JP2015014783A - Method for manufacturing transparent substrate with cured film, photosensitive resin composition, photosensitive element, and electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a transparent substrate with a cured film, which has a cured film capable of achieving high transparency and desired film characteristics (particularly, high rust-prevention property) even when the film is thin.SOLUTION: The method for manufacturing a transparent substrate with a cured film comprises: disposing a photosensitive layer containing a photosensitive resin composition which comprises a binder polymer, a photopolymerizable compound and a specific photopolymerization initiator, on a transparent substrate; curing a predetermined part of the photosensitive layer by irradiation with active rays; and then removing the photosensitive layer except for the predetermined part so as to form a cured film of the photosensitive resin composition that partially or entirely covers the substrate.

Description

  The present invention relates to a method for producing a transparent substrate with a cured film, a photosensitive resin composition and a photosensitive element used therefor, and an electronic component.

  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 and FA devices. These liquid crystal display elements or touch panels are provided with electrodes made of a transparent conductive electrode material. As the transparent conductive electrode material, indium tin oxide (Indium-Tin-Oxide: ITO), indium oxide or tin oxide is known. Since these materials exhibit high visible light transmittance, they are mainly used as electrode materials used for substrates for liquid crystal display elements.

  Various types of touch panels have already been put into practical use. In recent years, the use of capacitive touch panels has progressed. In a capacitive touch panel, when a fingertip that is a conductor comes into contact with a touch input surface, capacitance is coupled between the fingertip and the conductive film to form a capacitor. For this reason, the capacitive touch panel detects the coordinates by capturing the change in charge at the contact position of the fingertip.

  In particular, a projected capacitive touch panel has a good operability such that a complex instruction can be performed because multiple fingertip detection is possible. Due to its good operability, a projected capacitive touch panel has been used as an input device on a display surface in a device having a small display device such as a mobile phone or 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 axis and the Y axis. Is forming. ITO is used as these electrodes.

  By the way, since the frame region of the touch panel is a region where the touch position cannot be detected, reducing the area of the frame region is an important element for improving the product value. In the frame area, metal wiring is required to transmit a touch position detection signal, but 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, in the touch panel as described above, corrosive components such as moisture and salt may intrude into the inside from the sensing region when touching the fingertip. 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 disconnection.

  In order to prevent corrosion of metal wiring, a capacitive projection type touch panel in which an insulating layer is formed on a metal is disclosed (for example, see Patent Document 1 below). In this 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, since this method uses a plasma CVD method, there is a problem that a high temperature treatment is required, a base material is limited, and a manufacturing cost is increased.

  By the way, as a method of providing a cured film such as a resist film at a required location, a method of providing a photosensitive layer made of a photosensitive resin composition on a predetermined substrate, and exposing and developing the photosensitive layer is known. (For example, refer to Patent Documents 2 to 4 below). Patent Documents 5 and 6 disclose forming a cured film such as an insulating film or a protective film for a touch panel by the above method.

JP 2011-28594 A JP-A-7-253666 JP 2005-99647 A JP-A-11-133617 JP 2010-27033 A Japanese Patent Application Laid-Open No. 2011-232585

  The production of a cured film using a photosensitive resin composition can be expected to reduce costs compared to the plasma CVD method. However, when a cured film is formed on a transparent substrate such as a touch panel substrate, if the thickness of the cured film is large, a step may be noticeable between a portion where the film is present and a portion where the film is not present. Therefore, it is preferable to make the cured film formed as thin as possible.

  However, when a photosensitive layer containing a photosensitive resin composition is provided on a transparent substrate with a thickness of 10 μm or less to form a cured film, it is difficult to achieve both high transparency and high rust prevention. The inventors have found. Moreover, in the photosensitive resin composition described in the said patent document 5 or 6, although it is possible to form a cured film with high transparency with a thin film, in order to make it compatible with high rust prevention property, there is room for improvement. was there.

  An object of this invention is to provide the manufacturing method of the transparent base material with a cured film which has a cured film which can make high transparency and desired film characteristics compatible, even if it is a thin film. The present invention also provides a photosensitive resin composition capable of forming a cured film that can achieve both high transparency and desired film characteristics even when formed as a thin film on a transparent substrate. It is another object of the present invention to provide an electronic component comprising a photosensitive element and a transparent substrate with a cured film.

  As a result of intensive studies by the present inventors to solve the above problems, a cured film is formed with a thin film (for example, a thickness of 10 μm or less) by using a photosensitive resin composition containing a specific photopolymerization initiator. Even in this case, it was found that both high transparency and high rust prevention can be achieved, and the present invention has been completed.

  The present invention provides a binder polymer, a photopolymerizable compound, a compound represented by the following general formula (1), a compound represented by the following general formula (2), and the following general formula (3) on a transparent substrate. And a photosensitive layer containing a photosensitive resin composition containing at least one photopolymerization initiator selected from the group consisting of the compounds represented by: and curing a predetermined portion of the photosensitive layer by irradiation with actinic rays A method for producing a transparent substrate with a cured film is provided, in which a portion other than the predetermined portion of the photosensitive layer is removed and a cured film of the photosensitive resin composition covering a part or all of the substrate is formed.

［式（１）中、Ｒ及びＲ^１は、炭素数１〜１２のアルキル基、炭素数４〜１０のシクロアルキル基、又はフェニル基を示し、Ｒ^２は、ＯＨ、ＣＯＯＨ、Ｏ（ＣＨ_２）ＯＨ、Ｏ（ＣＨ_２）_２ＯＨ、ＣＯＯ（ＣＨ_２）ＯＨ又はＣＯＯ（ＣＨ_２）_２ＯＨを示す。］

［式（２）中、Ｒ^３は、各々独立に炭素数１〜６のアルキル基を示し、Ｒ^４は、ＮＯ_２又はＡｒＣＯ（ここで、Ａｒはアリール基を示す。）を示し、Ｒ^５及びＲ^６は、炭素数１〜１２のアルキル基、フェニル基又はトリル基を示す。］

［式（３）中、Ｒ^７は、炭素数１〜６のアルキル基を示し、Ｒ^８は、アセタール結合を有する有機基を示し、Ｒ^９及びＲ^１０は、炭素数１〜１２のアルキル基、フェニル基又はトリル基を示す。なお、芳香環には、Ｒ^８以外の置換基を有してもよい。］

[In the formula (1), R and R ¹ represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or a phenyl group, and R ² represents OH, COOH, O (CH ₂ ) OH, O (CH ₂ ) ₂ OH, COO (CH ₂ ) OH or COO (CH ₂ ) ₂ OH. ]

[In Formula (2), R ³ each independently represents an alkyl group having 1 to 6 carbon atoms, R ⁴ represents NO ₂ or ArCO (wherein Ar represents an aryl group), and R ⁵ And R ⁶ represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group. ]

[In Formula (3), R ⁷ represents an alkyl group having 1 to 6 carbon atoms, R ⁸ represents an organic group having an acetal bond, and R ⁹ and R ¹⁰ represent an alkyl group having 1 to 12 carbon atoms. Represents a phenyl group or a tolyl group. The aromatic ring may have a substituent other than R ⁸ . ]

  ADVANTAGE OF THE INVENTION According to this invention, even if it is a thin film, the transparent base material with a cured film which has a cured film which can make high transparency and desired film | membrane characteristic (especially high rust prevention property) compatible can be obtained.

  The present inventors consider the reason why the above effect can be obtained by the method of the present invention as follows. First, since the conventional photosensitive resin composition mainly uses a photoreaction utilizing light in the ultraviolet region to the visible light region, a photoinitiator component whose absorption extends in the visible light region is often used. In many cases, pigments, dyes and the like are needed, and it is difficult to ensure transparency. Moreover, in order to express high rust prevention property, it is thought that it is necessary to fully improve the sclerosis | hardenability of the photosensitive resin composition. In order to sufficiently improve the curability, it is necessary to increase the amount of the photoinitiator component to be absorbed in the visible light region or to irradiate the photoinitiator with a high energy amount of active light. However, yellowing of the photoinitiator due to irradiation with a high energy amount of actinic rays is considered, and it is considered more difficult to ensure transparency. In the present invention, the specific oxime ester compound has low absorption in the visible light region, and the spectrum in the ultraviolet light region such as a high-pressure mercury lamp overlaps with the absorption wavelength, thereby increasing the absorption efficiency while suppressing yellowing. The present inventors speculate that by promoting the photoreaction, the obtained cured film can achieve both rust prevention and high transparency.

  Moreover, in the manufacturing method of the transparent base material with a cured film of this invention, it is preferable that the said photosensitive layer has the minimum value of the visible light transmittance in 400-700 nm being 85% or more.

  When forming the cured film of a transparent substrate, it is preferable that the transparency of the cured film is higher in view of the visibility or aesthetics of the final product (for example, touch panel). However, since the conventional photosensitive resin composition mainly uses a photoreaction utilizing light in the ultraviolet region to the visible light region, a photoinitiator component whose absorption extends in the visible light region is often used. In many cases, pigments, dyes and the like are needed, and it is difficult to ensure transparency. On the other hand, in the method for producing a transparent substrate with a cured film of the present invention, the minimum value of the visible light transmittance of the photosensitive layer is 85% or more by providing the specific photosensitive layer and performing actinic ray irradiation. Even in this case, desired film characteristics (particularly sufficient rust prevention) can be obtained.

The photosensitive layer preferably has a b ^* in the CIELAB color system of -0.2 to 1.0. In this case, even if a pattern is formed as a protective film on the electrode in the sensing region of the touch panel, for example, the visibility and aesthetics can be sufficiently prevented from being impaired.

  Moreover, in the method for producing a transparent substrate with a cured film of the present invention, a photosensitive element comprising a support film and a photosensitive layer containing the photosensitive resin composition provided on the support film is prepared. The photosensitive layer of the photosensitive element can be transferred onto the substrate to provide a photosensitive layer. In this case, a photosensitive layer having a uniform film thickness can be easily formed by using a photosensitive element.

  The present invention also includes a binder polymer, a photopolymerizable compound, a compound represented by the general formula (1), a compound represented by the general formula (2), and a compound represented by the general formula (3). 1 or more types of photoinitiators selected from the group which consists of, The photosensitive resin composition used in order to form a cured film on a transparent base material is provided.

  According to the photosensitive resin composition of the present invention, a cured film capable of achieving both high transparency and desired film characteristics (particularly high rust prevention) even on a predetermined transparent substrate, even if it is a thin film. Can be formed.

In the photosensitive resin composition of the present invention, the minimum value of the visible light transmittance at 400 to 700 nm is preferably 85% or more from the viewpoint of visibility or aesthetics of an electronic component on which a transparent substrate is mounted. Moreover, it is preferable that b ^* in a CIELAB color system is -0.2-1.0.

  The present invention also provides a photosensitive element comprising a support film and a photosensitive layer comprising the photosensitive resin composition according to the present invention provided on the support film.

  According to the photosensitive element of the present invention, a high transparency and desired film characteristics (particularly high rust prevention) can be achieved on a predetermined transparent substrate, and a good pattern can be obtained. A cured film having a shape can be formed.

  The present invention also provides an electronic component comprising a transparent substrate with a cured film obtained by the method according to the present invention on a transparent substrate.

  ADVANTAGE OF THE INVENTION According to this invention, even if it is a thin film, the manufacturing method of the transparent base material with a cured film which has high transparency and desired film | membrane characteristic (especially high rust prevention property) which can make compatible both is provided. be able to. In addition, according to the present invention, a photosensitive resin capable of forming a cured film that can achieve both high transparency and desired film characteristics (particularly high rust prevention) even if it is a thin film. An electronic component comprising the composition and the photosensitive element, and a transparent substrate with a cured film can be provided.

Fig.1 (a) is a schematic cross section of the photosensitive element which concerns on one Embodiment of this invention, FIG.1 (b) is a manufacturing method of the base material for touchscreens with a protective film which concerns on one Embodiment of this invention. It is a schematic cross section for demonstrating. Fig.2 (a) is a schematic cross section for demonstrating the manufacturing method of the base material for touchscreen with a protective film which concerns on one Embodiment of this invention, FIG.2 (b) is one Embodiment of this invention. It is a schematic cross section of the base material for touchscreens with a protective film which concerns. FIG. 3 is a schematic plan view showing a capacitive touch panel according to an embodiment of the present invention. 4A is a partial cross-sectional view taken along line IVa-IVa in FIG. 3, and FIG. 4B corresponds to FIG. 4A in the capacitive touch panel according to another embodiment. It is a fragmentary sectional view of the part to do. FIG. 5 is a schematic plan view showing a capacitive touch panel according to another embodiment of the present invention. FIG. 6 is a schematic plan view showing an example of a capacitive touch panel in which transparent electrodes exist on the same plane. 7 is a partially cutaway perspective view of FIG. 8 is a partial cross-sectional view taken along line VIII-VIII in FIG. FIG. 9 is a diagram for explaining an example of a method for manufacturing a capacitive touch panel in which transparent electrodes are present on the same plane, and (a) is a partially cutaway perspective view showing a substrate provided with transparent electrodes. (B) is a partially cutaway perspective view showing the obtained capacitive touch panel. FIG. 10 is a diagram for explaining an example of a method for manufacturing a capacitive touch panel in which transparent electrodes are present on the same plane, and (a) is a partial cross-sectional view taken along line Xa-Xa in FIG. FIG. 10B is a partial cross-sectional view showing a step of providing an insulating film, and FIG. 10C is a partial cross-sectional view taken along line Xc-Xc in FIG. 9. FIG. 11 is a partial plan view showing a capacitive touch panel according to an embodiment of the present invention.

  Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the present specification, “(meth) acrylic acid” means acrylic acid or methacrylic acid, “(meth) acrylate” means acrylate or a corresponding methacrylate, and “(meth) acryloyl”. “Group” means an acryloyl group or a methacryloyl group.

  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. In the present specification, a 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 is the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. Means.

  The manufacturing method of the transparent base material with a cured film which concerns on this embodiment provides the photosensitive layer containing the photosensitive resin composition which concerns on this invention on a transparent base material, and hardens | cures the predetermined part of a photosensitive layer by irradiation of actinic light Then, a portion other than the predetermined portion of the photosensitive layer is removed to form a cured film of the photosensitive resin composition that covers a part or all of the substrate. The photosensitive resin composition according to the present invention contains a binder polymer, a photopolymerizable compound, and a specific photopolymerization initiator described later.

  Examples of the transparent substrate include glass plates such as white plate glass, blue plate glass, and silica-coated blue plate glass; plastic substrates such as polyethylene terephthalate, polycarbonate, and cycloolefin polymer; and substrates such as ceramic plates. The transparent substrate preferably has a minimum light transmittance of 85% or more in a wavelength range of 400 to 700 nm.

  The photosensitive layer is provided with a photosensitive element comprising a support film and a photosensitive layer containing the photosensitive resin composition provided on the support film, and the photosensitive layer of the photosensitive element is used as the transparent substrate. It can be provided by transferring it on top.

  Fig.1 (a) is a schematic cross section which shows one Embodiment of the photosensitive element which concerns on this invention. A photosensitive element 1 shown in FIG. 1A includes a support film 10, a photosensitive layer 20 including the photosensitive resin composition according to the present invention provided on the support film 10, and the support film 10 of the photosensitive layer 20. And a protective film 30 provided on the opposite side.

  The photosensitive element 1 of this embodiment can be suitably used for forming a cured film on a transparent substrate.

  In this specification, when using the cured film of a transparent base material for a touch panel, for example, it can be provided in a sensing region having electrodes, a frame region having metal wiring, or other regions. The cured film of the touch panel base material may be provided only in one of the regions, or may be provided in a plurality of regions. Furthermore, the position and range where the cured film is provided, such as being provided on a part of the electrode formed in the sensing region, can be appropriately selected according to the purpose of use.

  As the support film 10, a polymer film can be used. Examples of the polymer film include films made of polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, polyethersulfone, and the like.

  The thickness of the support film 10 is preferably 5 to 100 μm, and preferably 10 to 70 μm, from the viewpoint of ensuring coverage and suppressing a decrease in sensitivity when irradiating active light through the support film 10. More preferably, it is 15-40 micrometers, It is further more preferable, It is especially preferable that it is 20-35 micrometers.

  The photosensitive resin composition according to the present invention constituting the photosensitive 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 specific which will be described later. Photopolymerization initiator (hereinafter also referred to as component (C)).

  In this embodiment, the (A) component is preferably a copolymer containing a structural unit derived from (a1) (meth) acrylic acid and a structural unit derived from (a2) (meth) acrylic acid alkyl ester. is there.

  (A1) The content of the structural unit derived from (meth) acrylic acid is preferably 20% by mass or less, based on the total mass of the monomer constituting the component (A), from the viewpoint of excellent rust prevention. It is more preferably 18% by mass or less, and further preferably 15% by mass or less.

  (A2) Examples of (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, and Examples include (meth) acrylic acid hydroxyl ethyl ester.

  (A2) The content of the structural unit derived from the (meth) acrylic acid alkyl ester is preferably 90% by mass or less, and 89% by mass or less, based on the total mass of the monomers constituting the component (A). Is more preferable, and it is still more preferable that it is 88 mass%.

  The copolymer may further contain other monomers that can be copolymerized with the component (a1) and / or the component (a2) in the structural unit.

  Examples of the other monomer that can be copolymerized with the component (a1) and / or the component (a2) include (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, and (meth) acrylic. Acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate , (Meth) acrylamide, (meth) acrylonitrile, diacetone (meth) acrylamide, styrene, and vinyltoluene. When synthesizing the binder polymer as component (A), the above monomers may be used alone or in combination of two or more.

  The weight average molecular weight of the binder polymer as the component (A) is preferably 10,000 to 200,000, more preferably 15,000 to 150,000, and more preferably 30,000 to 30,000 from the viewpoint of resolution. It is more preferably 150,000, particularly preferably 30,000 to 100,000, and very preferably 40,000 to 100,000. In addition, the measurement conditions of a weight average molecular weight shall be the same measurement conditions as the Example of this-application specification.

  The acid value of the binder polymer as component (A) is preferably 75 to 200 mgKOH / g, more preferably 75 to 150 mgKOH / g, and more preferably 75 to 120 mgKOH in terms of excellent rust prevention and patterning properties. More preferably, it is / g.

The acid value of the binder polymer as the component (A) can be measured as follows.
That is, first, 1 g of the binder polymer that is the object of acid value measurement is precisely weighed. 30 g of acetone is added to the precisely weighed binder polymer and dissolved uniformly. Next, an appropriate amount of phenolphthalein as an indicator is added to the solution, and titration is performed using a 0.1N potassium hydroxide (KOH) aqueous solution. The acid value is determined by calculating the number of mg of KOH required to neutralize the acetone solution of the binder polymer to be measured. When a solution obtained by mixing a binder polymer with a synthetic solvent, a diluting solvent, or the like is an object to be measured, the acid value is calculated by the following formula.
Acid value = 0.1 × Vf × 56.1 / (Wp × I / 100)
In the formula, Vf represents the titration amount (mL) of the aqueous KOH solution, Wp represents the weight (g) of the solution containing the measured binder polymer, and I represents the ratio of the nonvolatile content in the solution containing the measured binder polymer. (Mass%) is shown.
In addition, when blending the binder polymer in a state mixed with volatile components such as a synthetic solvent and a diluting solvent, the mixture is preliminarily heated for 1 to 4 hours at a temperature higher than the boiling point of the volatile components by 1 to 4 hours before being volatile. The acid value can also be measured after removing the component.

  As the photopolymerizable compound as component (B), a photopolymerizable compound having an ethylenically unsaturated group can be used.

  Examples of the photopolymerizable compound having an ethylenically unsaturated group include a monofunctional vinyl monomer, a bifunctional vinyl monomer, and a polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups.

  Examples of the monofunctional vinyl monomer include (meth) acrylic acid, (meth) acrylic acid alkyl ester, and those co-polymerized as monomers used for the synthesis of a copolymer which is a preferred example of the component (A). Examples thereof include polymerizable monomers.

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

  Examples of the polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups include trimethylolpropane tri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, Polyhydric alcohols such as dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetraacrylate, and α, β-unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, etc.) Compound obtained by reaction; Compound obtained by addition reaction of glycidyl group-containing compound such as trimethylolpropane triglycidyl ether tri (meth) acrylate and α, β-unsaturated carboxylic acid; Diglycerin (meth) Diglycerol and α such acrylate, and compounds obtained by adding a β- unsaturated carboxylic acid.

  Among these, it is preferable to contain a polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups. Furthermore, from the viewpoint of electrode corrosion inhibition and ease of development, it has a (meth) acrylate compound having a skeleton derived from pentaerythritol, a (meth) acrylate compound having a skeleton derived from dipentaerythritol, and a skeleton derived from trimethylolpropane. It is preferable to include at least one selected from (meth) acrylate compounds, and at least selected from (meth) acrylate compounds having a skeleton derived from dipentaerythritol and (meth) acrylate compounds having a skeleton derived from trimethylolpropane. It is more preferable that 1 type is included.

  Here, (meth) acrylate having a skeleton derived from dipentaerythritol means an esterified product of dipentaerythritol and (meth) acrylic acid, and the esterified product is a compound modified with an alkyleneoxy group. Are also included. The esterified product preferably has 6 ester bonds in one molecule, but a compound having 1 to 5 ester bonds may be mixed therein.

  The (meth) acrylate compound having a skeleton derived from trimethylolpropane means an esterified product of trimethylolpropane and (meth) acrylic acid, and the esterified product is a compound modified with an alkyleneoxy group. Are also included. The esterified product preferably has 3 ester bonds in one molecule, but may contain a compound having 1 to 2 ester bonds. Further, as the (meth) acrylate compound having a skeleton derived from trimethylolpropane, a compound obtained by dimerizing a trimethylolpropane di (meth) acrylate compound may be used.

  Said compound can be used individually by 1 type or in combination of 2 or more types.

  When a monomer having at least three polymerizable ethylenically unsaturated groups 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 suppression of electrode corrosion are suppressed. From the viewpoint of obtaining strength, the proportion of the monomer having at least three polymerizable ethylenically unsaturated groups is 30 parts by mass or more with respect to 100 parts by mass of the total amount of the photopolymerizable compound contained in the photosensitive resin composition. It is preferable that it is 50 mass parts or more, and it is still more preferable that it is 75 mass parts or more.

  The content of the component (A) and the component (B) in the photosensitive resin composition of the present embodiment is such that the component (A) is 35 to 35 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). 85 parts by mass, component (B) is preferably 15-65 parts by mass, component (A) is 40-80 parts by mass, and component (B) is more preferably 20-60 parts by mass, (A It is more preferable that the component is 50 to 70 parts by mass, the component (B) is 30 to 50 parts by mass, the component (A) is 55 to 65 parts by mass, and the component (B) is 35 to 45 parts by mass. Is particularly preferred. In particular, in terms of maintaining transparency and forming a pattern, the content of the component (A) and the component (B) is (A) relative to 100 parts by mass of the total amount of the component (A) and the component (B). The component is preferably 35 parts by mass or more, more preferably 40 parts by mass or more, still more preferably 50 parts by mass or more, and particularly preferably 55 parts by mass or more.

  By setting the content of the component (A) and the component (B) within the above range, sufficient sensitivity can be obtained while sufficiently securing the coatability or film forming property of the photosensitive element, and photocurability, Sufficient developability and suppression of electrode corrosion can be secured.

  The photosensitive resin composition of the present embodiment is represented by a compound represented by the following general formula (1), a compound represented by the following general formula (2), and the following general formula (3) as a photopolymerization initiator. 1 or more types of photoinitiators selected from the group consisting of: By using such a photosensitive resin composition, a cured film having sufficient antirust property can be formed on a transparent substrate even if it is a thin film. The cured film is sufficiently excellent in transparency.

In formula (1), R and R ¹ represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or a phenyl group, and R ² represents OH, COOH, O (CH ₂ ). OH, O (CH ₂ ) ₂ OH, COO (CH ₂ ) OH or COO (CH ₂ ) ₂ OH is shown. Incidentally, the aromatic ring may have a substituent group other than R ^2.

In Formula (2), R ³ represents an alkyl group having 1 to 6 carbon atoms, R ⁴ represents NO ₂ or ArCO (where Ar represents an aryl group), and R ⁵ and R ⁶ represent Represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group. The aromatic ring may have a substituent other than R ⁴ .

In Formula (3), R ⁷ represents an alkyl group having 1 to 6 carbon atoms, R ⁸ represents an organic group having an acetal bond, R ⁹ and R ¹⁰ represent an alkyl group having 1 to 12 carbon atoms, A phenyl group or a tolyl group is shown. The aromatic ring may have a substituent other than R ⁸ (such as a methyl group).

In the general formula (1), R and R ¹ represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or a phenyl group, but an alkyl group having 1 to 8 carbon atoms, carbon It is preferably a cycloalkyl group having 4 to 6 carbon atoms or a phenyl group, more preferably an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms or a phenyl group, and a methyl group or a cyclopentyl group. Or it is still more preferable that it is a phenyl group. R ² represents OH, COOH, O (CH ₂ ) OH, O (CH ₂ ) ₂ OH, COO (CH ₂ ) OH or COO (CH ₂ ) ₂ OH, but O (CH ₂ ) OH, O (CH ₂ ) ₂ OH, COO (CH ₂ ) OH or COO (CH ₂ ) ₂ OH is preferred, and O (CH ₂ ) ₂ OH or COO (CH ₂ ) ₂ OH is more preferred.

In the general formula (2), R ³ represents an alkyl group having 1 to 6 carbon atoms, and is preferably a propyl group. R ⁴ represents NO ₂ or ArCO, Ar represents an aryl group, and Ar is preferably a tolyl group. R ⁵ and R ⁶ represent an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group, and are preferably a methyl group, a phenyl group, or a tolyl group.

In the general formula (3), R ⁷ represents an alkyl group having 1 to 6 carbon atoms, and is preferably an ethyl group. Although R ⁸ is an organic group having an acetal bond, it is preferably a substituent group of the compound represented by the following formula (3-1). Furthermore, R ⁹ and R ¹⁰ is an alkyl group having 1 to 12 carbon atoms, but a phenyl group or a tolyl group, a methyl group is preferably a phenyl group or a tolyl group, and more preferably a methyl group.

  Examples of the compound represented by the general formula (1) include a compound represented by the following formula (1-1). This is available as Adeka Cruise NCI-930 (trade name, manufactured by ADEKA Corporation).

  Examples of the compound represented by the general formula (2) include compounds represented by the following formulas (2-1) and (2-2). These compounds are available as DFI-091 and DFI-020 (both manufactured by Daitokemix Co., Ltd., trade names).

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

  The photopolymerization initiator is selected from the group consisting of a compound represented by the above general formula (1), a compound represented by the following general formula (2), and a compound represented by the following general formula (3). Photopolymerization initiators other than the above photopolymerization initiators (oxime ester compounds) can also be used in combination. Examples of such a photopolymerization initiator include benzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2- Aromatic ketones such as methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; benzoin, methyl benzoin and ethyl benzoin Benzoin compounds such as benzyl dimethyl ketal; benzyl derivatives such as benzyl dimethyl ketal; acridine derivatives such as 9-phenylacridine and 1,7-bis (9,9′-acridinyl) heptane; N-phenylglycine and N-phenylglycine derivatives; Compound; -Thioxanthone compounds such as chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone; tertiary amine compounds; Examples include oxazole compounds. Moreover, you may combine a thioxanthone type compound and a tertiary amine compound like the combination of diethyl thioxanthone and dimethylaminobenzoic acid.

  The content of the photopolymerization initiator that is the component (C) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B), and 1 to 10 parts by mass. More preferably, it is 2-5 mass parts. The content of the component (C) is preferably 0.1 parts by mass or more in terms of excellent photosensitivity and resolution, and is preferably 20 parts by mass or less in terms of excellent visible light transmittance.

  In addition to the photosensitive resin composition of the present embodiment, if necessary, adhesion imparting agents such as ultraviolet absorbers, silane coupling agents, leveling agents, plasticizers, fillers, antifoaming agents, flame retardants, A stabilizer, an antioxidant, a fragrance, a thermal crosslinking agent, a polymerization inhibitor, and the like may be contained in an amount of about 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). it can. These can be used alone or in combination of two or more.

  In the photosensitive resin composition of the present embodiment, the minimum value of visible light transmittance at 400 to 700 nm is preferably 85% or more, more preferably 92% or more, and further preferably 95% or more. preferable.

  Here, the visible light transmittance of the photosensitive resin composition can be determined as follows. First, a photosensitive resin composition layer (photosensitive layer) is coated by applying a coating solution containing the photosensitive resin composition on a support film so that the thickness after drying is 10 μm or less, and drying it. Form. Next, it laminates on a glass substrate using a laminator so that the photosensitive resin composition layer (photosensitive layer) is in contact. Thus, a measurement sample in which the photosensitive layer and the support film are laminated on the glass substrate is obtained. Next, after irradiating the obtained measurement sample with ultraviolet rays and photocuring the photosensitive layer, the transmittance in a measurement wavelength region of 400 to 700 nm is measured using an ultraviolet-visible spectrophotometer.

  If the minimum value of the transmittance in the wavelength range of 400 to 700 nm, which is a light beam in a general visible light wavelength range, is 85% or more, for example, when protecting the transparent electrode in the sensing area of the touch panel (touch sensor), the touch panel Image quality in the sensing area when the metal layer in the frame area of the (touch sensor) (for example, a layer in which a copper layer is formed on the ITO electrode) is protected and a cured film is visible from the edge of the sensing area. Further, it is possible to sufficiently suppress a decrease in hue and luminance.

In the photosensitive resin composition of the present embodiment, b ^* in the CIELAB color system is preferably −0.2 to 1.0, more preferably 0.0 to 0.7, More preferably, it is 0.1-0.4. Similarly to the case where the minimum value of the visible light transmittance is 85% or more, b ^* may be −0.2 or more and 1.0 or less from the viewpoint of image display quality in the sensing area and prevention of deterioration in hue. preferable. Note that b ^* in the CIELAB color system is, for example, a spectrophotometer “CM-5” manufactured by Konica Minolta, and a b ^* is 0.1 to 0.2 on a glass substrate having a thickness of 0.7 mm. It is obtained by forming a photosensitive resin composition layer having a thickness of 10 μm or less, irradiating with ultraviolet rays and photocuring the photosensitive resin composition layer, and then measuring by setting a D65 light source and a viewing angle of 2 °.

  Moreover, it is preferable that the light absorbency in 365 nm is 0.4 or less from the viewpoint of the photosensitive resin composition of this embodiment improving the resolution more. Moreover, it is preferable that the light absorbency in 334 nm is 0.4 or more. When the photosensitive layer containing the photosensitive resin composition has the light absorption characteristics described above, it becomes easier to absorb the leaked light, and the decomposition of the oxime ester compound due to the leaked light can be suppressed.

  The absorbance can be measured using a UV spectrophotometer (manufactured by Hitachi, Ltd., spectrophotometer U-3310). In the measurement, the photosensitive element having the above-mentioned photosensitive layer formed on the support film with an arbitrary film thickness is placed on the measurement side, the support film is placed on the reference side, and 300 to 700 nm is continuously measured in the absorbance mode, and 334 nm. This is done by reading the value at 365 nm.

  Examples of the method for adjusting the absorbance within the above range include the combined use of an oxime ester compound and an ultraviolet absorber, and the control of the film thickness of the photosensitive layer.

  The photosensitive resin composition of the present embodiment can be used for forming a photosensitive layer on a substrate. For example, by preparing a coating solution that can be obtained by uniformly dissolving or dispersing the photosensitive resin composition in a solvent, applying a coating on a transparent substrate, and then removing the solvent by drying. A photosensitive layer can be formed.

  Solvents include ketones, aromatic hydrocarbons, alcohols, glycol ethers, glycol alkyl ethers, glycol alkyl ether acetates, esters, diethylene glycol, chloroform, and chloride from the standpoints of solubility of each component and ease of film formation. Methylene or the like can be used. These solvents may be used alone or as a mixed solvent composed of two or more solvents.

  Among the above solvents, it is preferable to use ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like.

  The photosensitive resin composition of the present invention is preferably used after being formed on a photosensitive film like a photosensitive element. Laminating a photosensitive film on a transparent substrate having a touch panel electrode can easily realize a roll-to-roll process, shorten a solvent drying process, etc., and greatly contribute to shortening the manufacturing process and reducing costs. Can do.

  The photosensitive layer 20 of the photosensitive element 1 can be formed by preparing a coating solution containing the photosensitive resin composition of the present embodiment, and applying and drying the coating solution on the support film 10. The coating solution can be obtained by uniformly dissolving or dispersing each component constituting the photosensitive resin composition of the present embodiment described above in a solvent.

  The solvent is not particularly limited and known ones can be used. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, methanol, ethanol, propanol, butanol, methylene glycol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, Examples include 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, and methylene chloride. These solvents may be used alone or as a mixed solvent composed of two or more solvents.

  Application methods include, for example, 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 A die coating method may be mentioned.

  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 thickness of the photosensitive layer is the thickness after drying so that the step on the surface of the touch panel (touch sensor) produced by the formation of a partially cured film can be minimized as long as it is effective for protecting transparent substrates and electrodes. It is preferably 1 μm or more and 9 μm or less, more preferably 1 μm or more and 8 μm or less, further preferably 2 μm or more and 8 μm or less, and particularly preferably 3 μm or more and 8 μm or less.

In the present embodiment, the minimum value of the visible light transmittance of the photosensitive layer 20 is preferably 85% or more, more preferably 92% or more, and further preferably 95% or more. The b ^* in the CIELAB color system of the photosensitive layer 20 is preferably −0.2 to 1.0, more preferably 0.0 to 0.7, and 0.1 to 0.4. More preferably. Moreover, it is preferable that the light absorbency in 365 nm of the photosensitive layer 20 is 0.4 or less. The absorbance at 334 nm of the photosensitive layer 20 is preferably 0.4 or more.

  The viscosity of the photosensitive layer 20 is to prevent the photosensitive resin composition from exuding from the end face of the photosensitive element 1 for one month or more when the photosensitive element is rolled, and to cut the photosensitive element 1 From 30 to 100 mPa · s at 30 ° C., from the point of preventing exposure failure and residual development when irradiated with actinic rays caused by the fragments of the photosensitive resin composition adhering to the substrate. Preferably, the pressure is 20 to 90 mPa · s, more preferably 25 to 80 mPa · s.

The viscosity is 1.96 × at 30 ° C. and 80 ° C. in the thickness direction of this sample using a circular film of 7 mm in diameter and 2 mm in thickness formed from the photosensitive resin composition as a measurement sample. It is a value obtained by measuring the rate of change of thickness when a load of 10 ⁻² N is applied, and converting it to viscosity from the rate of change assuming a Newtonian fluid.

  A polymer film can be used as the protective film 30 (cover film). Examples of the polymer film include polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, polyethylene-vinyl acetate copolymer, and a film made of a laminated film of polyethylene-vinyl acetate copolymer and polyethylene.

  The thickness of the protective film 30 is preferably about 5 to 100 μm, but from the viewpoint of storing it in a roll shape, it is preferably 70 μm or less, more preferably 60 μm or less, and further preferably 50 μm or less. It is preferably 40 μm or less.

  The photosensitive element 1 can be stored in a roll or stored.

In this invention, the photosensitive resin composition of this embodiment mentioned above and the coating liquid containing a solvent are apply | coated on the transparent base material (base material for touchscreens) which has an electrode for touchscreens, it dries, and is photosensitive. A photosensitive layer 20 containing a resin composition may be provided. Even in this application, the photosensitive layer preferably satisfies the above-mentioned conditions of film thickness, visible light transmittance, b ^* in the CIELAB color system, and absorbance.

  Next, the manufacturing method of the transparent base material with a cured film which concerns on this invention is demonstrated. The manufacturing method of the transparent base material with a cured film of this invention is a protective film of the electronic components by which protection by a thin film is requested | required like the protective film of the electrode for touchscreens, Especially protection of the metal electrode of an electrostatic capacitance type touch panel It can be suitably used for forming a film.

  As an embodiment of the method for producing a transparent substrate with a cured film according to the present invention, a method for producing a substrate for a touch panel with a protective film having a protective film for an electrode for a touch panel will be described (FIGS. 1B and 2). reference). FIG.1 and FIG.2 is a schematic cross section for demonstrating an example of the manufacturing method of the base material for touchscreen with a protective film which concerns on one Embodiment of this invention.

  The manufacturing method of the base material for touchscreens with a protective film of this embodiment WHEREIN: On the transparent base material 200 (base material for touchscreens) which has the electrodes 210 and 220 for touchscreens, the photosensitive resin composition which concerns on said this embodiment is carried out. A first step of providing a photosensitive layer 20 having a thickness of 10 μm or less (see FIG. 1B), and a second step of curing a predetermined portion of the photosensitive layer 20 by irradiation with an actinic ray L including ultraviolet rays ( 2 (a)) and a photosensitive resin that covers a part or all of an electrode by removing a photosensitive layer other than a predetermined portion after irradiation with actinic rays (a portion of the photosensitive layer that has not been irradiated with actinic rays) A third step (see FIG. 2B) for forming a protective film 22 composed of a cured film pattern of the composition layer (photosensitive layer). In this way, the base material 300 for touchscreens with a protective film is obtained. The base material for touchscreens with a protective film obtained can be used as a touchscreen with a protective film (touch sensor) which is a touch input sheet.

  As a base material for touchscreens used by this embodiment, what provided the electrode for touchscreens on the transparent base material is mentioned. Examples of the transparent substrate 200 include substrates such as glass plates, plastic plates, and ceramic plates that are generally used for touch panels (touch sensors). On this board | substrate, the electrode for touchscreens used as the object which forms the cured film used as a protective film is provided. Examples of the electrode include electrodes such as ITO, Cu, Al, and Mo, and TFT. An insulating layer may be provided on the substrate between the substrate and the electrode. The touch panel substrate preferably has a minimum light transmittance of 85% or more in a wavelength region of 400 to 700 nm.

  The base material for touch panels which has the electrodes 210 and 220 for touch panels shown by FIG.1 (b) can be obtained in the following procedures, for example. After forming a metal film by sputtering in the order of ITO and Cu on a transparent substrate 200 such as a PET film, an etching photosensitive film is pasted on the metal film to form a desired resist pattern, and unnecessary Cu Is removed with an etching solution such as an aqueous iron chloride solution, and then the resist pattern is peeled off.

  In the first step of the present embodiment, after removing the protective film 30 of the photosensitive element 1 of the present embodiment, the touch panel electrodes 210 and 220 of the touch panel substrate are provided while the photosensitive element 1 is heated. The photosensitive layer 20 is transferred by pressure bonding to the existing surface and laminated (see FIG. 1B).

  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.

  The heating temperature for thermocompression bonding is a component of the photosensitive layer 20 while ensuring sufficient adhesion between the photosensitive layer 20 and the touch panel substrate, and sufficient adhesion between the photosensitive layer 20 and the touch panel electrodes 210 and 220. Is preferably set to 10 to 180 ° C., more preferably 20 to 160 ° C., and further preferably 30 to 150 ° C. so that is hard to be thermally cured or thermally decomposed.

In addition, the pressure during thermocompression bonding is 50 to 1 × 10 ⁵ N in terms of linear pressure from the viewpoint of suppressing deformation of the touch panel base material while ensuring sufficient adhesion between the photosensitive layer 20 and the touch panel base material. / M, preferably 2.5 × 10 ^{2 to} 5 × 10 ⁴ N / m, more preferably 5 × 10 ² to 4 × 10 ⁴ N / m.

  If the photosensitive element 1 is heated as described above, it is not necessary to pre-heat the base material for the touch panel, but from the point of further improving the adhesion between the photosensitive layer 20 and the base material for the touch panel, It is preferred to preheat the material. The preheating temperature at this time is preferably 30 to 180 ° C.

  In this embodiment, instead of using a photosensitive element, a coating liquid containing the photosensitive resin composition and solvent of this embodiment is prepared, and touch panel electrodes 210 and 220 of a touch panel substrate are provided. The photosensitive layer 20 can be formed by coating on the surface and drying.

The photosensitive layer 20 preferably satisfies the above-described conditions of film thickness, visible light transmittance, b ^* in the CIELAB color system, and absorbance.

  In the second step of the present embodiment, a predetermined portion of the photosensitive layer 20 is irradiated with an actinic ray L in a pattern via a photomask 230 (see FIG. 2A).

  When irradiating actinic light, if the support film 10 on the photosensitive layer 20 is transparent, it can be irradiated with actinic light as it is. From the viewpoint of protecting the photosensitive layer 20, it is preferable to use a transparent polymer film as the support film 10 and to irradiate actinic rays through the polymer film with the polymer film remaining.

  As a light source of actinic light used for irradiation of actinic light L, a known actinic light source can be used, and examples thereof include a carbon arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, etc. If it is, it will not be restrict | limited.

The irradiation amount of the actinic ray L at this time is usually 1 × 10 ² to 1 × 10 ⁴ J / m ² , and heating can be accompanied during irradiation. If the irradiation amount of actinic rays is less than 1 × 10 ² J / m ² , the effect of photocuring tends to be insufficient, and if it exceeds 1 × 10 ⁴ J / m ² , the photosensitive layer 20 tends to discolor. There is.

  In the present embodiment, the photosensitive layer 20 having an absorbance at 365 nm of 0.4 or less and an absorbance at 334 nm of 0.4 or more, and an actinic ray such as a UV laser having oscillation in an ultrahigh pressure mercury lamp, 355 nm, 364 nm, or the like. The combination with the light source is preferable.

  In the third step of the present embodiment, the photosensitive layer after irradiation with actinic rays is developed with a developer to remove a portion not irradiated with actinic rays (that is, other than a predetermined portion of the photosensitive layer), and a part of the electrode Or the protective film 22 which consists of the cured film pattern of the photosensitive resin composition of this embodiment of the thickness which covers the whole is 10 micrometers or less is formed (refer (b) of FIG. 2). The formed protective film 22 can have a predetermined pattern.

  When the support film 10 is laminated on the photosensitive layer 20 after irradiation with actinic rays, the support film 10 is removed, and then development for removing a portion not irradiated with actinic rays with a developer is performed.

  As a development method, development is performed by a known method such as spraying, showering, rocking dipping, brushing, scraping, etc., using a known developing solution such as an alkaline aqueous solution, an aqueous developer, or an organic solvent, and unnecessary portions are removed. Among them, it is preferable to use an alkaline aqueous solution from the viewpoint of environment and safety.

  Examples of the base of the alkaline aqueous solution include alkali hydroxide (lithium, sodium or potassium hydroxide, etc.), alkali carbonate (lithium, sodium or potassium carbonate or bicarbonate, etc.), alkali metal phosphate (potassium phosphate, etc.) , Sodium phosphate, etc.), alkali metal pyrophosphates (sodium pyrophosphate, potassium pyrophosphate, etc.), tetramethylammonium hydroxide, triethanolamine, etc. Among them, tetramethylammonium hydroxide, etc. are preferred. It is done.

  An aqueous solution of sodium carbonate is also preferably used. For example, a dilute solution of sodium carbonate (0.5 to 5% by mass aqueous solution) at 20 to 50 ° C. is preferably used.

  The development temperature and time can be adjusted according to the developability of the photosensitive resin composition of the present embodiment.

  Further, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like can be mixed in the alkaline aqueous solution.

  Further, the base of the alkaline aqueous solution remaining in the photosensitive layer 20 after development and photocuring is used by known methods such as spraying, rocking immersion, brushing, and scraping using an organic acid, an inorganic acid, or an acid aqueous solution thereof. Acid treatment (neutralization treatment) can be performed.

  Furthermore, the water washing process can also be performed after an acid treatment (neutralization treatment).

After development, the cured film pattern may be further cured by irradiation with actinic rays (for example, 5 × 10 ³ to 2 × 10 ⁴ J / m ² ) as necessary. The photosensitive resin composition of the present embodiment exhibits excellent adhesion to a metal without a heating step after development, but if necessary, instead of irradiation with actinic light after development or an active A heat treatment (80 to 250 ° C.) may be performed in combination with the irradiation of light.

  As described above, the photosensitive resin composition and photosensitive element of this embodiment are used for forming a cured film on a transparent substrate (use as a resin cured film pattern forming material as a cured film), a touch panel. It is suitable for use for forming a protective film of a base material for use (use as a resin-cured film pattern forming material as a protective film) and the like. About the said use of the photosensitive resin composition, a protective film can be formed using the coating liquid mixed with the solvent.

  Moreover, this invention can provide the resin cured film pattern forming material containing the photosensitive resin composition which concerns on this invention. This cured resin film pattern forming material can contain the photosensitive resin composition of the present embodiment described above, and is preferably a coating solution containing the solvent described above.

(Electronic components and manufacturing method thereof)
The electronic component according to the present embodiment includes the transparent substrate with a cured film according to the present embodiment. The transparent substrate with a cured film includes a cured product (cured film or the like) of the photosensitive resin composition according to the present embodiment on the transparent substrate. In the electronic component according to the present embodiment, the cured film can be used as, for example, a protective member (protective film or the like), an insulating member (insulating film or the like), or the like.

  As an electronic component which concerns on this embodiment, a touch panel, a liquid crystal display, an organic electroluminescent display, a solar cell module, a printed wiring board, and electronic paper are mentioned, for example.

  Hereinafter, with reference to FIGS. 3 to 5, the electronic component according to the present embodiment and the manufacturing method thereof (an example of use of a cured film pattern and a place where a protective film is used) will be further described.

  FIG. 3 is a schematic plan view showing an example of a capacitive touch panel according to an embodiment of the present invention. 4A is a partial cross-sectional view taken along line IVa-IVa in FIG. 3, and FIG. 4B corresponds to FIG. 4A in the capacitive touch panel according to another embodiment. FIG. 5 is a schematic plan view showing another example of a capacitive touch panel.

  A touch panel (capacitive touch panel) 400 shown in FIGS. 3 and 4A has a touch screen 402 for detecting touch position coordinates on one side of a transparent substrate (transparent base material) 401. . On the transparent substrate 401, transparent electrodes 403 and transparent electrodes 404 for detecting a change in capacitance in the area of the touch screen 402 are alternately arranged. The transparent electrodes 403 and 404 each detect a change in capacitance at the touch position. Thereby, the transparent electrode 403 detects the signal of the X position coordinate, and the transparent electrode 404 detects the signal of the Y position coordinate.

  On the transparent substrate 401, a lead-out wiring 405 for transmitting a touch position detection signal detected by the transparent electrodes 403 and 404 to an external circuit is disposed. The lead-out wiring 405 and the transparent electrodes 403 and 404 are directly connected, and are connected via a connection electrode 406 disposed on the transparent electrodes 403 and 404 (see FIG. 4A). Note that, as illustrated in FIG. 4B, the lead-out wiring 405 and the transparent electrodes 403 and 404 may be directly connected without using the connection electrode 406. One end of the lead wiring 405 is connected to the transparent electrodes 403 and 404, and the other end of the lead wiring 405 is connected to a connection terminal 407 for connecting to an external circuit.

  A protective film 422 is disposed over the lead wiring 405, the connection electrode 406, and the connection terminal 407. In the partial cross-sectional view shown in FIG. 4A, a part of the transparent electrode 404 and all of the lead-out wiring 405 and the connection electrode 406 are covered with the protective film 422. The photosensitive resin composition and photosensitive element according to the present embodiment are suitable for forming a cured product (cured film pattern) as a protective film 422 for protecting the lead wiring 405, the connection electrode 406, and the connection terminal 407. Can be used.

  Further, such a protective film 422 can simultaneously protect the electrodes in the sensing region. For example, in FIG. 3, the lead-out wiring 405, the connection electrode 406, some electrodes in the sensing region, and part of the connection terminal 407 are protected by the protective film 422. You may change suitably the position which arrange | positions a protective film. For example, as illustrated in FIG. 5, a protective film 423 may be disposed so as to protect the entire touch screen 402.

  The said touch panel can be produced similarly to the manufacturing method (refer FIG.1 (b) and FIG. 2) of the base material for touchscreens with a protective film mentioned above, for example.

  A method for manufacturing the touch panel 400 using the photosensitive element according to the present embodiment will be described. First, the transparent electrode 403 for detecting the X position coordinate is formed on the transparent substrate 401. Subsequently, a transparent electrode 404 for detecting the Y position coordinate is formed through an insulating layer (not shown). As a method of forming the transparent electrodes 403 and 404, for example, a method of etching a transparent electrode layer disposed on the transparent substrate 401 can be used.

  Next, on the transparent substrate 401, a lead-out wiring 405 for connecting to an external circuit, and a connection electrode 406 for connecting the lead-out wiring 405 and the transparent electrodes 403 and 404 are formed. The lead wiring 405 and the connection electrode 406 may be formed after the transparent electrodes 403 and 404 are formed, or may be formed at the same time as the transparent electrodes 403 and 404 are formed. As a method for forming the lead wiring 405 and the connection electrode 406, for example, a method of etching after metal sputtering can be used. The lead wiring 405 can be formed at the same time as the connection electrode 406 is formed by screen printing using a conductive paste material containing flaky silver, for example. Next, a connection terminal 407 for connecting the lead wiring 405 and an external circuit is formed.

  The photosensitive layer 20 of the photosensitive element according to this embodiment is pressure-bonded so as to cover the transparent electrode 403, the transparent electrode 404, the lead-out wiring 405, the connection electrode 406, and the connection terminal 407 formed on the transparent substrate 401 by the above-described process. Then, the photosensitive layer 20 is transferred onto these components. Next, the photocuring portion is formed by irradiating the photosensitive layer 20 with the actinic ray L in a pattern through a photomask having a desired shape. After irradiating the actinic ray L, development is performed, and portions other than the photocured portion in the photosensitive layer 20 are removed. Thereby, the protective film 422 which consists of the photocuring part of the photosensitive layer 20 is formed. As described above, a touch panel 400 including the protective film 422 (a touch panel including a base material for a touch panel with the protective film 422) 400 can be manufactured.

  Next, as a third embodiment of an electronic component obtained using a photosensitive element and a method for manufacturing the same using FIGS. 6 to 10, a capacitive touch panel in which transparent electrodes are present on the same plane and a method for manufacturing the same An example will be described. FIG. 6 is a schematic plan view showing an example of a touch panel. 7 is a partially cutaway perspective view of FIG. 8 is a partial cross-sectional view taken along line VIII-VIII in FIG. FIG. 9 is a partially cutaway perspective view for explaining a method of manufacturing a touch panel, and FIG. 9A is a partially cutaway perspective view showing a substrate provided with a transparent electrode, and FIG. FIG. 3 is a partially cutaway perspective view showing a capacitive touch panel. FIG. 10 is a partial cross-sectional view for explaining a method for manufacturing a touch panel, and FIG. 10A is a partial cross-sectional view taken along line Xa-Xa in FIG. 9A, and FIG. FIG. 10 is a partial cross-sectional view showing a step of forming an insulating film, and FIG. 10C is a partial cross-sectional view taken along line Xc-Xc in FIG. 9B.

  A touch panel (capacitance type touch panel) 500 shown in FIGS. 6 to 8 has a transparent electrode 503 and a transparent electrode 504 for detecting a change in capacitance on a transparent substrate (transparent substrate) 501. The transparent electrode 503 detects an X position coordinate signal. The transparent electrode 504 detects a signal of the Y position coordinate. The transparent electrode 503 and the transparent electrode 504 exist on the same plane. Connected to the transparent electrodes 503 and 504 are a lead-out wiring 505a and a lead-out wiring 505b for connection to a control circuit of a driver element circuit (not shown) that controls an electrical signal as a touch panel. An insulating film 524 is disposed between the transparent electrode 503 and the transparent electrode 504 at a portion where the transparent electrode 503 and the transparent electrode 504 intersect.

  A method for manufacturing the touch panel 500 will be described with reference to FIGS. In the manufacturing method of the touch panel 500, for example, a transparent electrode 503 and a substrate in which a conductive material portion for forming the transparent electrode 504 is formed on the transparent substrate 501 in advance by a known method using a transparent conductive material is used. May be. For example, as shown in FIGS. 9A and 10A, a substrate on which a transparent electrode 503 and a conductive material portion 504a for forming the transparent electrode 504 are formed in advance is prepared. Next, as shown in FIG. 10B, the transparent electrode 503 and the transparent electrode 504 that intersects the transparent electrode 503 (a portion sandwiched between the conductive material portions 504a in the transparent electrode 503), A photosensitive layer containing the photosensitive resin composition according to this embodiment is provided, and the insulating film 524 is formed by exposure and development. Subsequently, as shown in FIGS. 9B and 10C, a conductive pattern is formed on the insulating film 524 as a bridge portion 504b of the transparent electrode 504 by a known method. A transparent electrode 504 is formed by conducting the conductive material portions 504a through the bridge portion 504b. Then, the touch panel 500 is obtained by forming the lead wirings 505a and 505b. The photosensitive element according to the present embodiment can be suitably used for forming a cured product (cured film pattern) as the insulating film 524.

  The transparent electrodes 503 and 504 may be formed by a known method using ITO or the like, for example. The lead wires 505a and 505b can be formed by a known method using a metal such as Cu or Ag in addition to the transparent conductive material. Further, in the method for manufacturing the touch panel 500, a substrate on which the lead wirings 505a and 505b are formed in advance may be used.

  Next, an example of a touch panel will be described as a fourth embodiment of the electronic component with reference to FIG. FIG. 11 is a partial plan view showing an example of a touch panel. A touch panel 600 shown in FIG. 11 is intended to narrow the touch panel.

  The touch panel 600 includes a transparent substrate (transparent base material) 601, a transparent electrode 604, a wiring (transparent electrode wiring) 604 a, a lead-out wiring 605, and an insulating film (insulating film such as a transparent insulating film) 625. The transparent electrode 604 and the wiring 604a are disposed on the transparent substrate 601. The wiring 604a extends from the transparent electrode 604. The insulating film 625 is disposed on the end portion of the transparent electrode 604 and the wiring 604a. The lead wiring 605 is disposed on the insulating film 625. An opening 608 is formed in the insulating film 625 above the end of some of the transparent electrodes 604. The transparent electrode 604 and the lead wiring 605 are connected and conducted through the opening 608. The photosensitive element according to the present embodiment can be suitably used for forming a cured product (resin cured film pattern) as the insulating film 625.

  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)]
A flask equipped with a stirrer, a reflux condenser, an inert gas inlet and a thermometer was charged with (1) shown in Table 1, heated to 80 ° C. in a nitrogen gas atmosphere, and the reaction temperature was 80 ° C. ± 2 While maintaining the temperature, (2) shown in Table 1 was added dropwise uniformly over 4 hours. After dropping (2), stirring was continued at 80 ° C. ± 2 ° C. for 6 hours to obtain a binder polymer solution (solid content 45 mass%) (A1) having a weight average molecular weight of 65,000.

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
Sample concentration: 120 mg of NV (non-volatile content) 50% by mass resin solution was collected and dissolved in 5 mL of THF Injection amount: 200 μL
Pressure: 4.9 MPa
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd., product name)

[Measurement method of acid value]
Moreover, the acid value was measured as follows. First, the binder polymer solution was heated at 130 ° C. for 1 hour to remove volatile components to obtain a solid content. Then, after precisely weighing 1.0 g of the polymer whose acid value is to be measured, 30 g of acetone was added to this polymer and dissolved uniformly. Next, an appropriate amount of an indicator, phenolphthalein, was added to the solution, and titration was performed using a 0.1N aqueous KOH solution. Then, the number of mg of KOH required to neutralize the acetone solution of the binder polymer was calculated by the following formula, and the acid value was determined.
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 weight (g) of the measured resin solution, and I represents the ratio (mass%) of the non-volatile content in the measured resin solution.

Example 1
[Preparation of Coating Solution (V-1) Containing Photosensitive Resin Composition]
The materials shown in Table 2 were mixed for 15 minutes using a stirrer to prepare a coating solution containing a photosensitive resin composition for forming a cured film.

[Production of Photosensitive Element (E-1)]
Using a 50 μm thick polyethylene terephthalate film as the support film, uniformly apply the coating solution containing the photosensitive resin composition prepared above on the support film using a comma coater, and dry at 100 ° C. with hot air convection The solvent was removed by drying with a machine for 3 minutes to form a photosensitive layer (photosensitive resin composition layer) made of the photosensitive resin composition. The resulting photosensitive layer had a thickness of 5 μm.

  Next, a polyethylene film having a thickness of 25 μm was further laminated as a cover film on the obtained photosensitive layer to produce a photosensitive element (E-1) for forming a cured film.

[Measurement of transmittance of cured film]
A laminator (manufactured by Hitachi Chemical Co., Ltd., trade name: HLM-) is used so that the photosensitive layer is in contact with a glass substrate having a thickness of 1 mm while peeling the polyethylene film which is the cover film of the obtained photosensitive element (E-1). 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) was used. The laminate was laminated under the condition of a linear pressure of 9.8 × 10 ³ N / m), and a laminate in which a photosensitive layer and a support film were laminated on a glass substrate was produced.

Next, a parallel light exposure machine (EXM1201, manufactured by Oak Manufacturing Co., Ltd.) was used for the photosensitive layer of the obtained laminate, and an exposure amount of 5 × 10 ² J / m ² (i-line ( Measured value at a wavelength of 365 nm), after irradiating with ultraviolet rays, the support film is removed, and further the ultraviolet ray is irradiated at an exposure amount of 1 × 10 ⁴ J / m ² from above the photosensitive layer side (measured value at i-line (wavelength 365 nm)). Irradiated and heated to 140 ° C. for 30 minutes in a box dryer (Mitsubishi Electric Corporation, model number: NV50-CA). A transmittance measurement sample having a cured film (cured film pattern) of a photosensitive layer having a thickness of 5.0 μm was obtained.

  Subsequently, the minimum value of the visible light transmittance was measured for the obtained sample using a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.) in a measurement wavelength range of 400 to 700 nm.

  The minimum value of visible light transmittance of the obtained cured film was 92.09%, and good transmittance was secured.

[Measurement of b ^* of cured film]
Laminator (manufactured by Hitachi Chemical Co., Ltd., trade name: so that the photosensitive layer is in contact with a 0.7 mm thick glass substrate while peeling the polyethylene film which is the protective film of the obtained photosensitive element (E-1). HLM-3000 type), a roll temperature of 120 ° C., a substrate feed rate 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) was used. The substrate was laminated under the condition of a linear pressure of 9.8 × 10 ³ N / m), and a substrate in which a photosensitive layer and a support film were laminated on a glass substrate was produced.

Next, a parallel light exposure machine (EXM1201 manufactured by Oak Manufacturing Co., Ltd.) is used for the photosensitive layer of the obtained laminate, and the exposure amount is 5 × 10 ² J / m ² from the upper side of the photosensitive layer (i line). (Measured value at wavelength 365 nm), after irradiating with ultraviolet rays, the support film is removed, and further at an exposure amount of 1 × 10 ⁴ J / m ² from above the photosensitive layer side (measured value at i-line (wavelength 365 nm)) Was placed in a box dryer (model number: NV50-CA manufactured by Mitsubishi Electric Corporation) heated to 140 ° C. for 30 minutes. A b ^* measurement sample having a protective film (cured film pattern) made of a cured product of a photosensitive layer having a thickness of 5.0 μm was obtained.

Next, b ^* in the CIELAB color system was measured for the obtained sample using a spectrocolorimeter (CM-5) manufactured by Konica Minolta Co., Ltd. with a light source setting of D65 and a viewing angle of 2 °.

The b ^* of the cured film was 0.53, confirming that it had a good b ^* .

[Photosensitive characteristics of photosensitive layer]
Using a laminator (manufactured by Hitachi Chemical Co., Ltd., trade name: HLM-3000 type) while peeling the polyethylene film that is the cover film of the photosensitive element on the PET film (thickness 125 μm, manufactured by Toyobo, trade name A4300), Lamination was performed under the conditions of a roll temperature of 120 ° C., a substrate feed rate of 1 m / min, and a pressure bonding pressure (cylinder pressure) of 4 × 10 ⁵ Pa. Irradiation with actinic rays was carried out by placing on an exposure machine (manufactured by Oak Manufacturing Co., Ltd.) EXM-1201 Mylar PET having a high-pressure mercury lamp and irradiating a predetermined amount of actinic rays through the filter. After standing for 10 minutes at room temperature after irradiation with actinic rays, the support film, polyethylene terephthalate, was removed, and a portion of the photosensitive resin composition layer that was not irradiated with actinic rays with a 1% aqueous sodium carbonate solution at 30 ° C. Spray developed for 2 seconds. After spray development, ultraviolet irradiation of 1 J / cm ² was performed using an ultraviolet irradiation device manufactured by Oak Manufacturing Co., Ltd. The sensitivity in the evaluation was the exposure amount necessary to obtain 6/21 steps with a 41-step tablet manufactured by Hitachi Chemical Co., Ltd. Further, a PET photomask having a wiring pattern with a line width / space width of 6/6 to 47/47 (unit: μm) is closely attached, and the pattern at the exposure amount obtained 6/21 is observed with an optical microscope. The resolution (μm) was determined from the line width (μm) remaining as line and space.

[Salt spray test of cured film (artificial sweat resistance evaluation test)]
Laminator (manufactured by Hitachi Chemical Co., Ltd., trade name) so that the photosensitive layer is in contact with the polyimide film with sputtered copper (manufactured by Toray Film Processing Co., Ltd.) while peeling off the polyethylene film which is the cover film of the obtained photosensitive element. HLM-3000 type), a roll temperature of 120 ° C., a substrate feed rate 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) was used. The laminate was laminated with the photosensitive layer and the support film laminated on the sputtered copper under the condition that the linear pressure at that time was 9.8 × 10 ³ N / m).

Next, a parallel light exposure machine (EXM1201, manufactured by Oak Manufacturing Co., Ltd.) was used for the photosensitive layer of the obtained laminate, and an exposure amount of 5 × 10 ² J / m ² (i-line ( Measured value at a wavelength of 365 nm), after irradiating with ultraviolet rays, the support film is removed, and further the ultraviolet ray is irradiated at an exposure amount of 1 × 10 ⁴ J / m ² from above the photosensitive layer side (measured value at i-line (wavelength 365 nm)). Irradiated and heated to 140 ° C. for 30 minutes in a box dryer (Mitsubishi Electric Corporation, model number: NV50-CA). A sample for evaluating artificial sweat resistance with a cured film having a thickness of 5.0 μm was obtained.

Next, referring to the JIS standard (Z 2371), using the salt spray tester (Suga Test Instruments Co., Ltd., STP-90V2), the aforementioned sample was placed in the test tank, and the salt water having a concentration of 50 g / L. (PH = 6.7) was sprayed for 48 hours at a test bath temperature of 35 ° C. and a spray amount of 1.5 mL / h. After spraying, the salt water was wiped off, the surface state of the sample for evaluation was observed, and evaluation was performed according to the following scores. Table 3 shows the measurement results.
A: No change on the surface of the protective film.
B: Slight traces are visible on the surface of the protective film, but copper remains unchanged.
C: Traces are visible on the surface of the protective film, but copper is unchanged.
D: There is a trace on the surface of the protective film, and copper is discolored.

(Examples 2-5, Comparative Examples 1-7)
A photosensitive element was prepared in the same manner as in Example 1 except that the coating solution containing the photosensitive resin composition shown in Tables 2 and 3 was used, and measurement of transmittance, b ^* in the CIELAB color system, Photosensitivity and salt spray were evaluated. In addition, the numerical value in Table 2 and Table 3 has shown the mass part.

The symbols of the components in Table 2 and Table 3 have the following meanings.
(A) Component (A1): Propylene glycol monomethyl ether / toluene solution of copolymer having a monomer blending ratio (methacrylic acid / methyl methacrylate / ethyl acrylate = 12/58/30 (mass ratio)), weight average molecular weight 65,000, acid value 78mgKOH / g

(B) Component T-1420: KAYARAD T-1420 (T), ditrimethylolpropane tetraacrylate (manufactured by Nippon Kayaku Co., Ltd.)

(C) Component NCI-930: Adeka Cruz NCI-930 (manufactured by ADEKA Corporation)
N-1919: Adekaoptomer N-1919 (manufactured by ADEKA Corporation)
DFI-091: Other photopolymerization initiator NCI-831 manufactured by Daitokemix Co., Ltd. Adeka Cruise NCI-831 (manufactured by ADEKA Corporation)
IRGACURE OXE 02: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (manufactured by BASF Corporation)
DFI-020: Daitokemix Co., Ltd. I-907: IRGACURE 907, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (manufactured by BASF Corporation)
DETX: KAYACURE DETX-S, 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd.)
I-2959: IRGACURE 2959, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (manufactured by BASF Corporation)
N-1717: 1,7-bis (9-acridinyl) heptane (manufactured by ADEKA Corporation)
2-MBI: 2-mercaptobenzimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
EAB: 4,4′-bis (diethylamino) benzophenone (Hodogaya Chemical Co., Ltd.)

Other AW500: Antage W-500, 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (manufactured by Kawaguchi Chemical Co., Ltd.)
PM21: Phosphate ester containing a photopolymerizable unsaturated bond (manufactured by Nippon Kayaku Co., Ltd.)
B-6030: 5-amino-1H-tetrazole (manufactured by Chiyoda Chemical Co., Ltd., trade name: thioale B-6030)
SH-30: Silicone leveling agent (manufactured by Dow Corning Toray)
Methyl ethyl ketone: manufactured by Tonen Chemical Corporation

  As shown in Table 4 below, in Examples 1 to 4 using the specific oxime ester compound as a photopolymerization initiator, the film has a high antirust property (salt spray) while having high transparency at a film thickness of 5 μm. Test). On the other hand, in Comparative Examples 1 and 5, high antirust property (salt water spray test) could be obtained, but yellow was strong. In Comparative Example 1, the resolution was greatly reduced. In Comparative Examples 2-4 and 6-7, high antirust property (salt water spray test) could not be obtained.

  DESCRIPTION OF SYMBOLS 1 ... Photosensitive element, 10 ... Support film, 20 ... Photosensitive layer, 22,422,423 ... Protective film, 30 ... Protective film, 200 ... Transparent substrate, 210,220 ... Touch panel electrode, 230 ... Photomask, 300 ... Touch panel substrate with protective film, 400, 500, 600 ... Touch panel, 401, 501, 601 ... Transparent substrate, 402 ... Touch screen, 403, 404, 503, 504, 604 ... Transparent electrode, 405, 505a, 505b, Reference numeral 605... Lead wiring, 406. Connection electrode, 407. Connection terminal, 504 a. Conductive material portion, 504 b. Bridge portion, 524, 625 .. Insulating film, 604 a ... Wiring (transparent electrode wiring), 608.

Claims (10)

On a transparent substrate, a binder polymer, a photopolymerizable compound, a compound represented by the following general formula (1), a compound represented by the following general formula (2) and the following general formula (3) A photosensitive layer containing a photosensitive resin composition containing at least one photopolymerization initiator selected from the group consisting of compounds, and curing a predetermined portion of the photosensitive layer by irradiation with actinic rays; The manufacturing method of the transparent base material with a cured film which removes other than the said predetermined part of a photosensitive layer, and forms the cured film of the said photosensitive resin composition which coat | covers a part or all of the said base material.

[In the formula (1), R and R ¹ represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or a phenyl group, and R ² represents OH, COOH, O (CH ₂ ) OH, O (CH ₂ ) ₂ OH, COO (CH ₂ ) OH or COO (CH ₂ ) ₂ OH. ]

[In Formula (2), R ³ each independently represents an alkyl group having 1 to 6 carbon atoms, R ⁴ represents NO ₂ or ArCO (wherein Ar represents an aryl group), and R ⁵ And R ⁶ represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group. ]

[In Formula (3), R ⁷ represents an alkyl group having 1 to 6 carbon atoms, R ⁸ represents an organic group having an acetal bond, and R ⁹ and R ¹⁰ represent an alkyl group having 1 to 12 carbon atoms. Represents a phenyl group or a tolyl group. The aromatic ring may have a substituent other than R ⁸ . ]   The said photosensitive layer is a manufacturing method of the transparent base material with a cured film of Claim 1 whose minimum value of the visible light transmittance in 400-700 nm is 85% or more. The manufacturing method of the transparent base material with a cured film of Claim 1 or 2 whose b ^* in a CIELAB color system is -0.2-1.0.   Preparing a photosensitive element comprising a support film and a photosensitive layer comprising the photosensitive resin composition provided on the support film, transferring the photosensitive layer of the photosensitive element onto the substrate, and The manufacturing method of the transparent base material with a cured film as described in any one of Claims 1-3 which provides a photosensitive layer. Selected from the group consisting of a binder polymer, a photopolymerizable compound, a compound represented by the following general formula (1), a compound represented by the following general formula (2), and a compound represented by the following general formula (3) 1 or more types of photoinitiators used, The photosensitive resin composition used in order to form a cured film on a transparent base material.

[In the formula (1), R and R ¹ represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or a phenyl group, and R ² represents OH, COOH, O (CH ₂ ) OH, O (CH ₂ ) ₂ OH, COO (CH ₂ ) OH or COO (CH ₂ ) ₂ OH. ]

[In Formula (2), R ³ each independently represents an alkyl group having 1 to 6 carbon atoms, R ⁴ represents NO ₂ or ArCO (wherein Ar represents an aryl group), and R ⁵ And R ⁶ represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group. ]

[In Formula (3), R ⁷ represents an alkyl group having 1 to 6 carbon atoms, R ⁸ represents an organic group having an acetal bond, and R ⁹ and R ¹⁰ represent an alkyl group having 1 to 12 carbon atoms. Represents a phenyl group or a tolyl group. The aromatic ring may have a substituent other than R ⁸ . ]   The photosensitive resin composition of Claim 5 whose minimum value of the visible light transmittance in 400-700 nm is 85% or more. The photosensitive resin composition of Claim 5 or 6 whose b ^* in a CIELAB color system is -0.2-1.0.   A photosensitive element comprising: a support film; and a photosensitive layer comprising the photosensitive resin composition according to any one of claims 5 to 7 provided on the support film.   The photosensitive element of Claim 8 whose thickness of the said photosensitive layer is 10 micrometers or less.   An electronic component provided with the transparent base material with a cured film obtained by the method as described in any one of Claims 1-4.

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