorene skeleton can also be used. Thereby, the refractive index in wavelength 633nm can be improved.

  The thickness of the second resin layer 30 may be 10 to 1000 nm, preferably 50 to 500 nm, more preferably 60 to 300 nm, still more preferably 70 to 250 nm, 80 It is especially preferable that it is -200 nm. When the thickness is 50 to 500 nm, the reflected light intensity of the entire screen can be further reduced. Moreover, it is preferable that the thickness of the 2nd resin layer after hardening is also in the said range.

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 as follows using ETA-TCM (product name, manufactured by AudioDev GmbH). Can be requested. The following measurement is performed under the condition of 25 ° C.
(1) A coating solution for forming the second resin layer is uniformly applied on a glass substrate having a thickness of 0.7 mm, a length of 10 cm and a width of 10 cm by a spin coater, and a hot air residence type dryer at 100 ° C. Dry for 3 minutes to remove the solvent and form a second resin layer.
(2) Next, the sample is allowed to stand for 30 minutes in a box-type dryer heated to 140 ° C. (manufactured by Mitsubishi Electric Corporation, model number: NV50-CA) to obtain a sample for refractive index measurement having a second resin layer.
(3) Next, the refractive index at a wavelength of 633 nm is measured by ETA-TCM (manufactured by AudioDev GmbH, product name) for the obtained sample for refractive index measurement.

  The refractive index in a single photosensitive resin layer can also be measured by the same method. In addition, since it is difficult to measure the refractive index of the second resin layer single layer in the form of the transfer type photosensitive film, the value of the outermost surface layer on the protective film side of the second resin layer is used.

(Other layers)
The photosensitive refractive index adjusting film of the present embodiment may be provided with other appropriately selected layers as long as the effects of the present invention are obtained. There is no restriction | limiting in particular as said other layer, According to the objective, it can select suitably, For example, a cushion layer, an oxygen shielding layer, a peeling layer, an adhesive layer etc. are mentioned. The said photosensitive refractive index adjustment film may have these layers individually by 1 type, and may have 2 or more types. Moreover, you may have 2 or more of the same kind of layers.

(Protective film)
As the protective film 40, a polymer film can be used. Examples of the material of the polymer film include polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, polyethylene-vinyl acetate copolymer, and the like. The protective film 40 may be a laminated film in which polymer films made of different materials are laminated, for example, a laminated film in which a polyethylene-vinyl acetate copolymer film and a polyethylene film are laminated.

  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 50 μm from the viewpoint of storing the transfer type photosensitive film 1 in a roll shape. More preferably, it is more preferably 40 μm or less.

  Total light in a visible light region of a wavelength of 400 to 700 nm of a cured film portion (excluding the support film 10 and the protective film 40) obtained by curing the photosensitive resin layer 20 and the second resin layer 30 in the transfer type photosensitive film 1. The minimum value of the transmittance (Tt) is preferably 90.00% or more, more preferably 90.50% or more, and further preferably 90.70% or more. When the total light transmittance in a general visible light wavelength region of 400 to 700 nm is 90.00% or more, when protecting the transparent electrode in the sensing region of the touch panel (touch sensor), image display in the sensing region It can suppress sufficiently that quality, a hue, and a brightness | luminance fall.

  The photosensitive resin layer 20 and the second resin layer 30 of the transfer type photosensitive film 1 are prepared, for example, as a coating liquid containing a photosensitive resin composition and a coating liquid containing a second resin composition, This can be formed by coating and drying on the support film 10 and the protective film 40, respectively. The transfer type photosensitive film 1 includes a support film 10 on which the photosensitive resin layer 20 is formed, and a protective film 40 on which the second resin layer 30 is formed, and the photosensitive resin layer 20 and the second resin. It can form by bonding together in the state facing the layer 30. FIG. Further, the transfer type photosensitive film 1 is coated with a coating solution containing a photosensitive resin composition on the support film 10 and dried, and then contains a second resin composition on the photosensitive resin layer 20. It can also be formed by applying and drying a coating solution and attaching a protective film 40.

  The coating liquid can be obtained by uniformly dissolving or dispersing each component constituting the photosensitive resin composition and the second resin composition according to the present embodiment described above in a solvent.

  There is no restriction | limiting in particular in the solvent used as a coating liquid, A well-known thing can be used. Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, methanol, ethanol, propanol, butanol, methylene glycol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether , Diethylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, chloroform, methylene chloride and the like.

  Application methods include doctor blade coating method, Mayer bar coating method, roll coating method, screen coating method, spinner coating method, inkjet coating method, spray coating method, dip coating method, gravure coating method, curtain coating method, and die coating method. Etc.

  Although there is no restriction | limiting in particular in drying conditions, It is preferable that drying temperature shall be 60-130 degreeC, and it is preferable that drying time shall be 0.5-30 minutes.

  The viscosity of the photosensitive resin layer and the second resin layer is a viewpoint that prevents the resin composition from exuding from the end face of the transfer type photosensitive film 1 when the transfer type photosensitive film 1 is stored in a roll shape, and From the viewpoint of preventing debris of the resin composition from adhering to the substrate when the transfer type photosensitive film 1 is cut, it is preferably 15 to 100 mPa · s at 30 ° C., and 20 to 90 mPa · s. More preferably, it is more preferably 25 to 80 mPa · s.

  FIG. 2 is a schematic cross-sectional view showing a laminate comprising a cured film formed using a transfer type photosensitive film according to an embodiment of the present invention on a substrate with a transparent electrode pattern. The laminated body 100 shown by FIG. 2 is provided with the base material 50 with the transparent electrode pattern which has the transparent electrode pattern 50a, and the cured film 60 provided on the transparent electrode pattern 50a of the base material 50 with a transparent electrode pattern. The cured film 60 is a cured film composed of the cured photosensitive resin layer 22 and the cured second resin layer 32, and is formed using the transfer type photosensitive film 1 of the present embodiment. The cured film 60 satisfies both the protective function of the transparent electrode pattern 50a and the function of making the transparent electrode pattern 50a invisible or improving the visibility of the touch screen. Hereinafter, an embodiment of a method for producing a laminate in which a cured film is formed on a substrate with a transparent electrode pattern will be described.

  First, after removing the protective film 40 of the transfer type photosensitive film 1, the second resin layer 30, the photosensitive resin layer 20 and the support film 10 are placed on the surface of the substrate 50 with a transparent electrode pattern. Laminate (transfer) by pressing from the side. Examples of the pressing means include a pressing roll. The pressure roll may be provided with a heating means so that it can be heat-pressure bonded.

  In the case of thermocompression bonding, the heating temperature is determined from the viewpoint of adhesion between the second resin layer 30 and the substrate 50 with the transparent electrode pattern, and the constituent components of the photosensitive resin layer 20 or the second resin layer 30 are thermoset. Alternatively, from the viewpoint of preventing thermal decomposition, the temperature is preferably 10 to 160 ° C, more preferably 20 to 150 ° C, and still more preferably 30 to 150 ° C.

In addition, the pressing pressure at the time of thermocompression bonding is a line from the viewpoint of suppressing the deformation of the substrate 50 with the transparent electrode pattern while ensuring sufficient adhesion between the second resin layer 30 and the substrate 50 with the transparent electrode pattern. The pressure is preferably 50 to 1 × 10 ⁵ N / m, more preferably 2.5 × 10 ^{2 to} 5 × 10 ⁴ N / m, and 5 × 10 ² to 4 × 10 ⁴ N / m. More preferably.

  If the transfer type photosensitive film 1 is thermocompression bonded as described above, the pre-heat treatment of the substrate 50 with a transparent electrode pattern is not necessarily required, but the second resin layer 30 and the substrate 50 with a transparent electrode pattern are in close contact with each other. From the point of further improving the property, the substrate 50 with a transparent electrode pattern may be preheated. It is preferable that the processing temperature at this time shall be 30-150 degreeC.

  As a base material which comprises the base material 50 with a transparent electrode pattern, base materials, such as a glass plate used for a touch panel (touch sensor), a plastic plate, a ceramic board, are mentioned, for example. On this base material, an electrode to be a target for forming a cured film is provided. Examples of the electrode include electrodes such as ITO, Cu, Al, and Mo. In addition, an insulating layer may be provided on the base material between the base material and the electrode.

  Next, actinic rays are irradiated in a pattern form to a predetermined portion of the photosensitive resin layer and the second resin layer after transfer through a photomask. When irradiating the actinic ray, if the support film 10 on the photosensitive resin layer and the second resin layer is transparent, the actinic ray can be irradiated as it is. Irradiate. A known active light source can be used as the active light source.

The irradiation amount of actinic rays is 1 * 10 < ² > -1 * 10 < ⁴ > J / m < ² >, and it can also be accompanied with heating in the case of irradiation. If the irradiation amount of this actinic ray is 1 × 10 ² J / m ² or more, the photocuring of the photosensitive resin layer and the second resin layer can sufficiently proceed, and 1 × 10 ⁴ J / tends to be suppressed that if m ² or less photosensitive resin layer and second resin layer is discolored.

  Subsequently, the unexposed portions of the photosensitive resin layer and the second resin layer after irradiation with actinic rays are removed with a developer to form a cured film (cured resin pattern) 60 that covers part or all of the transparent electrode. To do. In addition, after irradiation of actinic rays, when the support film 10 is laminated | stacked on the photosensitive resin layer and the 2nd resin layer, after developing it, a image development process is performed.

  The development step can be performed by a known method such as spraying, showering, rocking dipping, brushing, or scrubbing using a known developer such as an aqueous alkaline solution, an aqueous developer, or an organic solvent. Of these, spray development is preferably performed using an alkaline aqueous solution from the viewpoint of environment and safety. The development temperature and time can be adjusted within a conventionally known range.

  The transfer type photosensitive film according to this embodiment can be applied to the formation of a protective film in various electronic components. The electronic component according to this embodiment includes a cured resin pattern formed using a transfer type photosensitive film. Examples of the electronic component include a touch panel, a liquid crystal display, an organic electroluminescence, a solar cell module, a printed wiring board, and electronic paper.

  FIG. 3 is a schematic top view showing a touch panel according to an embodiment of the present invention. FIG. 3 shows an example of a capacitive touch panel. The touch panel shown in FIG. 3 has a touch screen 102 for detecting a touch position coordinate on one side of a transparent substrate 101, and the transparent electrode 103 and the transparent electrode 104 for detecting a change in capacitance in this region are transparent. It is provided on the base material 101.

  The transparent electrode 103 and the transparent electrode 104 detect the X position coordinate and the Y position coordinate of the touch position, respectively.

  On the transparent substrate 101, a lead-out wiring 105 for transmitting a touch position detection signal from the transparent electrode 103 and the transparent electrode 104 to an external circuit is provided. The lead-out wiring 105 is connected to the transparent electrode 103 and the transparent electrode 104 by a connection electrode 106 provided on the transparent electrode 103 and the transparent electrode 104. A connection terminal 107 for connecting to an external circuit is provided at the end of the lead-out wiring 105 opposite to the connection portion between the transparent electrode 103 and the transparent electrode 104.

  As shown in FIG. 3, in the touch panel according to the present embodiment, using the transfer photosensitive film of the present embodiment, a cured resin pattern straddling a portion where the transparent electrode pattern is formed and a portion where the transparent electrode pattern is not formed. 123 is formed. The cured resin pattern 123 is a cured film including a cured photosensitive resin layer and a cured second resin layer. According to the cured resin pattern 123, the function of protecting the transparent electrode 103, the transparent electrode 104, the lead-out wiring 105, the connection electrode 106, and the connection terminal 107, and the bone of the sensing region (touch screen) 102 formed from the transparent electrode pattern. A visual phenomenon prevention function can be performed at the same time.

  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 (A1)]
The material (1) shown in Table 1 was charged into a flask equipped with a stirrer, a reflux condenser, an inert gas inlet, and a thermometer, and then heated to 80 ° C. in a nitrogen gas atmosphere. While maintaining the reaction temperature at 80 ° C. ± 2 ° C., the material (2) shown in Table 1 was uniformly added dropwise over 4 hours. After dripping the material (2), stirring was continued at 80 ° C. ± 2 ° C. for 6 hours, and a binder polymer solution (solid content 45% by mass) (A1) having a weight average molecular weight of 65,000 and an acid value of 78 mgKOH / g was obtained. Obtained.

[Preparation of binder polymer solution (A2)]
A solution of a binder polymer obtained by adding glycidyl methacrylate in a blending amount shown in Table 2 to a copolymer obtained by copolymerizing methacrylic acid, benzyl methacrylate and tricyclodecane methacrylate in a blending amount shown in Table 2 (solid content 34. 5 mass%) (A2) was prepared.

[Preparation of binder polymer solution (A3)]
A solution of a binder polymer obtained by adding glycidyl methacrylate in a blending amount shown in Table 2 to a copolymer obtained by copolymerizing methacrylic acid, benzyl methacrylate and tricyclodecane methacrylate in a blending amount shown in Table 2 (solid content 34. 5 mass%) (A3) was prepared.

  The weight average molecular weight and acid value of the binder polymer described above were measured by the following methods. The results are shown in Table 2.

[Method for 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 standard polystyrene calibration curve. The measurement conditions for GPC are shown below.
<GPC measurement conditions>
Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd., product name)
Column: Gelpack GL-R420, Gelpack GL-R430, Gelpack GL-R440 (above, manufactured by Hitachi Chemical Co., Ltd., product name)
Eluent: Tetrahydrofuran Measurement temperature: 40 ° C
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd., product name)

[Measurement method of acid value]
The acid value was measured as follows. First, the binder polymer solution was heated at 130 ° C. for 1 hour to remove volatile matter, thereby obtaining a solid content. And after precisely weighing 1 g of the polymer of the solid content, 30 g of acetone was added to the polymer, and this was uniformly dissolved. Next, an appropriate amount of an indicator, phenolphthalein, was added to the solution, and titration was performed using a 0.1N aqueous KOH solution. And the acid value was computed by following Formula.
Acid value = 0.1 × Vf × 56.1 / (Wp × I / 100)
In the formula, Vf represents the titration amount (mL) of the KOH aqueous solution, Wp represents the mass (g) of the measured polymer solution, and I represents the ratio (mass%) of the non-volatile content in the measured polymer solution.

(Examples 1-2 and Comparative Examples 1-11)
[Preparation of coating solution for forming photosensitive resin layer]
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 coating solution for forming a photosensitive resin layer. In Table 3, the blending amount of the component (A) indicates the blending amount of the solid content. Further, the total concentration of hydrophilic groups (—O—, —C—CO—, —OH, —N—CO—, and —COOH) in the photosensitive resin layer is obtained from the raw material composition of the photosensitive resin composition by calculation. It was. The calculated values are shown in Table 3.

The symbols of the components in Table 3 have the following meanings.
[Component (A)]
The binder polymer solution (A1, A2, A3) produced by the method described above was used.
[(B) component]
T-1420: Ditrimethylolpropane tetraacrylate (manufactured by Nippon Kayaku Co., Ltd., product name)
4G: Polyethylene glycol # 200 dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name)
TMPTA: Trimethylolpropane triacrylate (Nippon Kayaku Co., Ltd., product name)
A-TMMT: Pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name)
DPHA: Dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd., product name)
RP1040: Ethoxylated pentaerythritol tetraacrylate (product name, manufactured by Nippon Kayaku Co., Ltd.)
A-LEN-10: Ethoxylated o-phenylphenol acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name)
BPE-80: Ethoxylated bisphenol A dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name)
401P: o-phenylphenol glycidyl ether acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name)
A-9300: Isocyanuric acid EO-modified triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name)
A-DCP: Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name)
[Component (C)]
OXE01: 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)] (manufactured by BASF Japan Ltd., product name “IRGACURE OXE 01”)
[Component (D)]
B-6030: 5-amino-1H-tetrazole (Chiyoda Chemical Co., Ltd., product name)
[(E) component]
PM-21: Phosphate ester containing an ethylenically unsaturated bond (product name, manufactured by Nippon Kayaku Co., Ltd.)
[Other ingredients]
AW500: 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (product name, manufactured by Kawaguchi Chemical Co., Ltd.)
ADDITIVE 8032: Octamethylcyclotetrasiloxane (product name, manufactured by Toray Dow Corning Co., Ltd.)
〔solvent〕
MEK: Methyl ethyl ketone

[Preparation of second resin layer forming coating solution]
The components shown in Table 4 were mixed using a stirrer for 15 minutes to prepare a second resin layer forming coating solution (IM-1).

The symbol of the component in Table 4 has the following meaning.
[Component (A)]
(A4): Propylene glycol monomethyl copolymer having a monomer blending ratio (methacrylic acid / methyl methacrylate / butyl acrylate / butyl methacrylate = 24 / 43.5 / 15.2 / 17.3 (mass ratio)) Ether solution, weight average molecular weight 18,000, acid value 156.6 mg KOH / g
[(B) component]
BPE-1300: Ethoxylated bisphenol A dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name)
[Component (D)]
B-6030: 5-amino-1H-tetrazole (Chiyoda Chemical Co., Ltd., product name)
[(E) component]
PM-21: Phosphoric acid ester having a photopolymerizable unsaturated group (manufactured by Nippon Kayaku Co., Ltd., product name) [(F) component]
OZ-S30K: Zirconia dispersion (manufactured by Nissan Chemical Industries, Ltd., product name: Nanouse OZ-S30K)
[Other ingredients]
L-7001: Octamethylcyclotetrasiloxane (product name, manufactured by Toray Dow Corning Co., Ltd.)

[Production of transfer-type photosensitive film]
Using a polypropylene film having a thickness of 30 μm (product name: E-201F, manufactured by Oji F-Tex Co., Ltd.) as the protective film, the second coating solution for forming a resin layer (IM-1) produced above is applied on the protective film. The film was uniformly coated using a die coater, dried for 3 minutes with a hot air retention dryer at 100 ° C. to remove the solvent, and a second resin layer having a thickness of 70 nm and a refractive index of 1.61 was formed.

  Using a polyethylene terephthalate film (product name: FB40, manufactured by Toray Industries, Inc.) having a thickness of 16 μm as a support film, the photosensitive resin layer forming coating solution prepared above is uniformly applied on the support film using a comma coater. The solvent was removed by drying with a hot air convection dryer at 100 ° C. for 3 minutes to form a photosensitive resin layer having a thickness of 8 μm.

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

[Measurement of moisture permeability]
The protective film of the photosensitive film obtained by the Example and the comparative example was peeled, and this was applied to a filter paper (Advantech Toyo Co., Ltd., No. 5C, φ90 mm circle, thickness 130 μm), roll temperature 100 ° C., substrate feed Lamination was performed under the conditions of a speed of 0.6 m / min and a pressure bonding pressure (cylinder pressure) of 0.5 MPa. Thereafter, the support film was peeled off. A new photosensitive film was laminated on the second resin layer and the photosensitive resin layer laminated on the filter paper by peeling off the protective film. By repeating this operation, a laminate in which five second resin layers and five photosensitive resin layers were alternately laminated on the filter paper and a support film was laminated on the outermost surface was produced. The total thickness of the photosensitive resin layers in this laminate is 40 μm.

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

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

Next, moisture permeability measurement was performed with reference to JIS standards (Z0208, cup method). A hygroscopic material (20 g of calcium chloride (anhydrous)) was placed in a measuring cup (φ 60 mm, depth 15 mm, Imoto Seisakusho Co., Ltd.). The measuring cup was covered with a circular sample piece cut with scissors to a diameter of 70 mm from the moisture permeability measurement sample. The sample was left in a constant temperature and humidity chamber at 60 ° C. and 90% RH for 24 hours. The moisture permeability (g / m ² · 24 h) according to JIS Z0208 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. The results are shown in Table 3.

[Evaluation of adhesion]
While peeling off the protective film of the photosensitive film obtained in Examples and Comparative Examples, a laminator (manufactured by Hitachi Chemical Co., Ltd., product name) so that the second resin layer is in contact with a glass substrate having a thickness of 0.7 mm. : HLM-3000 type), a roll temperature of 120 ° C., a substrate feed speed of 1 m / min, a pressure bonding pressure (cylinder pressure) of 4 × 10 ⁵ Pa (thickness of 1 mm, length of 10 cm × width of 10 cm) is used. Therefore, a laminate in which the linear pressure at this time is laminated under the condition of 9.8 × 10 ³ N / m), and the second resin layer, the photosensitive resin layer, and the support film are laminated on the glass substrate. Was made.

Next, the obtained laminate was subjected to an exposure amount of 6 × 10 J / m ² (measured value at a wavelength of 365 nm) from above the photosensitive resin layer side using a scattered light exposure machine (EXP-2805, manufactured by Oak Manufacturing Co., Ltd.). ), The support film was removed, and ultraviolet rays were irradiated from above the photosensitive resin layer with an exposure amount of 1 × 10 ⁴ J / m ² (measured value at a wavelength of 365 nm). Then, it left still for 30 minutes in the box-type dryer (Mitsubishi Electric Corporation make, model number: NV50-CA) heated at 140 degreeC, and obtained the adhesiveness measurement sample.

Next, 100 square grid cuts were put into the obtained adhesion measurement sample with a cutter. Then, it stuck on the scotch tape (made by 3M Japan) sample, and peeled off 30 seconds afterward. The peeling rate in 100 square grids at that time was investigated and evaluated according to the following criteria.
A: Peeling rate 0% or more and 5% or less B: Peeling rate 5% or more and 35% or less C: Peeling rate 35% or more and 100% or less

DESCRIPTION OF SYMBOLS 1 ... Transfer type photosensitive film, 10 ... Support film, 20 ... Photosensitive resin layer, 22 ... Hardened photosensitive resin layer, 30 ... Second resin layer, 32 ... Hardened second resin layer, 40 ... Protection Film: 50 ... Substrate with transparent electrode pattern, 50a ... Transparent electrode pattern, 60 ... Cured film, 100 ... Laminated body, 101 ... Transparent substrate, 102 ... Sensing region, 103, 104 ... Transparent electrode, 105 ... Lead-out wiring, 106: connection electrode, 107: connection terminal, 123: cured resin pattern (cured film).

Claims (12)

A support film, and a photosensitive resin layer provided on the support film,
In the photosensitive resin layer, a transfer type photosensitive resin in which the total concentration of hydrophilic groups selected from —O—, —C—CO—, —OH, —N—CO—, and —COOH is 0.020 mol / g or less. Sex film.   The transfer type photosensitive film according to claim 1, wherein the photosensitive resin layer contains a binder polymer, a photopolymerizable compound, and a photopolymerization initiator.   The transfer type photosensitive film according to claim 2, wherein the photopolymerizable compound includes a compound having a tricyclodecane skeleton or a tricyclodecene skeleton.   The transfer type photosensitive film of Claim 2 or 3 in which the said photoinitiator contains an oxime ester compound and / or a phosphine oxide compound.   The transfer type photosensitive film according to any one of claims 2 to 4, wherein the binder polymer has a carboxyl group.   The binder polymer is (meth) acrylic acid, (meth) acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, styrene, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid A binder polymer having a structural unit derived from at least one compound selected from the group consisting of butyl ester, (meth) acrylic acid 2-ethylhexyl ester and (meth) acrylic acid tricyclodecyl ester. The transfer type photosensitive film as described in any one of the above.   The transfer type photosensitive film according to claim 1, wherein the photosensitive resin layer further contains a phosphate ester containing an ethylenically unsaturated bond.   The transfer type photosensitive film as described in any one of Claims 1-7 further equipped with the 2nd resin layer containing the metal oxide particle provided on the said photosensitive resin layer.   The second resin layer includes at least one metal oxide particle selected from the group consisting of zirconium oxide, titanium oxide, tin oxide, zinc oxide, indium tin oxide, indium oxide, aluminum oxide, and yttrium oxide. The transfer type photosensitive film according to claim 8.   The transfer type photosensitive film of Claim 8 or 9 whose thickness of said 2nd resin layer is 10-1000 nm. Laminating the photosensitive resin layer of the transfer type photosensitive film according to any one of claims 1 to 10 on a substrate;
After exposing a predetermined portion of the photosensitive resin layer on the substrate, removing other than the predetermined portion, forming a cured resin pattern;
A method for forming a cured resin pattern.   A touch panel provided with the cured resin pattern containing the hardened | cured material of the said photosensitive resin layer in the transfer type photosensitive film as described in any one of Claims 1-10.

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