JP2019197113A - Wiring member and method for manufacturing wiring member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a wiring member capable of producing a flexible display with high definition and high prevention of breaking of a bent portion. A wiring member having an active region and an inactive region, a flexible substrate, a plurality of conductive layers provided on the flexible substrate, and an organic insulation disposed between the plurality of conductive layers. Layer and a connecting portion that connects two layers of the plurality of conductive layers in the thickness direction through tapered openings OA and OB formed in the organic insulating layer, and the opening OA located in the active region is formed. The taper angle θA formed by the wall surface and the surface parallel to the surface of the flexible substrate and the taper angle θB formed by the wall surface of the opening OB located in the inactive region and the surface parallel to the surface of the flexible substrate are mutually Different wiring members. [Selection diagram] Figure 2

Description

    The present invention relates to a wiring member and a method for manufacturing the wiring member.

  As mobile devices become thinner and smaller, flexible displays with thinner thickness and higher shape flexibility are being developed. As these flexible displays, an organic EL display, a liquid crystal display, or the like produced using a resin film as a base material is used. In these devices, in order to maximize the display area of the screen in mobile devices, a technique has been proposed in which the non-display portion and the peripheral circuit portion of the flexible display are folded toward the back side of the screen to reduce the frame ( Patent Document 1).

  In a flexible display with a bent part in the non-display part, the wiring part is connected via an organic flattening layer that absorbs or disperses stress in the bent part in order to prevent disconnection due to bending and to make the wiring redundant and reduce resistance. A technique has been proposed in which an upper layer and a lower metal layer are electrically connected through a contact hole formed in an organic planarization layer while forming two layers (Patent Document 2).

Special table 2014-512556 gazette US Patent Application Publication No. 2017/0277288

  However, it has been found that particularly in a wiring member for a high-definition flexible display, the connection between the upper metal layer and the contact hole cannot be maintained at the time of bending, resulting in a disconnection failure between them.

  An object of this invention is to provide the wiring member which can produce a high-definition flexible display with high disconnection prevention property of a bending part.

  As a result of intensive studies on the above problems, the present inventors have thought that the miniaturization of the contact hole has an influence on the disconnection of the wiring. That is, in the high-definition flexible display, the in-pixel flatness needs to be improved in order to improve the display quality of the display unit. In order to increase the area of the flat portion, it is necessary to reduce the opening of the contact hole. For this reason, it is desirable that the angle of rise (taper angle) from the lower ground of the contact hole in the display portion is steep. From the viewpoint of production efficiency, generally, these contact holes are collectively formed on the corresponding organic flat film. However, if stress at the time of bending is concentrated in a miniaturized contact hole, disconnection of the wiring is likely to occur. As a result of further investigation in view of these circumstances, the present inventors have found that the above-described problems can be solved by adopting the following configuration, and have completed the present invention.

That is, the present invention, in one embodiment, is a wiring member having an active region and an inactive region,
A plurality of conductive layers provided on the flexible substrate; an organic insulating layer disposed between the plurality of conductive layers; and a plurality of tapered openings formed in the organic insulating layer. A connecting portion for connecting two of the conductive layers in the thickness direction;
_A taper angle θ _A formed by a wall surface of the opening located in the active region and a surface parallel to the surface of the flexible substrate, and a wall surface of the opening located in the inactive region and a surface parallel to the surface of the flexible substrate. Nasu and the taper angle theta _B is relates to different wiring members together.

In the wiring member, the taper angle θ _A in the active region and the taper angle θ _B in the inactive region are made different from each other with respect to the taper angle of the contact hole forming opening. Thereby, a taper angle can be changed according to the formation position of a contact hole, and it can prevent the disconnection in the bending part at the time of especially applying a wiring member to a high-definition flexible display.

In one embodiment, the taper angle θ _B is preferably smaller than the taper angle θ _A. As a result, the taper angle θ _A in the active region is sharpened to improve the flatness, and the taper angle θ _B in the inactive region is made gentler, and the disconnection at the bent portion located in the inactive region is more efficient. Can be prevented.

In one embodiment, the taper angle theta _A is less than and 110 ° to 60 °, it is preferable that the taper angle theta _B is 5 ° to 60 °. By specifically setting the taper angle θ _A and the taper angle θ _B within the above ranges, both the steepness of the contact hole in the active region and the disconnection prevention property at the bent portion of the inactive region can be achieved at a high level. Can be made.

In one embodiment, the coefficient of determination R ² in the single regression analysis when plotting the transmittance of the thick viewed portion relative to the thickness of the organic insulating layer from one end of the tapered portion of the opening up to the other end 0. It is preferable that it is 90 or more. The organic insulating film is suitably formed by a photolithography technique using the photosensitive film forming composition. Since the change in transmittance with respect to the thickness is linear, the change in the thickness of the opening slope that gives the taper angle can be easily controlled by adjusting the exposure amount, and the opening having the desired taper angle can be efficiently formed. Can do.

  In one embodiment, a part of the wiring member may have a bent portion.

  In one embodiment, the polydispersity obtained by gel permeation chromatography measurement of the polymer contained in the organic insulating layer is preferably 1.1 or more and 1.6 or less. In order to control the thickness of the opening slope and the exposure amount in a linear relationship, it is preferable to reduce the low molecular weight component in the composition for forming a photosensitive film as much as possible. When the low molecular weight component is large, the low molecular weight component elutes first from the opening slope when developing the photosensitive film after exposure, and the shape of the opening slope tends to be convex outward rather than linear. By setting the polydispersity of the polymer in the above range, the influence of the low molecular weight component can be suppressed to narrow the molecular weight distribution, and an opening having a desired taper angle and shape can be accurately formed.

  In one embodiment, the organic insulating layer is preferably a cured film of a photosensitive film. A wiring member in which openings having different taper angles are formed according to the formation position can be efficiently manufactured using an existing process.

  In a specific embodiment, the wiring member is suitably used as a display substrate or a touch panel substrate having an active region and an inactive region that is in contact with the active region via a boundary region.

In one embodiment, the present invention is a method for manufacturing the wiring member,
Forming a coating film of the composition for forming a photosensitive film on a flexible substrate on which a conductive layer is formed,
Exposing the coating film through a mask;
A step of developing the coating film after the exposure, and a step of forming the opening having the taper angle A and the taper angle B by performing at least one of heating and exposure to the coating film after the development,
In the chromatogram obtained by gel permeation chromatography measurement of the polymer having an alkali-soluble group contained in the composition for forming a photosensitive film, the total area ratio of each peak of the unreacted monomer and the polymerization initiator with respect to the total area of the peak is It is related with the manufacturing method of the wiring member which is 5% or less.

  As described above, in order to control the thickness of the opening slope and the exposure amount in a linear relationship, the composition for forming a photosensitive film is used to suppress preferential elution of low molecular weight components from the opening slope during development. It is preferable to reduce the low molecular weight component in it as much as possible. After synthesizing the polymer for the composition for forming a photosensitive film, the amount of unreacted monomer and polymerization initiator is removed to the above range, thereby suppressing the elution of low molecular weight components from the opening slope, An opening having a taper angle can be formed with high accuracy and efficiency.

In a specific embodiment, the photosensitive film forming composition comprises:
(A) a polymer having an alkali-soluble group,
It preferably contains (B) a radiation sensitive compound, and (C) a solvent.

  As a specific embodiment, in the exposure step, it is preferable to use a halftone mask or a gray tone mask having an inclined transmittance around the opening as a mask for forming the opening in the inactive region. Thereby, the thickness of the opening slope can be controlled more efficiently by adjusting the exposure amount.

  As an embodiment, a positive opening pattern may be formed using an alkaline developer in the developing step.

It is sectional drawing which shows typically the flexible organic EL element which concerns on one Embodiment. It is an expanded sectional view which shows typically the taper angle of opening of the flexible organic EL element of FIG. It is sectional drawing which shows typically one manufacturing process of the flexible organic EL element which concerns on one Embodiment. It is sectional drawing which shows typically one manufacturing process of the flexible organic EL element which concerns on one Embodiment. It is sectional drawing which shows typically one manufacturing process of the flexible organic EL element which concerns on one Embodiment. It is sectional drawing which shows typically one manufacturing process of the flexible organic EL element which concerns on one Embodiment. It is sectional drawing which shows typically one manufacturing process of the flexible organic EL element which concerns on one Embodiment. It is sectional drawing which shows typically one manufacturing process of the flexible organic EL element which concerns on one Embodiment. It is sectional drawing which shows typically one manufacturing process of the flexible organic EL element which concerns on one Embodiment. It is sectional drawing which shows typically one manufacturing process of the flexible organic EL element which concerns on one Embodiment. It is sectional drawing which shows typically another manufacturing process of the flexible organic EL element which concerns on one Embodiment. It is sectional drawing which shows typically another manufacturing process of the flexible organic EL element which concerns on one Embodiment. It is sectional drawing which shows typically another manufacturing process of the flexible organic EL element which concerns on one Embodiment. It is sectional drawing which shows typically another manufacturing process of the flexible organic EL element which concerns on one Embodiment. It is sectional drawing which shows typically another manufacturing process of the flexible organic EL element which concerns on one Embodiment. It is sectional drawing which shows typically another manufacturing process of the flexible organic EL element which concerns on one Embodiment. It is sectional drawing which shows typically another manufacturing process of the flexible organic EL element which concerns on one Embodiment. It is sectional drawing which shows typically another manufacturing process of the flexible organic EL element which concerns on one Embodiment. It is sectional drawing which shows typically one manufacturing process of the flexible liquid crystal display element which concerns on one Embodiment. It is sectional drawing which shows typically one manufacturing process of the flexible liquid crystal display element which concerns on one Embodiment. It is sectional drawing which shows typically one manufacturing process of the flexible liquid crystal display element which concerns on one Embodiment. It is sectional drawing which shows typically one manufacturing process of the flexible liquid crystal display element which concerns on one Embodiment. It is sectional drawing which shows typically one manufacturing process of the flexible liquid crystal display element which concerns on one Embodiment. It is sectional drawing which shows typically one manufacturing process of the flexible liquid crystal display element which concerns on one Embodiment. It is sectional drawing which shows typically another manufacturing process of the flexible liquid crystal display element which concerns on one Embodiment. It is sectional drawing which shows typically another manufacturing process of the flexible liquid crystal display element which concerns on one Embodiment. It is sectional drawing which shows typically another manufacturing process of the flexible liquid crystal display element which concerns on one Embodiment. It is sectional drawing which shows typically another manufacturing process of the flexible liquid crystal display element which concerns on one Embodiment. It is sectional drawing which shows typically another one manufacturing process of the flexible liquid crystal display element which concerns on one Embodiment. It is sectional drawing which shows typically another one manufacturing process of the flexible liquid crystal display element which concerns on one Embodiment.

  A wiring member and its peripheral technology according to an embodiment of the present invention will be described with reference to the drawings as appropriate. In addition, all of the following drawings are schematically shown, and an actual dimensional ratio and a dimensional ratio on the drawing do not necessarily match. Further, the dimensional ratio may be different between the drawings. First, the structure of the wiring member and the method for manufacturing the wiring member will be specifically described in accordance with an embodiment in which the wiring member is applied to a flexible organic EL element, and then materials suitable for each member will be described.

<< First Embodiment >>
(Structure of flexible organic EL device)
FIG. 1 is a cross-sectional view schematically showing a flexible organic EL device according to an embodiment of the present invention. The flexible organic EL element 1 has an active area AR and an inactive area NAR. In the flexible organic EL element 1 according to the present embodiment, the inactive region NAR is a bent portion.

  The flexible organic EL element 1 includes a flexible substrate 10, a first inorganic insulating layer 11 formed on the surface of the flexible substrate 10, and a semiconductor formed in a predetermined region of the first inorganic insulating layer 11 mainly in the active region AR. A layer 22, a interlayer insulating layer 12 covering the first inorganic insulating layer 11, a gate insulating layer 21 covering the semiconductor layer 22, a gate electrode 23 formed at a position corresponding to the semiconductor layer 22 on the gate insulating layer 21, The second inorganic insulating layer 13 covering the gate electrode 23 and the interlayer insulating layer 12, the source wiring layer (the source electrode 25a, the drain electrode 25b, and the first wiring layer 61 are formed later), these structures are covered, and the opening OA , OB formed, and an anode electrode layer 30 formed on the organic flat layer 14 so as to include the opening OA. The wiring member 100 of this embodiment is comprised by these elements.

  Further, the flexible organic EL element 1 is formed on the pixel separation layer 31 so as to include a pixel separation layer 31 in which an opening for communication with the anode electrode layer 30 is formed and a surface of the anode electrode layer 30 in the active region AR. The organic light emitting layer 32, the cathode electrode layer 33 formed on the organic light emitting layer 32, the first inorganic sealing layer 41 formed on the cathode electrode layer 33, the organic sealing layer 42, and the second An inorganic sealing layer 43 and a surface protective layer 50 are provided.

  The flexible organic EL element 1 includes a second wiring layer 62 formed on the organic flat layer 14 so as to be connected to the first wiring layer 61 through the opening OB in the inactive region NAR, and a surface protective layer 50.

  The flexible substrate 10 is a member made of a material such as polyimide and having flatness and flexibility.

  The first inorganic insulating layer 11 has a function of protecting the flexible substrate 10 from the heat of the upper layer process and preventing intrusion of moisture, oxygen and the like from the flexible substrate 10 side.

  The semiconductor layer 22, the gate insulating layer 21, the gate electrode 23, the second inorganic insulating layer 13 and the source wiring layer form a thin film transistor (TFT) 20 with these. An electric field is applied to the semiconductor layer 22 through the gate insulating layer 21 by applying a specific voltage to the gate electrode 23, and a resistance value of the semiconductor layer 22 is controlled to form a source electrode formed based on the source wiring layer It is possible to control the amount of current flowing between 25a and the drain electrode 25b.

  The source wiring layer is made of a laminated film of a metal such as Al, and provides the first wiring layer 61 in the inactive region NAR (bent portion) together with the source electrode 25a and the drain electrode 25b in the active region AR.

  The organic flat layer 14 is an organic insulating layer, and is formed of a material having photosensitivity described later over the active area AR and the inactive area NAR. In the organic flat layer 14, openings OA and OB for connecting upper and lower electrodes or wirings to each other are formed. The taper angle that is the rising angle of the wall surfaces (slopes) of the openings OA and OB has a predetermined relationship as described later.

  The polydispersity obtained by gel permeation chromatography measurement of the polymer contained in the organic flat layer 14 is preferably 1.1 or more and 1.6 or less. The polydispersity is more preferably 1.5 or less, and further preferably 1.3 or less. By setting the polydispersity of the polymer in the above range, the influence of the low molecular weight component can be suppressed to narrow the molecular weight distribution, and an opening having a desired taper angle and shape can be accurately formed.

  The anode electrode layer 30 is made of a conductive material such as Ag or ITO, and has a role of supplying a current to the upper organic light emitting layer 32. The anode electrode layer 30 connects the source wiring layer (drain electrode 25b) through the opening OA, thereby forming a contact hole CH1 which is a connection portion between the upper and lower wirings.

  The pixel separation layer 31 is an insulating member and is made of a material having photosensitivity described later.

  The organic light emitting layer 32 is a part that emits light by recombination of carriers, and is configured to include an organic material corresponding to any of R, G, and B colors. Examples of materials that can be used for the organic light emitting layer 32 include polyparaphenylene vinylene (PPV) and derivatives thereof, polyacetylene and derivatives thereof, polyfluorene and derivatives thereof, polyphenylene and derivatives thereof, polyparaphenylene ethylene and derivatives thereof, poly Examples include 3-hexylthiophene and derivatives thereof.

  The cathode electrode layer 33 is made of a metal material such as Ag or ITO, and has a role of receiving a current flowing through the organic light emitting layer 32.

  The first inorganic sealing layer 41, the organic sealing layer 42, and the second inorganic sealing layer 43 seal a plurality of arranged organic light emitting elements (elements including the organic light emitting layer 32), and oxygen from the outside. It is provided for the purpose of preventing intrusion of water and moisture, thereby improving the lifetime of the organic EL element. As the material of the first inorganic sealing layer 41 and the second inorganic sealing layer 43, SiON, SiO, SiN or the like can be used, and as the material of the organic sealing layer 42, UV curable acrylic resin or epoxy resin is used. it can.

  The surface protective layer 50 functions as a protective layer that prevents external scratches, abrasion, and the like.

Next, the taper angle of the openings OA and OB will be described. FIG. 2 is an enlarged cross-sectional view schematically showing the opening of the flexible organic EL element. In the present embodiment, the taper angle θ _A formed by the wall surface (slope) of the opening OA located in the active area AR and the plane P parallel to the surface of the flexible substrate 10, and the wall surface of the opening OB located in the inactive area NAR ( The taper angle θ _B formed by the (slope) and the plane P parallel to the surface of the flexible substrate 10 are different from each other. As a result, the respective taper angles can be changed according to the positions where the contact holes CH1 and CH2 are formed. In particular, the disconnection in the inactive region NAR corresponding to the bent portion when the wiring member 100 is applied to a high-definition flexible display. Can be prevented.

The taper angle θ _B is preferably smaller than the taper angle θ _A. As a result, the taper angle θ _A of the rising edge in the active region AR is sharpened to improve the flatness, while the taper angle θ _B in the non-active region NAR is made gentler to increase the stress dispersibility. It is possible to more efficiently prevent disconnection at the positioned bent portion.

The taper angle θ _A is preferably more than 60 °, more preferably 65 ° or more, and further preferably 70 ° or more. The taper angle θ _A is preferably 110 ° or less, more preferably 90 ° or less, and still more preferably 80 ° or less. On the other hand, the taper angle θ _B is preferably 5 ° or more, more preferably 20 ° or more, and further preferably 30 ° or more. The taper angle θ _B is preferably 60 ° or less, more preferably 50 ° or less, and further preferably 45 ° or less. By specifically setting the taper angle θ _A and the taper angle θ _B within the above ranges, the steepness of the contact hole CH1 in the active region AR and the prevention of disconnection at the bent portion of the inactive region NAR are high. Can be balanced at the level.

Opening OA, the coefficient of determination R ² in the single regression analysis when plotting the transmittance of the thick solid portion of the organic thickness of the flat layer 14 from one end up to the other end of the tapered portion of the OB (slope) is 0. It is preferably 90 or more, more preferably 0.92 or more, and further preferably 0.94 or more. The organic flat layer 14 that is an organic insulating film is suitably formed by a photolithography technique using a composition for forming a photosensitive film. Since the change in transmittance with respect to the thickness is linear, the change in the thickness of the slopes of the openings OA and OB that give the taper angles θ _A and θ _B can be easily controlled by adjusting the exposure amount, and the desired taper angle The openings OA and OB having θ _A and θ _B can be formed efficiently.

(Method for producing flexible organic EL element)
Hereinafter, with reference to FIG. 3A-FIG. 3H, the manufacturing method of a flexible organic EL element is demonstrated. 3A to 3H are cross-sectional views schematically showing one manufacturing process of the flexible organic EL element.

First, as shown in FIG. 3A, first, the flexible substrate 10 is formed on the glass substrate G. Subsequently, the first inorganic insulating layer 11 is formed in a predetermined region on the upper surface of the flexible substrate 10 by a technique such as CVD, and only a predetermined region of the inactive region NAR is removed by photolithography and etching. Next, the semiconductor layer 22 is formed by a technique such as CVD, and is crystallized by a laser or the like, and is removed by leaving only a predetermined region of the active region AR by photolithography and etching. Further, the gate insulating layer 21 and the interlayer insulating layer 12 are formed by a technique such as CVD, and only a predetermined region of the inactive region NAR is removed by photolithography and etching. Subsequently, the gate electrode 23 is formed by a technique such as sputtering, and is removed by photolithography and etching, leaving only a predetermined region in the active region AR. Next, the second inorganic insulating layer 13 is formed by a technique such as CVD, and a predetermined region of the inactive region NAR and a source electrode 25a and a drain electrode 25b of the TFT 20 (see FIG. 1) are formed by a photolithography and etching. 22 is removed so as to form a contact hole communicating with 22.

  Next, as shown in FIG. 3B, a source wiring layer is formed by a technique such as sputtering, and a predetermined region, that is, a region of the source electrode 25a and the drain electrode 25b in the active region AR, and an inactive region are formed by photolithography and etching. Only the region including the portion of the first wiring layer 61 of the NAR is left and removed.

  Next, as shown in FIG. 3C, the organic planarization layer 14 in which the openings OA and OB are formed is formed by a photolithography technique including a coating, baking, exposure, and development process using the photosensitive film forming composition. .

  A composition for forming a photosensitive film made of a material to be described later is applied to the upper surfaces of the source wiring layer, the second inorganic insulating layer 13 and the interlayer insulating layer 12 so that the film thickness becomes, for example, 0.1 to 100 μm. Thereafter, using an oven or a hot plate, the solvent is removed by drying, for example, at a temperature of 50 to 140 ° C. and a time of 10 to 360 seconds. Thereby, the coating film which consists of a composition for photosensitive film formation is formed.

The coating film is exposed to light using, for example, a contact aligner, a stepper, or a scanner, through a mask patterned according to the shape of the regions to be the openings OA and OB. Examples of the exposure light include ultraviolet light and visible light. For example, light having a wavelength of 200 to 500 nm (eg, g-line = 436 nm, h-line = 405 nm, i-line = 365 nm, a mixture thereof, etc.) is used. . The irradiation amount of actinic rays varies depending on the type of each component in the constituent material of the coating film, the blending ratio, the thickness of the coating film, etc., but when i-line is used for exposure light, the exposure amount is usually 100 to it is a 1500mJ / cm ^2.

  After this exposure processing, heat treatment (hereinafter also referred to as “PEB processing”) may be performed. The PEB conditions vary depending on the content and film thickness of each component of the composition for forming a photosensitive film, but are usually 70 to 150 ° C., preferably 80 to 120 ° C., and about 1 to 60 minutes.

  Next, the coating film is developed with an alkaline developer, and the exposed portion (in the case of positive type) or the non-exposed portion (in the case of negative type) is dissolved and removed. Thereby, the predetermined area | region of a coating film is opened.

  Examples of the development method include shower development, spray development, immersion development, and paddle development. Development conditions are, for example, 20 to 40 ° C. and about 0.5 to 5 minutes. Moreover, as an alkaline developing solution, alkaline compounds, such as sodium hydroxide, potassium hydroxide, ammonia water, tetramethylammonium hydroxide, choline, were dissolved in water so that it might become 1-10 mass% concentration, for example. Alkaline aqueous solution is mentioned. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution. In addition, after developing a coating film with an alkaline developing solution, you may wash | clean with water and dry.

  After developing the coating film with an alkaline developer, an exposure process (post-exposure process) and a heating process (middle bake process) may be further performed. By this treatment, the shape of the coated film after the post-bake treatment described later can be more stably maintained.

  After the development step, if necessary, the coating film is cured by heat treatment (post-bake) in order to develop characteristics as an insulating film. The curing conditions are not particularly limited, and examples include heating at a temperature of 100 to 250 ° C. for about 15 minutes to 10 hours. In order to allow the curing to proceed sufficiently and to prevent the deformation of the pattern shape, it can be heated in two stages. For example, in the first stage, it is heated at a temperature of 50 to 100 ° C. for about 10 minutes to 2 hours. In the second stage, heating is further performed at a temperature of more than 100 ° C. and not more than 250 ° C. for about 20 minutes to 8 hours. If it is such curing conditions, a general oven, an infrared furnace, etc. can be used as heating equipment. By this heat treatment, the coating film is transformed into the organic planarizing layer 14.

Thus, in the organic planarization layer 14, a part of the source wiring layer in the active region AR (drain electrode 25b) and a part of the source wiring layer in the inactive region NAR (first wiring layer 61) are exposed. Openings OA and OB are formed respectively. In the present embodiment, at this time, the taper angle θ _A formed by the wall surface (slope) of the opening OA located in the active region AR and the plane P parallel to the surface of the flexible substrate 10 exceeds 60 ° and becomes 110 ° or less. Each opening is formed such that the taper angle θ _B formed by the wall surface (slope) of the opening OB located in the inactive region NAR and the plane P parallel to the surface of the flexible substrate 10 is 5 ° or more and 60 ° or less. This angle adjustment can be suitably realized by a method of providing a region for adjusting the exposure amount by imparting a gradient of transmittance to the mask pattern during photolithography, that is, an exposure method using a so-called halftone mask or gray tone mask. Can do. The slope of the transmittance may be linear or may be given as a multi-level gradation.

  Next, as shown in FIG. 3D, an anode wiring layer is formed by a technique such as sputtering, and contact between the opening OA of the organic planarization layer 14 in the active region AR, that is, the source wiring layer is performed by photolithography and etching. The anode electrode layer 30 is formed by removing the region that overlaps the hole CH1.

  Subsequently, as shown in FIG. 3E, the pixel separation layer 31 is formed by a photolithography technique including coating, baking, exposure, and development steps. As the material for forming the pixel separation layer 31, a composition for forming a photosensitive film can be used as in the organic planarization layer 14. When the pixel isolation layer 31 is formed, an opening is made so that a part of the anode electrode layer 30 in the active region AR is exposed. The organic light emitting layer 32 is formed by a technique such as vapor deposition using a material film that has an appropriate light emission color for each pixel so as to include the exposed upper surface of the anode electrode layer 30.

  Next, as shown in FIG. 3F, a cathode wiring layer is formed by a technique such as vapor deposition / sputtering, and operates as a cathode electrode layer 33 so as to overlap a light emitting pixel in a predetermined region, that is, the active region AR, by photolithography and etching. The region and the region that operates as the second wiring layer 62 of the inactive region NAR are left and removed. In the inactive region NAR, the first wiring layer 61 and the second wiring layer 62 exposed through the opening OB are connected to form a contact hole CH2.

  Next, as illustrated in FIG. 3G, a first inorganic sealing layer 41, an organic sealing layer 42, and a second inorganic sealing layer sealing layer 43 are formed in order on the cathode electrode layer 33. The first inorganic sealing layer 41 and the second inorganic sealing layer sealing layer 43 are formed by a technique such as CVD, and the organic sealing layer 42 is formed by a technique such as a printing method or a vapor deposition method. These seal a plurality of arranged organic light emitting elements (elements including the organic light emitting layer 32), and prevent oxygen, moisture, and contamination from the outside. Although not shown in the figure, the respective layers are appropriately formed, and the first inorganic insulating layer 11 and the second inorganic insulating layer 13, the second inorganic insulating layer 13 and the first inorganic sealing layer 41, the first By making the inorganic sealing layer 41 and the second inorganic sealing layer 43 in contact with each other around the side surface of the active region AR and surrounding the structure of the active region AR, Oxygen and moisture can be prevented from entering.

  Subsequently, as shown in FIG. 3H, a surface protective layer 50 is formed on the entire surface of the substrate by a technique such as printing or photolithography. Subsequently, after attaching a protective film to the surface on the opposite side to a glass substrate and giving intensity | strength, the flexible organic EL element 1 can be formed by peeling a glass substrate and finally peeling a protective film. Thereafter, stress may be applied to the flexible substrate 10 to bend the inactive region NAR.

<< Second Embodiment >>
In the first embodiment, the organic planarization layer 14 in the active area AR and the inactive area NAR is formed in a lump, whereas in the second embodiment, the pixel isolation film in the active area AR is used in the inactive area NAR. Use as an organic planarization layer. Hereinafter, a description will be given centering on points different from the first embodiment. In addition, the same code | symbol is attached | subjected about the component same as 1st Embodiment. 4A to 4H are cross-sectional views schematically showing another manufacturing process of the flexible organic EL element.

  As shown in FIG. 4A, first, the flexible substrate 10 is formed on the glass substrate G. Subsequently, the first inorganic insulating layer 11 is formed in a predetermined region on the upper surface of the flexible substrate 10 by a technique such as CVD, and only a predetermined region of the inactive region NAR is removed by photolithography and etching. Next, the semiconductor layer 22 is formed by a method such as CVD, and is crystallized by a laser or the like, and removed by leaving only a predetermined region of the active region AR by photolithography and etching. Further, the gate insulating layer 21 and the interlayer insulating layer 12 are formed by a technique such as CVD, and only a predetermined region of the inactive region NAR is removed by photolithography and etching. Subsequently, the gate electrode 23 is formed by a technique such as sputtering, and is removed by photolithography and etching, leaving only a predetermined region in the active region AR. Next, the second inorganic insulating layer 13 is formed by a technique such as CVD, and a predetermined region of the inactive region NAR and a source electrode 25a and a drain electrode 25b of the TFT 20 (see FIG. 1) are formed by a photolithography and etching. 22 is removed so as to form a contact hole communicating with 22.

  Next, as shown in FIG. 4B, a source wiring layer is formed by a technique such as sputtering, and a predetermined region, that is, a region of the source electrode 25a and the drain electrode 25b in the active region AR, and an inactive region are formed by photolithography and etching. Only the region including the portion of the first wiring layer 61 of the NAR is left and removed.

  Next, as shown in FIG. 4C, in the active region AR, the organic planarization layer 14 in which the opening OA is formed is applied using a photosensitive film forming composition by a photolithography technique including application, baking, exposure, and development steps. Form. In the organic planarization layer 14 of the present embodiment, the opening OA is formed so that a part of the source wiring layer (drain electrode 25b) in the active region AR is exposed. The entire surface of the inactive area NAR is exposed.

  Next, as shown in FIG. 4D, an anode wiring layer is formed by a technique such as sputtering, and contact between the opening OA of the organic planarization layer 14 in the active region AR, that is, the source wiring layer is performed by photolithography and etching. The anode electrode layer 30 is formed by removing the region that overlaps the hole CH1.

Subsequently, as shown in FIG. 4E, the pixel isolation layer 31 and the organic planarization layer 31 in the inactive region NAR are collectively formed by a photolithography technique including coating, baking, exposure, and development steps. As a material for forming the pixel separation layer 31 and the organic planarization layer 31, a composition for forming a photosensitive film can be used as in the organic planarization layer 14. When the pixel isolation layer 31 and the organic planarization layer 31 are formed, an opening is made so that a part of the anode electrode layer 30 in the active area AR is exposed, and a part of the first wiring layer 61 in the inactive area NAR is formed. Open each to be exposed. In the present embodiment, the taper angle θ _A formed by the wall surface (slope) of the opening OA2 of the pixel isolation layer 31 located in the active area AR and the plane parallel to the surface of the flexible substrate is more than 60 ° and not more than 110 °, Each opening is formed such that the taper angle θ _B formed by the wall surface (slope) of the opening OB located in the non-active region NAR and the plane parallel to the surface of the flexible substrate is 5 ° or more and 60 ° or less. The wall surface (slope) of the opening OA2 may be a curved surface as shown in FIG. 4E. In this case, the taper angle theta _A, the tangent plane parallel to the surface of the flexible substrate on the wall surface at the contact point between the wall and the anode electrode layer 30 of the opening OA2 becomes angle. The opening can be suitably realized by an exposure method using a halftone mask or a gray tone mask.

  Next, the organic light emitting layer 32 is formed by a technique such as vapor deposition using a material film that has an appropriate emission color for each pixel so as to include the exposed upper surface of the anode electrode layer 30. Furthermore, a cathode wiring layer is formed by a technique such as vapor deposition / sputtering, and is removed by photolithography and etching, leaving a predetermined region, that is, a region overlapping with the light emitting pixels in the active region AR and operating as the cathode electrode layer 33.

  Subsequently, as shown in FIG. 4F, the second wiring layer 62 is formed in the inactive region NAR by a technique such as vapor deposition / sputtering. As a result, the first wiring layer 61 and the second wiring layer 62 exposed through the opening OB are connected to form a contact hole CH2.

  4G, a first inorganic sealing layer 41, an organic sealing layer 42, and a second inorganic sealing layer sealing layer 43 are sequentially formed on the cathode electrode layer 33. The first inorganic sealing layer 41 and the second inorganic sealing layer sealing layer 43 are formed by a technique such as CVD, and the organic sealing layer 42 is formed by a technique such as a printing method or a vapor deposition method. These seal a plurality of arranged organic light emitting elements (elements including the organic light emitting layer 32), and prevent oxygen, moisture, and contamination from the outside. Although not shown in the figure, the respective layers are appropriately formed, and the first inorganic insulating layer 11 and the second inorganic insulating layer 13, the second inorganic insulating layer 13 and the first inorganic sealing layer 41, the first By making the inorganic sealing layer 41 and the second inorganic sealing layer 43 in contact with each other around the side surface of the active region AR and surrounding the structure of the active region AR, Oxygen and moisture can be prevented from entering.

  Subsequently, as shown in FIG. 4H, a surface protective layer 50 is formed on the entire surface of the substrate by a technique such as printing or photolithography. Subsequently, after attaching a protective film to the surface on the opposite side to a glass substrate and giving intensity | strength, the flexible organic EL element 1 can be formed by peeling a glass substrate and finally peeling a protective film. Thereafter, stress may be applied to the flexible substrate 10 to bend the inactive region NAR.

<< Third Embodiment >>
The wiring member can be applied not only to the flexible organic EL element as described in the first embodiment and the second embodiment but also to a liquid crystal display element. In the first embodiment, a predetermined composition for forming a photosensitive film is used as the planarizing layer of the flexible organic EL element. In the present embodiment, the same point is used in which a predetermined photosensitive film forming composition is used as a flattening layer of the TFT substrate of the flexible liquid crystal display element, but in this embodiment, a counter substrate is formed in addition to the TFT substrate, The difference is that both substrates are bonded together and a liquid crystal layer is sealed between the substrates.

  Hereinafter, a description will be given centering on points different from the first embodiment. In addition, the same code | symbol is attached | subjected about the component same as 1st Embodiment. FIGS. 5-1A to 5-1F, FIGS. 5-2A to 5-2D, and FIGS. 5-3A to 5-3B are cross-sectional views schematically showing one manufacturing process of the flexible liquid crystal display element.

(Production of TFT substrate)
Hereinafter, the manufacturing process of the TFT substrate of the flexible liquid crystal display element will be described with reference to FIGS. 5-1A to 5-1F.

  As illustrated in FIG. 5A, the flexible substrate 10 is first formed on the glass substrate G. Subsequently, the first inorganic insulating layer 11 is formed in a predetermined region on the upper surface of the flexible substrate 10 by a technique such as CVD, and only a predetermined region of the inactive region NAR is removed by photolithography and etching. Next, the semiconductor layer 22 is formed by a method such as CVD, and is crystallized by a laser or the like, and removed by leaving only a predetermined region of the active region AR by photolithography and etching. Further, the gate insulating layer 21 and the interlayer insulating layer 12 are formed by a technique such as CVD, and only a predetermined region of the inactive region NAR is removed by photolithography and etching. Subsequently, the gate electrode 23 is formed by a technique such as sputtering, and is removed by photolithography and etching, leaving only a predetermined region in the active region AR. Next, the second inorganic insulating layer 13 is formed by a technique such as CVD, and a predetermined region of the inactive region NAR and a source electrode 25a and a drain electrode 25b of the TFT 20 (see FIG. 1) are formed by a photolithography and etching. 22 is removed so as to form a contact hole communicating with 22.

  Next, as shown in FIG. 5B, a source wiring layer is formed by a technique such as sputtering, and a predetermined region, that is, a region of the source electrode 25a and the drain electrode 25b in the active region AR, and a non-pattern are formed by photolithography and etching. The active region NAR is removed leaving only the region including the portion of the first wiring layer 61.

  Next, as shown in FIG. 5C, in the active region AR, the organic color filter layers 71 and 72 in which the opening OC is formed are applied using a photosensitive film forming composition, and the photo including the steps of applying, baking, exposing and developing. It is formed by a lithography method. In the organic color filter layers 71 and 72 of this embodiment, the opening OC is formed so that a part of the source wiring layer (drain electrode 25b) in the active region AR is exposed. The opening OC has a larger taper angle than the opening OA formed in the organic planarization layer 14 provided in the next step. The entire surface of the inactive area NAR is exposed. The organic color filter layers 71 and 72 are formed a plurality of times depending on the color required by the pixel at the time of image display.

  Next, as shown in FIG. 5D, the organic planarization layer 14 with the openings OA and OB formed thereon is coated with a photosensitive film forming composition, baked, exposed, and developed by a photolithography technique including exposure and development processes. Form. The formation method, shape, characteristics, and the like of the organic planarization layer 14 are the same as those in the first embodiment.

  Thus, in the organic planarization layer 14, a part of the source wiring layer in the active region AR (drain electrode 25b) and a part of the source wiring layer in the inactive region NAR (first wiring layer 61) are exposed. Openings OA and OB are formed respectively. In the present embodiment, at this time, the taper angle θA formed by the wall surface (slope) of the opening OA located in the active area AR and the plane parallel to the surface of the flexible substrate 10 exceeds 60 ° and is 110 ° or less. Each opening is formed such that a taper angle θB formed by a wall surface (slope) of the opening OB located in the active region NAR and a plane parallel to the surface of the flexible substrate 10 is 5 ° or more and 60 ° or less. This angle adjustment can be suitably realized by a method of providing a region for adjusting the exposure amount by imparting a gradient of transmittance to the mask pattern during photolithography, that is, an exposure method using a so-called halftone mask or gray tone mask. Can do. The slope of the transmittance may be linear or may be given as a multi-level gradation.

  Next, as shown in FIG. 5E, the pixel electrode layer 30a is formed by a technique such as sputtering, and the opening OA of the organic planarization layer 14 in the active region AR, that is, the source wiring layer is formed by photolithography and etching. The pixel electrode layer 30a is formed by removing the region that overlaps the contact hole CH1 therebetween.

  Subsequently, as shown in FIG. 5A, a liquid crystal alignment film layer 75 is formed on the pixel electrode layer by a spin coating method, a printing method, an ink jet method, or the like. By controlling the printing area, it is possible not to form the liquid crystal alignment film layer in the inactive area NAR. The TFT substrate 200 can be manufactured by the above procedure.

(Preparation of counter substrate)
Hereinafter, the manufacturing process of the counter substrate of the flexible liquid crystal display element will be described with reference to FIGS. 5-2A to 5-2D.

  As shown in FIG. 5A, the flexible substrate 10a is first formed on the glass substrate Ga.

  Subsequently, as shown in FIG. 5B, the counter pixel electrode layer 30b is formed in a predetermined region on the upper surface of the flexible substrate 10a. Note that in the case of adopting a liquid crystal alignment mode (for example, FFS mode, IPS mode, or the like) in which the liquid crystal alignment can be defined only by the pixel electrode layer 30a on the TFT substrate 200 side, the step of forming the counter pixel electrode 30b is omitted. be able to.

  Subsequently, as shown in FIG. 5-2C, the spacer layer 80 is formed on the counter pixel electrode layer 30b using a photosensitive film forming composition by a photolithography technique including coating, baking, exposure, and development steps. To do.

  Subsequently, as illustrated in FIG. 5D, the liquid crystal alignment film layer 75a is formed on the counter pixel electrode layer 30b and the spacer layer 80 by a spin coating method, a printing method, an ink jet method, or the like. The counter substrate 201 can be manufactured by the above procedure.

(Production of flexible liquid crystal display elements)
Subsequently, as shown in FIG. 5-3A, a liquid crystal sealing layer (not shown) is formed so as to surround the entire active area AR of the TFT substrate 200 by a technique such as a printing method, and the liquid crystal material LC is formed in the active area AR. Then, the counter substrate 201 is bonded together, and the liquid crystal seal layer is cured, thereby encapsulating the liquid crystal material LC in the liquid crystal display element.

  Then, the flexible liquid crystal display element 2 (FIGS. 5-3B) can be formed by peeling the glass substrates G and Ga of both substrates. Thereafter, stress may be applied to the flexible substrate 10 to bend the inactive region NAR.

<< Fat composition for photosensitive film formation >>
The composition for forming a photosensitive film according to this embodiment contains [A] a binder polymer, [B] a polymerizable compound, and [C] a radiation-sensitive compound. Hereinafter, each component will be described in detail.

[[A] Binder polymer]
[A] The binder polymer is not particularly limited, and any binder polymer may be used as long as it can be a base material of a cured film.

  Moreover, [A '] alkali-soluble resin which is illustrated below as a [A] binder polymer can also be used. [A] By using [A ′] alkali-soluble resin as the binder polymer, patterning with an alkaline developer becomes possible.

[[A '] alkali-soluble resin]
[A ′] The alkali-soluble resin is a resin having an alkali-soluble group and soluble in an alkaline solution. [A ′] As the alkali-soluble resin, a polymer obtained by radical polymerization using an unsaturated compound containing a carboxy group as an alkali-soluble group as a monomer (hereinafter, also referred to as “[a] polymer”), polyimide, Polysiloxanes, novolac resins, and combinations thereof are preferred. Hereinafter, each of [a] polymer, polyimide, polysiloxane, and novolak resin will be described in detail.

[[A] polymer]
[A] The polymer has a structural unit containing a carboxy group. Moreover, you may have a structural unit containing a polymeric group for a sensitivity improvement. The structural unit containing a polymerizable group is preferably a structural unit containing an epoxy group, a structural unit containing a (meth) acryloyl group, or a structural unit containing a vinyl group. [A] When the polymer has a structural unit containing the specific polymerizable group, a composition for forming a photosensitive film excellent in surface curability and deep part curability can be obtained. [A] The polymer may have a structural unit containing a hydroxyl group and other structural units.

  The structural unit containing the carboxy group includes, for example, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, anhydrides of unsaturated dicarboxylic acids, and mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids. Using a saturated compound as a monomer, it can be formed by radical polymerization with other monomers as appropriate.

  Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid.

  Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like.

  Examples of the anhydride of the unsaturated dicarboxylic acid include anhydrides of the compounds exemplified as the unsaturated dicarboxylic acid.

  Examples of the mono [(meth) acryloyloxyalkyl] ester of the polyvalent carboxylic acid include succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] and the like. It is done.

  Among these carboxylic acid-based unsaturated compounds, acrylic acid, methacrylic acid, maleic anhydride and mono [2- (meth) acryloyloxyethyl] succinate are preferable from the viewpoint of polymerizability.

  These carboxylic acid unsaturated compounds may be used alone or in combination of two or more.

  [A] As a minimum of the content rate of the structural unit containing the carboxy group in a polymer, 1 mol% is preferable with respect to all the structural units which comprise a [a] polymer, 5 mol% is more preferable, 10 More preferred is mol%. Moreover, as an upper limit of the said content rate, 80 mol% is preferable, 70 mol% is more preferable, and 60 mol% is further more preferable. When the content rate of the structural unit containing a carboxy group is in the above range, the solubility in an alkaline developer can be further improved.

  The structural unit containing an epoxy group can be formed, for example, by radical polymerization with other monomers as appropriate using an epoxy group-containing unsaturated compound as a monomer. Examples of the epoxy group-containing unsaturated compound include unsaturated compounds containing an oxiranyl group (1,2-epoxy structure), an oxetanyl group (1,3-epoxy structure), and the like.

  Examples of the unsaturated compound having an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, and 6,7 acrylic acid. -Epoxy heptyl, 3,4-epoxycyclohexyl methacrylate, etc. are mentioned.

  Examples of the unsaturated compound having an oxetanyl group include 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- And methacrylic acid esters such as (methacryloyloxymethyl) -2-phenyloxetane, 3- (2-methacryloyloxyethyl) oxetane, and 3- (2-methacryloyloxyethyl) -2-ethyloxetane.

  Among these epoxy group-containing unsaturated compounds, glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate and 3- (methacryloyloxymethyl) -3-ethyloxetane are preferable from the viewpoint of polymerizability.

  These epoxy group-containing unsaturated compounds may be used alone or in admixture of two or more.

  The structural unit containing the (meth) acryloyl group is, for example, a method of reacting a polymer having an epoxy group with (meth) acrylic acid, a polymer having a carboxy group and a (meth) acrylic acid ester having an epoxy group. It can be formed by a method, a method of reacting a polymer having a hydroxyl group with a (meth) acrylic acid ester having an isocyanate group, a method of reacting a polymer having an acid anhydride group and (meth) acrylic acid, or the like. Among these methods, a method in which a polymer having a carboxy group and a (meth) acrylic acid ester having an epoxy group are reacted is preferable.

  The structural unit containing a hydroxyl group can be formed, for example, by radical polymerization with another monomer as appropriate using a hydroxyl group-containing unsaturated compound as a monomer. Examples of the hydroxyl group-containing unsaturated compound include (meth) acrylic acid ester having an alcoholic hydroxyl group, (meth) acrylic acid ester having a phenolic hydroxyl group, and hydroxystyrene.

Examples of the acrylic acid ester having an alcoholic hydroxyl group include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, and 6-hydroxyhexyl acrylate. .
Examples of the methacrylic acid ester having an alcoholic hydroxyl group include 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, and 6-hydroxyhexyl methacrylate. .

Examples of the acrylic acid ester having a phenolic hydroxyl group include 2-hydroxyphenyl acrylate and 4-hydroxyphenyl acrylate.
Examples of the methacrylic acid ester having a phenolic hydroxyl group include 2-hydroxyphenyl methacrylate and 4-hydroxyphenyl methacrylate.

Examples of the hydroxystyrene include o-hydroxystyrene, p-hydroxystyrene, and α-methyl-p-hydroxystyrene.
Of these hydroxyl group-containing unsaturated compounds, 2-hydroxyethyl methacrylate and α-methyl-p-hydroxystyrene are preferred from the viewpoint of polymerizability.

  These hydroxyl group-containing unsaturated compounds may be used alone or in combination of two or more.

  [A] When the polymer has a structural unit containing a hydroxyl group, the lower limit of the content of the structural unit is preferably 1 mol%, preferably 5 mol%, based on all structural units constituting the polymer. Is more preferable, and 10 mol% is further more preferable. Moreover, as an upper limit of the said content rate, 30 mol% is preferable and 20 mol% is more preferable. When the content rate of the structural unit containing a hydroxyl group is in the above range, the solubility in an alkaline developer can be further improved.

  Examples of the monomer that gives other structural units include methacrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, acrylic acid chain alkyl ester, acrylic acid cyclic alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated Examples include dicarboxylic acid diesters, maleimide compounds, unsaturated aromatic compounds, conjugated dienes, unsaturated compounds having a tetrahydrofuran skeleton, and other unsaturated compounds.

  Examples of the methacrylic acid chain alkyl ester include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n methacrylate. -Lauryl, tridecyl methacrylate, n-stearyl methacrylate and the like.

Examples of the cyclic alkyl ester of methacrylic acid include tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, norbornyl methacrylate, adamantyl methacrylate, and cyclohexyl methacrylate.

  Examples of the acrylic acid cyclic alkyl ester include isobornyl acrylate, norbornyl acrylate, adamantyl acrylate, cyclohexyl acrylate, and the like.

  Examples of the methacrylic acid aryl ester include phenyl methacrylate and benzyl methacrylate.

  Examples of the acrylic acid aryl ester include phenyl acrylate and benzyl acrylate.

Examples of the maleimide compound include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide, N-succinimidyl-3-maleimidobenzoate. Etc.

  Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and p-methoxystyrene.

  Examples of the unsaturated compound having a tetrahydrofuran skeleton include tetrahydrofurfuryl methacrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran-2-one, and the like.

Among the monomers giving the other structural units, from the viewpoint of polymerizability, styrene, methyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, t-butyl methacrylate, n-lauryl methacrylate, benzyl methacrylate, acrylic Acid isobornyl, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, and tetrahydromethacrylate Furfuryl is preferred.

  The monomer which gives the said other structural unit may be used independently, and 2 or more types may be mixed and used for it.

  Polymers other than the above acrylic copolymers include polyimide resins, resins containing cardo skeletons, phenol novolac resins, cresol novolac resins, biphenyl resins, bisphenol A resins, bisphenol F resins, dicyclo Resin having a pentanyl skeleton, resin having a trisphenolmethane skeleton, bisphenol F type epoxy resin, polyfunctional epoxy resin, flexible epoxy resin, brominated epoxy resin, glycidyl ester type epoxy resin, phenoxy resin, biphenyl type epoxy Resin, siloxane resin, polyhydroxystyrene resin, styrene-hydroxystyrene copolymer resin bisphenol A, bisphenol F, bisphenol AD, bromo-containing bisphenol A, phenol novolac, crezo Glycidyl ether type epoxy resins such as novolak, polyphenol, straight chain aliphatic, butadiene, and urethane; hexahydrophthalic acid glycidyl ester, dimer acid glycidyl ester, aromatic, cycloaliphatic, aliphatic glycidyl An ester type epoxy resin or the like can be used.

  The lower limit of the weight average molecular weight (Mw) of the polymer is preferably 1,000, more preferably 2,000, and still more preferably 3,000. The upper limit of the Mw is preferably 30,000, more preferably 20,000, and further preferably 15,000. [A] By making Mw of a polymer into the said range, storage stability and a sensitivity can be improved more.

  The lower limit of the ratio of the Mw to the number average molecular weight (Mn) of the polymer (a), that is, the molecular weight distribution (Mw / Mn) is usually 1, 1.2 is preferable and 1.5 is preferably 1.5. More preferred. The upper limit of Mw / Mn is preferably 5, more preferably 4, and even more preferably 3. [A] By making Mw / Mn of a polymer into the said range, storage stability and a sensitivity can be improved more.

In addition, Mw and Mn in this specification are values measured by gel permeation chromatography (GPC) under the following conditions.
Equipment: For example, “GPC-101” from Showa Denko
Column: For example, “GPC-KF-801”, “GPC-KF-802”, “GPC-KF-803”, and “GPC-KF-804” manufactured by Showa Denko KK Mobile phase: Tetrahydrofuran Column temperature: 40 ℃
Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene

(Polymer synthesis method)
The method for synthesizing the polymer is not particularly limited, and a known method can be adopted. For example, it can be synthesized by polymerizing the above-described monomers in a solvent in the presence of a polymerization initiator.

  Examples of the solvent include alcohol, glycol ether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, propylene glycol monoalkyl. Examples include ether propionate, other esters, and ketones.

  As said polymerization initiator, what is generally known as a radical polymerization initiator can be used. Examples of the radical polymerization initiator include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4- And azo compounds such as methoxy-2,4-dimethylvaleronitrile).

  In the composition for forming a photosensitive film according to this embodiment, in the chromatogram obtained by gel permeation chromatography measurement of a polymer having an alkali-soluble group, the sum of each peak of the unreacted monomer and the polymerization initiator with respect to the total area of the peak. The area ratio is 5% or less. The area ratio is preferably 4% or less, more preferably 3% or less, further preferably 2% or less, and particularly preferably 1.5% or less. After synthesizing the polymer for the composition for forming a photosensitive film, the amount of unreacted monomer and polymerization initiator is removed to the above range, thereby suppressing the elution of low molecular weight components from the opening slope, An opening having a taper angle can be formed with high accuracy and efficiency.

  Removal of unreacted monomer and polymerization initiator is a distillation method in which a poor solvent is added to the copolymer solution after synthesis, the copolymer is precipitated, and dissolved again in the solvent to distill off the low molecular weight component, The precipitation method etc. which superpose | polymerize in the middle of superposition | polymerization, precipitate a copolymer under cooling, and filter a copolymer can be employ | adopted suitably.

  Examples of the poor solvent in the distillation method include hexane, heptane, isopropyl alcohol, and the like. As the solvent for re-dissolution, the solvent for the above polymerization can be suitably used. Distillation can be performed by heating the redissolved solution under reduced pressure as necessary. What is necessary is just to set heating temperature according to the boiling point etc. of the monomer to be used, for example, what is necessary is just 30-80 degreeC.

  Examples of the polymerization inhibitor in the precipitation method include p-methoxyphenol, 4-tert-butylpyrocatechol, tert-butylhydroquinone, 1,4-benzoquinone, phenothiazine and the like. The cooling temperature is not particularly limited as long as the copolymer is precipitated and the unreacted monomer and polymerization initiator are in a dissolved state, and examples thereof include 0 to 40 ° C.

[[B] polymerizable compound]
[B] The polymerizable compound is not particularly limited as long as it is a compound that is polymerized by irradiation or heating, but a compound having a (meth) acryloyl group, an epoxy group, a vinyl group, or a combination thereof is preferable from the viewpoint of improving sensitivity. A compound having two or more (meth) acryloyl groups in the molecule is more preferable.

  Examples of the [B] polymerizable compound having two or more (meth) acryloyl groups in the molecule include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, Tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl Glycol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate 1,6-hexanediol diacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate , Pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, tetrapentaerythritol nonaacrylate, tetrapentaerythritol decaacrylate, pentapentaerythritol undecaacrylate, penta Pentaerythritol Decaacrylate, tripentaerythritol heptamethacrylate, tripentaerythritol octamethacrylate, tetrapentaerythritol nonamethacrylate, tetrapentaerythritol decamethacrylate, pentapentaerythritol undecamethacrylate, pentapentaerythritol dodecamethacrylate, dimethylol-tricyclodecane diacrylate, ethoxylation Bisphenol A diacrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [4- (2-methacryloyloxyethoxy) phenyl] fluorene, 9,9-bis [4 -(2-Methacryloyloxyethoxy) -3-methylphenyl] fluorene, (2-acryloyloxypropoxy) -3 -Methylphenyl] fluorene, 9,9-bis [4- (2-acryloyloxyethoxy) -3, 5-dimethylphenyl] fluorene, 9,9-bis [4- (2-methacryloyloxyethoxy) -3,5 -Dimethylphenyl] fluorene and the like.

  [A] The lower limit of the content of the polymerizable compound [B] with respect to 100 parts by mass of the binder polymer is preferably 1 part by mass, more preferably 10 parts by mass, and still more preferably 20 parts by mass. Moreover, as an upper limit of the said content, 200 mass parts is preferable, 150 mass parts is more preferable, and 120 mass parts is further more preferable. By setting the content within the above range, it is possible to form a cured film having higher hardness and higher solvent resistance while further improving storage stability and sensitivity.

  [C] Examples of the radiation-sensitive compound include a radiation-sensitive radical polymerization initiator, a radiation-sensitive acid generator, a radiation-sensitive base generator, and combinations thereof.

  For example, when a radical polymerizable compound is used as the [B] polymerizable compound, the radiation sensitive radical polymerization initiator can further accelerate the curing reaction by radiation of the photosensitive film forming composition.

  As the radiation-sensitive radical polymerization initiator, for example, active species capable of initiating radical polymerization reaction of the polymerizable compound [B] are generated by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. And the like.

  Specific examples of the radiation-sensitive radical polymerization initiator include, for example, O-acyl oxime compounds, α-amino ketone compounds, α-hydroxy ketone compounds, acyl phosphine oxide compounds, and the like.

  Examples of the O-acyloxime compound include 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate, 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime) and the like.

  Examples of the α-aminoketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- ( 4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, and the like.

  Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one. 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone and the like.

  Examples of the acylphosphine oxide compound include diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like.

  The radiation-sensitive radical polymerization initiator is preferably an O-acyl oxime compound, an α-amino ketone compound, and an acyl phosphine oxide compound from the viewpoint of further promoting the curing reaction by radiation. Etanone, 1- [9-ethyl-6 -(2-Methylbenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], 2-methyl-1- (4-Methylthiophenyl) -2-morpholinopropan-1-one and diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide are more preferred.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. “Parts” and “%” are based on mass unless otherwise specified.

<Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn)>
[P] The weight average molecular weight (Mw) of the polymer component was measured by the following method.
That is, Mw and Mn were measured by gel permeation chromatography (GPC) under the following conditions. The molecular weight distribution (Mw / Mn) was calculated from the obtained Mw and Mn.
Equipment: “GPC-101” from Showa Denko
GPC column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are combined (manufactured by Shimadzu LLC)
Mobile phase: Tetrahydrofuran Column temperature: 40 ° C
Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene

<Polymer synthesis>
[Synthesis Example 1]
In a flask equipped with a condenser and a stirrer, 7 parts by weight of 2,2 ″ -azobis (2,4-dimethylvaleronitrile), 200 parts by weight of propylene glycol monomethyl ether acetate, 15 parts by weight of methacrylic acid, 30 parts by weight of glycidyl methacrylate Then, 20 parts by weight of styrene, 5 parts by weight of 2-hydroxyethyl acrylate, and 30 parts by weight of isobornyl acrylate were charged, and the mixture was purged with nitrogen. After raising the reaction solution to 62 ° C., this temperature was maintained for 5 hours to obtain a polymer solution containing the acrylic copolymer [a-1]. The obtained polymer solution (a-1) was loaded with 900 parts by weight of hexane to precipitate a copolymer. The precipitated copolymer solution was separated, 150 parts by weight of propyllenglycol mono-methylethyl acetate was added, heated to 40 ° C., and distilled under reduced pressure to obtain a copolymer (A-1). The resulting copolymer solution had a solid content concentration of 30% by weight, GPC analysis results showed that the area of unreacted monomer and polymerization initiator was 2.3%, and the weight average molecular weight (Mw) in terms of polystyrene was 12800. .

[Synthesis Example 2]
In a flask equipped with a condenser and a stirrer, 2 parts by weight of 2,2 ″ -azobis (2,4-dimethylvaleronitrile), 200 parts by weight of tetrahydrofuran, 15 parts by weight of methacrylic acid, 30 parts by weight of glycidyl methacrylate, 20 parts by weight of styrene , 5 parts by weight of 2-hydroxyethyl acrylate, and 30 parts by weight of isoboronyl acrylate were substituted with nitrogen, and then gently stirred. After raising the reaction solution to 62 ° C., this temperature was maintained for 8 hours to obtain a polymer solution containing the acrylic copolymer (a-2). The obtained polymer solution (a-2) was loaded with 900 parts by weight of hexane to precipitate a copolymer. The precipitated copolymer solution was separated, 150 parts by weight of propyllenglycol mono-methylethyl acetate was added, heated to 40 ° C., and distilled under reduced pressure to obtain a copolymer (A-2). The solid content concentration of the obtained copolymer solution was 30% by weight, the GPC analysis result showed that the area of unreacted monomer and polymerization initiator was 0.5%, and the polystyrene-equivalent weight average molecular weight (Mw) was 9400. .

[Synthesis Example 3]
In a flask equipped with a condenser and a stirrer, 7 parts by weight of 2,2 ″ -azobis (2,4-dimethylvaleronitrile), 200 parts by weight of propylene glycol monomethyl ether acetate, 13 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate , Α-methyl-p-hydroxystyrene 10 parts by weight, N-cyclohexylmaleimide 15 parts by weight, tetrahydrofurfuryl methacrylate 12 parts by weight, n-lauryl methacrylate 10 parts by weight, and α-methylstyrene dimer as a molecular weight regulator After 3 parts by mass were charged and the atmosphere was replaced with nitrogen, stirring was started gently. After raising the reaction solution to 62 ° C., this temperature was maintained for 5 hours to obtain a polymer solution containing the acrylic copolymer (a-3). The obtained polymer solution (a-3) was loaded with 900 parts by weight of hexane to precipitate a copolymer. The precipitated copolymer solution was separated, 150 parts by weight of propyllenglycol mono-methylethyl acetate was added, heated to 40 ° C., and distilled under reduced pressure to obtain a copolymer (A-3). The obtained copolymer solution had a solid content concentration of 30% by weight, GPC analysis results showed that the area of unreacted monomer and polymerization initiator was 1.3%, and the polystyrene-equivalent weight average molecular weight (Mw) was 8,000. .

[Synthesis Example 4]
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2 ″ -azobis (2,4-dimethylvaleronitrile), 200 parts by weight of propylene glycol monomethyl ether acetate, and 150 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, 27 parts by mass of styrene, 15 parts by mass of methacrylic acid, and 58 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate were charged. After nitrogen substitution, the mixture was gently stirred. After raising the reaction solution to 62 ° C., this temperature was maintained for 5 hours to obtain a polymer solution containing the acrylic copolymer (a-4). The obtained polymer solution (a-4) was loaded with 900 parts by weight of hexane to precipitate a copolymer. The precipitated copolymer solution was separated, 150 parts by weight of propyllenglycol mono-methylethyl acetate was added, heated to 40 ° C., and distilled under reduced pressure to obtain a copolymer (A-4). The solid content concentration of the obtained copolymer solution was 35% by weight, the GPC analysis result showed that the area of the unreacted monomer and the polymerization initiator was 1.1%, and the polystyrene equivalent weight average molecular weight (Mw) was 7,000. .

[Synthesis Example 5]
A 2 L flask equipped with a condenser and a stirrer was charged with a mixed solution of 400 parts by weight of isopropyl alcohol, 27 parts by weight of styrene, 15 parts by weight of methacrylic acid, and 58 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate. The liquid composition was thoroughly mixed at 600 rpm in a mixing vessel, and 15 parts by weight of 2,2 ″ -azobis (2,4-dimethylvaleronitrile) was added. The polymerization mixed solution was slowly raised to 62 ° C., and this temperature was maintained for 6 hours to obtain a copolymer solution. 500 ppm of p-methoxyphenol was added to the obtained polymer as a polymerization inhibitor. The temperature of the flask in which the polymerization was stopped was lowered to 18 ° C. and left to stand for 1 hour, and then a precipitate formed was obtained and filtered. Acrylic copolymer (A-5) was obtained by adding propylene glycol monomethyl ether acetate so that the content of the precipitate was 45% by weight using 85 parts by weight of the precipitate obtained by filtration as a solvent. As a result of GPC analysis of the polymer solution obtained at this time, the area of the unreacted monomer and the polymerization initiator was 0.8%, and the weight average molecular weight (Mw) in terms of polystyrene was 7000.

[Synthesis Example 6]
A 2 L flask equipped with a condenser and a stirrer was charged with a mixed solution of 400 parts by weight of isopropyl alcohol, 30 parts by weight of methacrylic acid, 30 parts by weight of styrene, 25 parts by weight of glycidyl methacrylate, and 15 parts by weight of 2-hydroxyethyl acrylate. After the liquid composition was sufficiently mixed at 600 rpm in a mixing container, 15 parts by weight of 2,2 ″ -azobis (2,4-dimethylvaleronitrile) was added. The polymerization mixed solution was slowly raised to 62 ° C., and this temperature was maintained for 6 hours to obtain a copolymer solution. 500 ppm of p-methoxyphenol was added to the obtained polymer as a polymerization inhibitor. The temperature of the flask in which the polymerization was stopped was lowered to 18 ° C. and allowed to recover for 1 hour, and a precipitate formed was obtained and filtered. Acrylic copolymer (A-6) was obtained by adding propylene glycol monomethyl ether acetate so that the content of the precipitate was 45% by weight using 85 parts by weight of the precipitate obtained by filtration as a solvent. As a result of GPC analysis of the polymer solution obtained at this time, the area of the unreacted monomer and the polymerization initiator was 0.9%, and the weight average molecular weight (Mw) in terms of polystyrene was 8,000.

[Synthesis Example 7]
In a 2 L flask equipped with a condenser and a stirrer, 400 parts by weight of isopropyl alcohol, 15 parts by weight of methacrylic acid, 30 parts by weight of glycidyl methacrylate, 50 parts by weight of (tetrahydropyran-2-yl) methyl methacrylate, 2-hydroxyethyl acrylate 5 parts by weight of the mixed solution was added. The liquid composition was thoroughly mixed at 600 rpm in a mixing vessel, and 15 parts by weight of 2,2 ″ -azobis (2,4-dimethylvaleronitrile) was added. The polymerization mixed solution was slowly raised to 62 ° C., and this temperature was maintained for 6 hours to obtain a copolymer solution. 500 ppm of p-methoxyphenol was added to the obtained polymer as a polymerization inhibitor. The temperature of the flask in which the polymerization was stopped was lowered to 18 ° C. and allowed to recover for 1 hour, and a precipitate formed was obtained and filtered. Acrylic copolymer (A-7) was obtained by adding propylene glycol monomethyl ether acetate so that the content of the precipitate was 45% by weight using 85 parts by weight of the precipitate obtained by filtration as a solvent. As a result of GPC analysis of the polymer solution obtained at this time, the area of the unreacted monomer and the polymerization initiator was 1.0%, and the weight average molecular weight (Mw) in terms of polystyrene was 1,1000.

[Synthesis Example 8]
In a flask equipped with a condenser and a stirrer, 11 parts by mass of 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 1,12-dodecane 34 parts by mass of diamine and 156 parts by mass of N-methyl-2-pyrrolidone were added. After stirring at room temperature to dissolve each monomer, 40 parts by mass of 1,2,3,4-butanetetracarboxylic dianhydride was added. After stirring at 120 ° C. for 5 hours in a nitrogen atmosphere, the temperature was raised to 180 ° C. and dehydration reaction was performed for 5 hours. After completion of the reaction, the reaction mixture was poured into water to reprecipitate the product, which was filtered and vacuum dried to obtain Resin (A-8). As a result of the GPC analysis, the area of the unreacted monomer and the polymerization initiator was 1%, and the polystyrene equivalent weight average molecular weight (Mw) was 24100.

[Comparative Synthesis Example 1]
In a flask equipped with a condenser and a stirrer, 7 parts by weight of 2,2 ″ -azobis (2,4-dimethylvaleronitrile), 200 parts by weight of propyllenglycol mono-methylethyl acetate, 15 parts by weight of methacrylic acid, glycidyl methacrylate After 30 parts by weight, 20 parts by weight of styrene, 5 parts by weight of 2-hydroxyethyl acrylate, and 30 parts by weight of isoboronyl acrylate were purged with nitrogen, stirring was started gently. After raising the reaction solution to 62 ° C., this temperature was maintained for 5 hours to obtain a polymer solution containing an acrylic copolymer (A-9). The resulting copolymer solution had a solid content concentration of 34% by weight, GPC analysis results showed that the area of unreacted monomer and polymerization initiator was 20%, and the polystyrene-equivalent weight average molecular weight (Mw) was 12800.

[Comparative Synthesis Example 2]
In a flask equipped with a condenser and a stirrer, 7 parts by weight of 2,2 ″ -azobis (2,4-dimethylvaleronitrile), 200 parts by weight of propyllenglycol mono-methylethyl acetate, 10 parts by weight of methacrylic acid, glycidyl methacrylate 30 parts by weight, 20 parts by weight of styrene, 10 parts by weight of 2-hydroxyethyl acrylate, and 30 parts by weight of isoboronyl acrylate were charged. After the atmosphere was replaced with nitrogen, stirring was started gently. After raising the reaction solution to 62 ° C., this temperature was maintained for 9 hours to obtain a polymer solution containing an acrylic copolymer (A-10). The solid content concentration of the obtained copolymer solution was adjusted to 30% by weight. As a result of GPC analysis, the area of the unreacted monomer and the polymerization initiator was 15%, and the weight average molecular weight (Mw) in terms of polystyrene was 16800. It was.

<Preparation of photosensitive film forming composition>
[A] to [E] used for the preparation of the composition for forming a photosensitive film of Examples are shown below.
[A] Resin [B] Photosensitizer B-1: 4,4 ′-[1- [4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) And a condensate [C] of 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) B-2: 1,2-octanedione, 1- [4- (phenylthio) -2 -(O-benzoyloxime)] ("Irgacure OXE01" from BASF)
B-3: N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester [C] additive C-1: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (“KAYARAD DPHA” of Nippon Kayaku Co., Ltd.)
C-2: Trimethoxysilylpropyl isocyanate (“KBE-9007” from Shin-Etsu Chemical Co., Ltd.)
C-3: 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (“Kyowanol M” manufactured by Kyowa Hakko Kirin Co., Ltd.)

[Example 1]
25 parts by mass of photosensitizer (B-1), 5 parts by mass of additive (C-1), and additive (C-) with respect to an amount corresponding to 100 parts by mass (solid content) of copolymer (A-1). 3) 10 parts by mass and SH28PA (Toray Dow Corning) were mixed, dissolved in a mixture of diethylene glycol ethyl methyl ether so that the solid content concentration was 18% by mass, and then with a membrane filter having a pore size of 0.2 μm. Filtration was performed to prepare a composition for forming a photosensitive film (S-1).

[Examples 2-8 and Comparative Examples 1-2]
Except having used each component of the kind shown in Table 1 below, it operate | moved similarly to Example 1, and the composition (S-2)-(S-) for Examples 2-8 and Comparative Examples 1-2 of Comparative film | membrane formation. 8) and (CS-2) to (CS-2) were prepared.

<Evaluation of Composition for Forming Photosensitive Film>
Using the photosensitive film forming compositions of Examples and Comparative Examples, radiation sensitivity, development defects, cured film dielectric constant, cured film chemical resistance, cured film transparency, and contact hole taper shape evaluation were performed. . The evaluation results are shown in Table 1.

[Evaluation of radiation sensitivity]
The composition for forming a photosensitive film shown in Table 1 was applied on a silicon substrate using a spinner, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. Subsequently, using an exposure machine (Canon's “MPA-600FA” (ghi line mixing)), the exposure dose was changed to the coating film through a mask having a 10 μm line and space pattern. Irradiated. Then, it developed by the piling method for 60 seconds at 23 degreeC with 2.38 mass% tetramethylammonium hydroxide aqueous solution. Next, running water was washed with ultrapure water for 1 minute and then dried to form a pattern. At this time, the exposure amount necessary for completely dissolving the 10 μm space pattern was examined. The case where the value of the exposure amount is less than 150mJ / cm ² A, the case where the value of the exposure amount is 150~200mJ / cm ² or less B, and when the value of the exposure amount exceeds 200 mJ / cm ² was C.

[Fabrication of electrical property evaluation board]
Each composition for forming a photosensitive film shown in Table 1 was applied on an ITO substrate, which is a glass substrate with an ITO film, with a spin coater so as to have a film thickness of 3 μm, and then on a hot plate at 90 ° C. for 2 minutes. Each coating film was formed by pre-baking and evaporating the organic solvent. Next, as an electrode extraction site for measuring electrical characteristics, a part of the edge of the substrate coated with the photosensitive film forming composition was wiped with acetone to expose the underlying ITO. Using a proximity exposure machine (Canon's “MA-1200” (ghi line mixing)), the entire surface of the substrate was irradiated with 300 mJ / cm ² light, and then heated (post-baked) at 230 ° C. for 30 minutes in an oven. And an insulating film was formed on the ITO substrate.

[Measurement of dielectric constant]
An Al (aluminum) electrode for measuring the capacitance is formed on a vacuum deposition apparatus (JEOL VACUUM) on the insulating film of each electrical property evaluation substrate produced by the method described in [Production of electrical property evaluation substrate]. It was prepared using EVAPROTOR JEE-420). Next, a lead wire for electrode connection is soldered to the ITO portion exposed in advance, and the lead wire and the Al electrode produced by the vacuum deposition apparatus are respectively positive terminals of an LCR meter (HEWRET PACKARD 4284A PRECISION LCR METER) The capacitance C of the insulating film was measured under the conditions of an applied voltage of 100 mV and a frequency of 10 kHz. The value of the dielectric constant ε was determined by substituting the measured value of the capacitance C, the area S (m ² ) of the Al electrode, and the film thickness d (m) of the cured film into the following equation.
Dielectric constant ε = capacitance C × cured film thickness d (m) ÷ electrode area S (m ² )

[Evaluation of dielectric constant of cured film]
For the composition for forming a photosensitive film shown in Table 1, the value of the dielectric constant ε of the cured film obtained by the method described in the above [Measurement of dielectric constant] was used as an index of low dielectric constant. The case where the dielectric constant was less than 3.0 was A, the case where the dielectric constant was 3.0 to 3.5 was B, and the case where it exceeded 3.5 was C.

[Evaluation of transparency of cured film]
The composition for forming a photosensitive film shown in Table 1 was applied on a glass substrate using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. Subsequently, the entire surface of the substrate was irradiated with 300 mJ / cm ² light using a proximity exposure machine (“MA-1200” manufactured by Canon Inc. (mixed with ghi line)), and then heated using an oven heated to 230 ° C. Baking for a minute to form a cured film. The transmittance of this film was measured at 25 ° C. using an ultraviolet-visible spectrophotometer (“V-670” manufactured by JASCO Corporation), and used as an index of transparency. The case where the transmittance of the cured film at 400 nm was 95% or more was evaluated as A, the case where it was 90% or more and less than 95% was evaluated as B, and the case where it was less than 90% was evaluated as C.

[Evaluation of change in remaining film against change in transmittance of mask]
The composition for forming a photosensitive film shown in Table 1 was applied on a silicon substrate using a spinner, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. Subsequently, using an exposure machine (Canon's “MPA-600FA” (ghi line mixture)), a square pattern of 1 mm square was made to have a transmittance of 10% T, 20% T, and 30% T, respectively, by a chromium sputtering method. Through the mask, the coating film was irradiated with the exposure amount of radiation obtained in the above sensitivity evaluation. Then, it developed by the piling method for 60 seconds at 23 degreeC with 2.38 mass% tetramethylammonium hydroxide aqueous solution. Next, running water was washed with ultrapure water for 1 minute and then dried to form a pattern. This pattern was irradiated with 300 mJ / cm ² light on the entire surface of the substrate using a proximity exposure machine (Canon “MA-1200” (ghi line mixing)) and then heated to 230 ° C. using an oven. The cured film was formed by baking for 30 minutes. In order to observe the tapered shape of the contact hole pattern, the hole pattern was cut along with the substrate, and platinum was deposited on the pattern surface using a vacuum deposition apparatus, and then observed with a scanning electron microscope. At this time, plotting the radiation irradiation part film thickness and the change in transmittance around the hole, and when regressing linearly, the R ² value is 0.90 or more, and A is 0.70 or more and less than 0.89. , Less than 0.70 was C.

[Evaluation of contact hole shape controllability]
The composition for forming a photosensitive film shown in Table 1 was applied on a silicon substrate using a spinner, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. Subsequently, using an exposure machine (Canon's “MPA-600FA” (ghi line mixing)), a transmittance of 10% T, 20% T, and about 1 μm around the 5 μm contact hole pattern by chromium sputtering, respectively. Through the mask with 30% T, the coating film was irradiated with the exposure amount of radiation obtained in the sensitivity evaluation described above. Then, it developed by the piling method for 60 seconds at 23 degreeC with 2.38 mass% tetramethylammonium hydroxide aqueous solution. Next, running water was washed with ultrapure water for 1 minute and then dried to form a pattern. This pattern was irradiated with 300 mJ / cm ² light on the entire surface of the substrate using a proximity exposure machine (Canon “MA-1200” (ghi line mixing)) and then heated to 230 ° C. using an oven. The cured film was formed by baking for 30 minutes. In order to observe the tapered shape of the contact hole pattern, the hole pattern was cut along with the substrate, and platinum was deposited on the pattern surface using a vacuum deposition apparatus, and then observed with a scanning electron microscope. In this case, plotting the transmittance change of the angle and the hole around the pattern in contact with each substrate, where R ² value is 0.90 or more A when the regression linear expression, less than 0.70 0.89 In the case of B, B and less than 0.70 were C.

DESCRIPTION OF SYMBOLS 1 Flexible organic EL element 10 Flexible board 14 Organic planarization layer 25a Source electrode 25b Drain electrode 30 Anode electrode layer 61 1st wiring layer 62 2nd wiring layer CH1, CH2 Contact hole OA, OA2, OB opening

Claims (12)

A wiring member having an active region and an inactive region,
A plurality of conductive layers provided on the flexible substrate; an organic insulating layer disposed between the plurality of conductive layers; and a plurality of tapered openings formed in the organic insulating layer. A connecting portion for connecting two of the conductive layers in the thickness direction;
_A taper angle θ _A formed by a wall surface of the opening located in the active region and a surface parallel to the surface of the flexible substrate, and a wall surface of the opening located in the inactive region and a surface parallel to the surface of the flexible substrate. Nasu and the taper angle theta _B is different wiring member. The wiring member according to claim 1, wherein the taper angle θ _B is smaller than the taper angle θ _A. The wiring member according to claim 1, wherein the taper angle θ _A is greater than 60 ° and not greater than 110 °, and the taper angle θ _B is not less than 5 ° and not greater than 60 °. Billing determination coefficient R ² in the simple linear regression analysis at the time of plotting the transmittance of the thick viewed portion relative to the thickness of the organic insulating layer from one end of the tapered portion of the opening up to the other end is not less than 0.90 Item 4. The wiring member according to any one of Items 1 to 3.   The wiring member according to claim 1, wherein a part of the wiring member has a bent portion.   The wiring member according to any one of claims 1 to 5, wherein a polydispersity obtained by gel permeation chromatography measurement of a polymer contained in the organic insulating layer is 1.1 or more and 1.6 or less.   The wiring member according to claim 1, wherein the organic insulating layer is a cured film of a photosensitive film.   The wiring member according to claim 1, wherein the wiring member is used as a display substrate or a touch panel substrate having an active region and an inactive region in contact with the active region via a boundary region. It is a manufacturing method of the wiring member given in any 1 paragraph of Claims 1-8,
Forming a coating film of the composition for forming a photosensitive film on a flexible substrate on which a conductive layer is formed,
Exposing the coating film through a mask;
A step of developing the coating film after the exposure, and a step of forming the opening having the taper angle θ _A and the taper angle θ _B by performing at least one treatment of heating and exposure on the coating film after the exposure. ,
In the chromatogram obtained by gel permeation chromatography measurement of the polymer having an alkali-soluble group contained in the composition for forming a photosensitive film, the total area ratio of each peak of the unreacted monomer and the polymerization initiator with respect to the total area of the peak is The manufacturing method of the wiring member which is 5% or less. The photosensitive film forming composition is:
(A) a polymer having an alkali-soluble group,
The manufacturing method of the wiring member of Claim 9 containing (B) a radiation sensitive compound and (C) solvent.   11. The method for manufacturing a wiring member according to claim 9, wherein in the exposure step, a halftone mask or a gray tone mask having an inclination in the transmittance around the opening is used as a mask for forming the opening in the inactive region.   The method for manufacturing a wiring member according to claim 9, wherein a positive opening pattern is formed using an alkaline developer in the developing step.

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