TW201935442A - Wiring member not causing cracking or peeling of a cured film when bending the wiring member - Google Patents

Abstract

The present invention provides a wiring member which is excellent in bending characteristics and capable of forming wiring at a narrow pitch. The wiring member of the present invention includes a substrate and a cured film disposed on the upper layer of the substrate, and cracking or peeling of the cured film does not occur when the substrate surface of the wiring member on the side opposite to the cured film is bent by 180DEG along a core rod having an outer diameter of 0.5 mm.

Description

Wiring member

The present invention relates to a wiring member.

In recent years, a flexible display device has been developed using a flexible material of the display device instead of the display device on a flat panel. The flexible display device has a characteristic of being able to be bent. Therefore, a variety of display devices are provided in which the width of the inactive area (non-display area) is reduced by using the characteristic (for example, refer to Patent Documents 1 and 2).
[Prior Art Literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 2014-512556
[Patent Document 2] Japanese Patent Laid-Open No. 2017-111435

[Problems to be Solved by the Invention]
In a general flexible display device, in order to minimize a frame corresponding to a part of a non-display area, a form may be adopted in which a bending area is buckled with a very small curvature, and is used for drawing. Connection terminals such as image output or touch screen signal output and control chip are arranged on the back side of the screen.

However, if a connection terminal, a control chip, or the like is disposed on the back side of the screen in a state where the bending region has a large bending shape, a large tensile stress is applied to the protective layer of the wiring located outside the bending region to cause elongation. As a result, cracks or peeling may occur on the film surface of the protective layer, which may cause disconnection of the wiring.

In addition, in the buckling area, in order to prevent disconnection of the wiring, a disconnection prevention structure such as a zigzag shape or a figure-eight shape may be used. However, in the case of adopting such a configuration, when the protective layer itself is cracked or peeled off, there is a possibility that the deformation may be concentrated at the above-mentioned portion and the wire may be disconnected.

Furthermore, in recent years, high-definition display devices or touch screens have been required to form wirings at narrow pitches.

The present invention has been made in view of the problems described above, and an object thereof is to provide a wiring member having excellent bending characteristics and capable of forming wirings at a narrow pitch.
[Technical means to solve the problem]

The wiring member of the present invention includes a substrate and a cured film disposed on an upper layer of the substrate, and the wiring member is characterized by:
When the substrate surface of the wiring member on the side opposite to the cured film was bent 180 ° along a mandrel with an outer diameter of 0.5 mm, the cured film did not crack or peel.

The wiring member includes a cured film on a substrate. The cured film can function as a protective layer of a wiring layer formed on a substrate. The cured film has a characteristic that a pattern can be formed by a photolithography method, and therefore, patterning performance at a high resolution can be achieved.

In addition, the hardened film did not crack or peel when it buckled 180 ° along a mandrel with an outer diameter of 0.5 mm. Since it has such characteristics, it has excellent bending characteristics.

Therefore, according to a wiring member including such a cured film, for example, even when a wiring layer having a narrow pitch is formed in a buckling portion of a thin film having a thickness of 0.3 μm to 20 μm at the thickest position, it is difficult to cause disconnection of the wiring. line.

In addition, as a preferred embodiment, the elongation at break represented by the following formula when the cured film is converted to a film thickness of 10 μm is 10% or more.

Elongation at break (%) = {(L ₁ -L ₀ ) / L ₀ } × (10 / T) × 100

(In the formula, T is the thickness [μm] of the cured film, L ₀ is the initial length of the test piece, and L ₁ is the length of the test piece when it is broken.)

Since the cured film has the above-mentioned characteristics and has high elongation characteristics, the effect of preventing disconnection in the buckled portion can be further enhanced. In addition, even when a physical impact is applied to the electronic device on which the wiring member is mounted from the outside, it functions to suppress the appearance of cracks or peeling.

As a specific aspect, a configuration having a buckled portion in a part of the wiring member may be adopted. In addition, the buckling portion may be provided at one portion of the wiring member, or may be provided at a plurality of portions.

In a specific aspect, the wiring member can be used as a display substrate or a touch screen substrate having an active area and a non-active area adjacent to the active area in a direction parallel to the substrate surface.

In this case, the inactive region may be configured to be bent from a main surface side of the display substrate or the touch screen substrate toward a back surface side opposite to the main surface. According to this configuration, the inactive area can be provided on a surface different from the active area, specifically, the side or the back side. Therefore, the proportion of the active area on the plane can be increased, and the frame width can be reduced. In addition, the starting point of buckling in this case may be set as an inactive region. In addition, the present invention does not exclude a configuration in which the wiring member is bent from the back surface side of the display substrate or the touch screen substrate to the main surface side.

The non-active area may be bent by 180 ° in a manner that the back surface of the non-active area faces the back surface of the active area. Here, the term "opposing" includes both a case of being in contact with and a case of being separated from each other. That is, at least a part of the back surface of the non-active area may be in contact with at least a part of the back surface of the active area, or it may be located at a position spaced in a direction orthogonal to both back surfaces. According to this configuration, the ratio of the active area on the plane can be maximized, and thus it can contribute to the realization of a display device with an extremely narrow frame width. In addition, since it is possible to achieve 180 ° buckling, it is possible to realize a wiring member with a small thickness even though a plurality of wiring patterns are mounted.

In a specific aspect, the cured film located in the inactive region has a pattern formed by a photolithography method with respect to a photosensitive film. The pattern may be at least one of a hole pattern and a circuit pattern.

Here, the hole pattern refers to a pattern for forming an electrical connection between an upper wiring layer and a lower wiring layer by filling a conductive layer into the pattern. The circuit pattern is a pattern for arranging a plurality of electrodes or wirings in a direction parallel to the substrate surface.

In a specific aspect, the cured film included in the wiring member is a coating film of a composition for forming a photosensitive film, and the composition for forming a photosensitive film includes:
(A) a polymer having an alkali-soluble group,
(B) a radiation-sensitive compound, and (C) a solvent.

The (A) polymer preferably has a structural unit (m1) containing a crosslinkable functional group different from the alkali-soluble group. This improves the heat resistance and insulation of the cured film.

It is preferable that the composition for forming a photosensitive film further contains (D) a crosslinkable compound. This improves the heat resistance and insulation of the cured film.

In one aspect, the (A) polymer may include a structural unit (m2) derived from at least one of (meth) acrylate, butadiene, isoprene, and chloroprene. Thereby, high elongation characteristics can be achieved. The structural unit (m2) may be a non-cyclic structural unit. As used herein, the "non-cyclic structural unit" refers to a structural unit that does not have a cyclic structure.

The content of the polymer including the structural unit (m2) is preferably 10% by mass or more and 90% by mass or less, and more preferably 25% by mass of the total mass of components other than the solvent in the photosensitive film forming composition. % To 55% by mass. With such a configuration, while maintaining high elongation characteristics, it is possible to show stable holding properties for wiring.

In one aspect, the composition for forming a photosensitive film further contains at least one of (E) an adhesion promoter and (F) a surfactant. By including the (E) adhesion aid, the adhesion to the substrate is improved, and by including the (F) surfactant, the film formability is improved.
[Effect of the invention]

According to the present invention, a wiring member having excellent bending characteristics and capable of forming wirings at a narrow pitch can be realized.

An embodiment of the wiring member of the present invention will be described with reference to the drawings. In addition, the following drawings are schematic representations, and the actual size ratio is not the same as the size ratio on the drawings. In addition, there may be cases where the size ratio is different between the drawings.

[First Embodiment]
(structure)
FIG. 1 schematically illustrates an example of a flexible printed board as one embodiment of a wiring member of the present invention. The flexible printed board 1 includes a flexible substrate 2, a conductive layer 3 formed on the flexible substrate 2, a conductive layer 4 electrically connected to the conductive layer 3, and an insulating cured film (10, 10 a).

The flexible substrate 2 contains, for example, resins such as polyimide, polyimide, polyester, and polyfluorene.

The conductive layer 3 and the conductive layer 4 only need to be conductive materials, such as metals including aluminum, titanium, chromium, nickel, and copper; or alloys containing them as the main component; or indium tin, indium tin oxide (Indium Tin) Oxide (ITO), metal oxides such as indium oxide containing tungsten.

The cured film 10 is made of a material described later, and is an insulating material having bending characteristics. The cured film 10 a may include the same material as the cured film 10 or may include a different material.

As shown in FIG. 1, a flexible printed circuit board 1 has a conductive layer 4 formed in a bent portion. By forming the cured film 10 using a material described later, it is possible to achieve excellent bending characteristics while achieving patterning performance.

(Production method)
Hereinafter, a method of manufacturing the flexible printed circuit board 1 will be described with reference to FIGS. 2A to 2E.

As shown in FIG. 2A, a conductive layer 3 is formed in a predetermined region on the upper surface of the flexible substrate 2. The conductive layer 3 can be formed by forming a resist mask after forming a conductive film, and etching the conductive film to remove the resist mask.

As shown in FIG. 2B, the coating film 8 is formed so as to cover the upper surface of the conductive layer 3. The coating film 8 includes a constituent material of the cured film 10.

A composition for forming a photosensitive film containing a material described later is applied to the upper surfaces of the conductive layer 3 and the flexible substrate 2 so that the film thickness becomes, for example, 0.1 μm to 100 μm. In this case, from the viewpoint of suppression of cracking or peeling, or flexibility, the film thickness is preferably in the range of 0.2 μm to 50 μm, and more preferably 0.3 μm to 20 μm. Thereafter, using an oven or a hot plate, the solvent is removed by drying at, for example, a temperature: 50 ° C to 140 ° C and a time: 10 seconds to 360 seconds. As a result, a coating film 8 containing a composition for forming a photosensitive film is formed on the upper surfaces of the conductive layer 3 and the flexible substrate 2.

As shown in FIG. 2C, a predetermined area 9 of the coating film 8 is opened. Specifically, it is performed by the following method, for example.

The patterned mask corresponding to the shape of the area 9 that becomes the opening area is exposed to the coating film 8 using, for example, a contact aligner, a stepper, or a scanner. Examples of the exposure light include ultraviolet light and visible light. For example, light having a wavelength of 200 nm to 500 nm (for example, i-ray (365 nm)) can be used. The amount of actinic ray exposure varies depending on the type of each component in the constituent materials of the coating film 8, the blending ratio, the thickness of the coating film 8, and the like. When i-rays are used as the exposure light, the exposure is usually 100 mJ. / cm ² to 1500 mJ / cm ² .

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

Then, the coating film 8 is developed with an alkaline developer to dissolve and remove the exposed portion (in the case of a positive type) or the non-exposed portion (in the case of a negative type). The region 9 is thereby opened.

Examples of the development method include a shower development method, a spray development method, an immersion development method, and a liquid-covered development method. The developing conditions are, for example, about 0.5 to 5 minutes at 20 ° C to 40 ° C. Examples of the alkaline developing solution include dissolving a basic compound such as sodium hydroxide, potassium hydroxide, ammonia, tetramethylammonium hydroxide, and choline in water at a concentration of 1% to 10% by mass. The resulting alkaline aqueous solution. An appropriate amount of a water-soluble organic solvent such as methanol, ethanol, and a surfactant may be added to the alkaline aqueous solution. In addition, after the coating film is developed with an alkaline developer, it may be washed with water and dried.

Furthermore, after developing a coating film with an alkaline developing solution, you may perform exposure processing (post-exposure processing) and heat processing (intermediate baking processing). By this process, the shape of the hardened coating film 8 after the post-baking process mentioned later can be maintained more stably.

After the development step, in order to make the coating film 8 exhibit the characteristics as an insulating film, it is hardened (post-baking) by heat treatment if necessary. The curing conditions are not particularly limited, and examples include heating at a temperature of 100 ° C to 250 ° C for about 15 minutes to about 10 hours. In order to fully harden and prevent deformation of the pattern shape, heating may be performed in two stages. For example, in the first stage, heating is performed at a temperature of 50 ° C to 100 ° C for about 10 minutes to 2 hours; in the second stage, further heating is performed. It is heated at a temperature exceeding 100 ° C and below 250 ° C for about 20 minutes to about 8 hours. If such hardening conditions are used, ordinary ovens, infrared ovens, and the like can be used as heating equipment. Through the heat treatment, the coating film 8 becomes a cured film 10.

In addition, as shown in FIG. 2C, the inclined surface of the opening region 9 formed in the coating film 8 preferably has a tapered shape having a width that increases in a direction parallel to the surface of the substrate 2 as it approaches the flexible substrate 2. . By forming the opening region 9 in such a shape, the effect of reducing the disconnection of the wiring layer including the conductive layer 3 and the conductive layer 4 formed later can be improved. The angle (taper angle) of the inclined surface of the coating film 8 with respect to the surface of the flexible substrate 2 is preferably 10 ° or more and 80 ° or less, and more preferably 20 ° or more and 50 ° or less.

As a method of forming such a cone shape, a half tone exposure technique in which a mask for patterned exposure processing is set in a mask pattern region that partially transmits light to a predetermined region can be used. Melt flow rate control technology for temperature rise control during baking, etc. In order to form a conical shape with a low angle on the inactive portion, a semi-exposure technique is more preferably used.

As shown in FIG. 2D, a conductive layer 4 is formed at a predetermined portion including the opening 9. The constituent material and formation method of the conductive layer 4 may be the same as those of the conductive layer 3. Through the above steps, the conductive layer 4 is electrically connected to the conductive layer 3 disposed on the flexible substrate 2 side than the conductive layer 4. That is, the opening 9 functions as a contact hole for electrically connecting wiring rooms (between the conductive layers 3 and 4). In this way, by connecting two or more conductive layers (3, 4) to each other, it is possible to ensure low resistance and redundancy due to multilayering of wirings, or to switch current paths among a plurality of wirings.

As shown in FIG. 2E, an insulating cured film 10 a is formed so as to cover the conductive layer 4. As described above, the cured film 10a may be configured using the same material as the cured film 10, or may be configured using other insulating materials. Among them, when the cured film 10 a is realized by using a material different from that of the cured film 10, it is preferable that the cured film 10 a be formed of a material having excellent bending performance. The cured film 10 a may be formed in a state inclined to the surface of the flexible substrate 2 (state having a taper angle) similarly to the cured film 10 (coating film 8).

Thereafter, stress is applied to the flexible substrate 2 to bend the whole, and more specifically, the flexible substrate 2 is bent toward the side opposite to the cured film (10, 10a), thereby realizing FIG. 1 Shape. At this time, since the cured film 10 has high elongation and excellent bending performance, even if the entirety is bent by applying a stress as shown in FIG. 1, cracking or peeling does not occur. Therefore, according to the flexible printed circuit board 1, it is also possible to realize the inclusion of a curved region including a wiring pattern including fine contact holes in the flexible printed circuit board as in the conductive layer (3, 4). The wiring pattern of the fine contact hole 9.

In particular, by forming the opening regions (opening regions 9 in FIG. 2C) of the cured film (10, 10a) in a state inclined with respect to the surface of the flexible substrate 2, it is possible to disperse the end portions of the opening regions and Deformation and stress of the layer formed on the upper layer can suppress cracking and peeling of the conductive layer (3, 4), which is preferable.

(Another manufacturing method)
In the above, the description has been given in the form of using a resist mask when the conductive layer 3 is formed in a predetermined area. However, a composition for forming a photosensitive film containing a material described later, that is, a composition with a cured film 10 may be used. (Coating film 8) The same material is used for the same treatment. In this case, the coating film 8 disposed as a mask can be removed by performing a cleaning step without performing heating after exposure for changing from the coating film 8 to the cured film 10.

[Second Embodiment]
The following description focuses on parts different from the first embodiment. The same components as those in the first embodiment are denoted by the same reference numerals. The same applies to the following third embodiment.

(structure)
FIG. 3 schematically illustrates an example of an organic EL element (hereinafter referred to as “OLED”) as one embodiment of the wiring member of the present invention. The OLED 1a includes a flexible substrate 2, a conductive layer 3 formed on an upper layer of the flexible substrate 2, a wiring layer 21, a display electrode 22, a wiring pattern 23, an organic light emitting layer 24, and an insulating cured film (10, 10a). 10b), the sealing layer 25, the polarizing film 26, and the control wafer 27. In addition, although not shown in FIG. 3, the OLED 1 a includes, between the wiring layer 21 and the flexible substrate 2, a transistor element (such as a thin film transistor) for pixel selection and pixel lighting. , TFT)). In addition, although not shown in FIG. 3, a display electrode is formed on the upper layer of the organic light emitting layer 24.

As shown in FIG. 3, the OLED 1a has an active area A1 and a non-active area A2. The active region A1 corresponds to a region where the organic light emitting layer 24 is formed. The inactive area A2 is an area other than the active area A1 and is an area in which the control wafer 27 and the wiring pattern 23 are formed.

The wiring layer 21, the display electrode 22, and the wiring pattern 23 can be made of the same material as the conductive layer 3 and the conductive layer 4 described in the first embodiment.

The cured film 10 is made of a material described later, and is an insulating material having bending characteristics. The cured film 10 a and the cured film 10 b may include the same material as the cured film 10 or may include different materials.

The organic light emitting layer 24 is a part that emits light by recombination of carriers, and is configured to include an organic material corresponding to any one of R, G, and B colors. Examples of the material that can be used as the organic light-emitting layer 24 include poly-phenylene vinylene (PPV) and its derivatives, polyacetylene and its derivatives, polyfluorene and its derivatives, and polybenzene and its derivatives. , Poly-p-styrene and its derivatives, poly 3-hexylthiophene and its derivatives, etc. Examples of other materials that can be used as the organic light-emitting layer 24 include anthracene, naphthalene, pyrene, tetracene, coronene, pyrene, phthaloperylene, naphthaloperylene, and dibenzene. Butadiene, tetraphenylbutane, coumarin, oxadiazole, bisbenzoxazoline, bisstyrene, cyclopentadiene, quinoline metal complex, tris (8-hydroxyquinoline) ) Aluminum complex, tris (4-methyl-8-quinoline) aluminum complex, tris (5-phenyl-8-quinoline) aluminum complex, aminoquinoline metal complex, benzene Benzoquinoline metal complex, tris (p-terphenyl-4-yl) amine, pyran, quinacridone, rubrene or derivatives of these, or 1-aryl-2,5-bis (2 -Thienyl) pyrrole derivatives, diphenylethenylbenzene derivatives, phenylethenylarylene derivatives, phenethylenylamine derivatives, or those having a group containing these luminescent compounds in a part of the molecule Compounds etc.

The sealing layer 25 is provided for the purpose of sealing the arrayed organic light-emitting elements (elements including the organic light-emitting layer 24) to prevent oxygen or moisture from being mixed from the outside, thereby increasing the life of the OLED 1 a. As the material of the sealing layer 25, if it is an organic substance, UV-curable acrylic resin, epoxy resin, etc. can be used, and if it is an inorganic substance, SiON, SiO, SiN, etc. can be used.

As the polarizing film 26, an existing polarizing plate can be used. The polarizing film 26 may not be included.

(Production method)
Hereinafter, with reference to FIGS. 4A to 4G, the manufacturing method of the OLED 1 a will be described with respect to parts different from the first embodiment. In addition, for the convenience of illustration, in FIGS. 4A to 4G, the illustration of each layer constituting the transistor element for element selection is omitted as in FIG. 3.

First, a transistor element (not shown) for element selection is suitably formed in a predetermined region on the upper surface of the flexible substrate 2, and then the conductive layer 3 and the wiring layer 21 are formed. The layer constituting the transistor element may include a gate electrode, a gate insulating film, a semiconductor layer, a source electrode, a drain electrode, and a passivation film.

The wiring layer 21 is electrically connected to a source electrode of a transistor element included in each picture element of the OLED 1a. That is, the wiring layer 21 is electrically connected to the source electrode through an opening provided in the passivation film above the region where the active electrode is formed. The method for forming the conductive layer 3 and the wiring layer 21 is the same as the method for forming the conductive layer 3 in the first embodiment. In addition, in this embodiment, the area where the wiring layer 21 is formed corresponds to the active area A1 (display area) of the OLED 1a, and the areas other than the active area A1 correspond to the non-active area A2 (non-display area) of the OLED 1a. . A conductive layer 3 is formed in the inactive area A2.

As shown in FIG. 4B, a photosensitive film-forming composition containing a material described later is applied so as to cover the upper surface of the wiring layer 21 and a part of the upper surface of the conductive layer 3 to form a coating film 8.

As shown in FIG. 4C, after a predetermined portion of the coating film 8 is opened through an exposure process, the display electrode 22 and the wiring pattern 23 are formed at a predetermined portion including the opening region. The specific method is the same as that described with reference to FIGS. 2C and 2D of the first embodiment.

That is, the coating film 8 is exposed through a mask. Thereafter, if necessary, a post-exposure heat treatment (PEB treatment) is performed, and then development is performed using an alkaline developer to remove the unnecessary coating film 8. Thereafter, the coating film 8 is heat-treated to harden (post-bake), and becomes the cured film 10. Thereafter, a conductive material film is formed in a predetermined region including the opening. Thereby, the display electrode 22 is electrically connected to the wiring layer 21, and the wiring pattern 23 is electrically connected to the conductive layer 3. In addition, for the purpose of improving the shape stability after the post-baking process, the exposure process and the heating process may be performed after the exposure process and before the post-baking process is performed, as described in the first embodiment.

As shown in FIG. 4D, an insulating hardened film 10 b having a part of the upper surface of the display electrode 22 opened and an insulating hardened film 10 a formed so as to cover the upper layer of the wiring pattern 23 are formed. Thereafter, as shown in FIG. 4E, an organic light emitting layer 24 is formed on the exposed upper surface of the display electrode 22 by a material film having an appropriate emission color for each picture element.

Next, as shown in FIG. 4F, a sealing layer 25 made of an insulating material is formed so as to cover the entire surface of the display electrode 22 and the cured film 10 b arranged in the active region A1. Thereafter, as shown in FIG. 4G, a control wafer 27 is formed on the upper layer of the conductive layer 3 in the non-active region A2 as necessary. If necessary, a polarizing film 26 is attached to the upper layer of the sealing layer 25.

Thereafter, as in the first embodiment, stress is applied to the flexible substrate 2 to bend the whole, and more specifically, the flexible substrate 2 in the non-active area A2 is directed toward the cured film (10, 10a). The opposite side is bent, thereby realizing the form shown in FIG. 3. At this time, since the cured film 10 has high extensibility and excellent bending performance, even when the entirety is bent by applying stress as shown in FIG. 3, no cracking or peeling occurs. Therefore, it is also possible to realize a fine electrode pattern in a curved region where it is difficult to form a wiring layer for the conventional OLED. Therefore, fine wiring for realizing a complicated control mechanism can be formed in the curved area portion corresponding to the non-active area A2, so that the OLED 1a with a narrow frame width and a multifunctionality can be realized.

In addition, since all the hardened films (10, 10a, 10b) are made of the same material, the steps of applying the materials constituting the hardened film (10, 10a, 10b) can be shared as appropriate, so the number of steps can be reduced.

[Third Embodiment]
The following description focuses on parts different from the first embodiment. FIG. 5 schematically illustrates an example of a touch screen as one embodiment of the wiring member of the present invention. The touch screen 1b includes a flexible substrate 2, a conductive layer 3 formed on the upper layer of the flexible substrate 2, a detection electrode 31 and a wiring electrode 32 formed on the upper layer of the flexible substrate 2, and an insulating hardened film ( 10, 10c), a bridge electrode layer 33 that connects the detection electrodes 31 to each other, a wiring pattern 23 that is electrically connected to the conductive layer 3, and a control wafer 27.

The detection electrode 31 is an electrode that detects when a conductive body approaches, and transmits the detection signal to an external circuit via the wiring electrode 32. A plurality of detection electrodes 31 are formed at the center of the active area of the flexible substrate 2 to form a detection area. The wiring electrodes 32 connected to the plurality of detection electrodes 31 are collectively formed outside the detection area.

The touch screen 1b shown in FIG. 5 has an active area A1 and a non-active area A2 similarly to the OLED 1a shown in FIG. 3. The active area A1 corresponds to an area where the detection electrode 31 is formed. The inactive area A2 is an area other than the active area A1 and is an area in which the control wafer 27 and the wiring pattern 23 are formed.

In addition, as in the second embodiment, the flexible substrate 2 has a curved region, and a control wafer 27 is formed in the curved region. For example, the control wafer 27 may be electrically connected to the wiring electrode 32 and output a signal for performing a predetermined process based on a signal input through the wiring electrode 32. In addition, the wiring electrode 32 itself may be arranged in a curved region of the flexible substrate 2.

As the detection electrode 31, a transparent conductive film formed by depositing indium tin oxide (ITO), tin oxide, zinc oxide, a conductive polymer, or the like can be used. As the wiring electrode 32, a transparent electrode film or a metal film can be used.

The detection electrodes 31 are arranged in a matrix in the detection area of the flexible substrate 2, and the detected signals corresponding to the coordinates are output through the wiring electrodes 32. That is, the active area A1 corresponds to the detection area of the flexible substrate 2. In addition, since the plurality of detection electrodes 31 are arranged in a matrix, in order to specify the positions where the conductors are close to each other, for example, a bridge electrode layer 33 that connects the detection electrodes 31 in the same row or the detection electrodes 31 in the same column is provided. In addition, the bridge electrode layer 33 may be formed so as to intersect in an oblique direction. The bridge electrode layer 33 can be made of the same material as the detection electrode 31.

As shown in FIG. 5, the bridge electrode layer 33 is electrically connected to a predetermined detection electrode 31 through a contact hole opened in a predetermined area in the cured film 10 c. Therefore, the cured film 10c preferably contains a photosensitive insulating material.

When the conductive body approaches a specific position in the detection area, the capacitance between the detection electrode 31 of the row and the detection electrode 31 of the column that the conductive body approaches is changed. The signal of the capacitance change is input to the control wafer 27 via the wiring electrode 32. The control wafer 27 specifies the row and column in which the capacitance is changed, and thereby specifies the position where the conductor approaches. In addition, the detection electrode 31 and the bridge electrode layer 33 can interact with each other. That is, the pattern of the bridge electrode layer 33 located on the upper layer can be used as a detection electrode, and the layer of the detection electrode 31 on the lower layer can be used as the pattern of the bridge electrode.

In this embodiment, the wiring pattern 23 is also formed in the curved region of the flexible substrate 2. Therefore, by electrically connecting the wiring pattern 23 and the control wafer 27, the control wafer 27 can perform not only the position detection. You can also input / output multiple processed signals. In addition, since the wiring electrode 32 may be provided in a curved region of the flexible substrate 2, the area of the active region of the touch screen can be sufficiently secured. In addition, the active area of the touch screen is an area that can accept touch operations.

The method of manufacturing the touch screen 1b according to this embodiment is the same as that of the first and second embodiments, and is therefore omitted.

[Another embodiment]
In the OLED 1a and the touch screen 1b in the second embodiment, the case where each layer is formed on the upper surface of the flexible substrate 2 is described for both the active area A1 and the non-active area A2. However, as the portion constituting the active region A1, a substrate having no flexibility such as a glass substrate may be used.

[material]
The material (the composition for forming a photosensitive film) constituting the cured film 10 (coating film 8) described in each embodiment will be described below.

The composition constituting the cured film 10 contains a polymer (A) having an alkali-soluble group, a radiation-sensitive compound (B), and a solvent (C), and optionally contains a crosslinkable compound (D), an adhesion promoter (E), and Surfactant (F).

<Polymer (A) having alkali-soluble group>
The polymer (A) has an alkali-soluble group. As an example, the polymer (A) has at least one functional group selected from a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group. More specifically, examples of the material constituting the polymer (A) include a novolac resin, an alkali-soluble resin having a phenolic hydroxyl group (excluding the novolac resin), an unsaturated carboxylic acid, and a polyfluorene. Polyamidoacids of imine precursors and some of their fluorenimides, polyhydroxyamidoamines as polybenzoxazole precursors, and the like.

The novolak resin can be obtained, for example, by condensing phenols and aldehydes in the presence of an acid catalyst. Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, and p-butylphenol. Phenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, catechol, resorcinol, pyrogallol, α-naphthol, β- Naphthol. Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, and salicylaldehyde.

Specific examples of the novolac resin include phenol / formaldehyde condensation novolac resin, cresol / formaldehyde condensation novolac resin, cresol / salicylaldehyde condensation novolac resin, phenol-naphthol / formaldehyde condensation novolac Resin and novolac resin are modified by a rubber-like polymer having a polymerizable vinyl group such as a butadiene-based polymer.

When the polymer (A) contains an alkali-soluble resin having a phenolic hydroxyl group, the polymer (A) preferably has a structural unit represented by the following formula (a1) (hereinafter referred to as "structural unit (a1)").

[Chemical 1]

In the formula (a1), a plurality of R ¹ each independently represent a hydrogen atom or a hydroxyl group (phenolic hydroxyl group). Among them, at least one of the plurality of R ¹ is a hydroxyl group (phenolic hydroxyl group) as an alkali-soluble group. Particularly preferably, R ¹ at the p-position is a hydroxyl group, and other R ¹ is a hydrogen atom. R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom or a methyl group.

Examples of the alkali-soluble resin having a phenolic hydroxyl group include p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, o-isopropenylphenol, and the like. A solitary or copolymer having a phenolic hydroxyl group, a phenol-xylylene glycol condensation resin, a cresol-xylylene glycol condensation resin, and a phenol-dicyclopentadiene condensation resin.

The alkali-soluble resin having a phenolic hydroxyl group may be an AB-type block polymer or an ABA-type block polymer. Examples of the block polymer include a block polymer including a polymer block including the structural unit (a1) and a polymer block including the structural unit (m2), and the structural unit (m2) It is derived from at least one kind of monomer selected from (meth) acrylate, 1,3-butadiene, isoprene, and chloroprene. As the block polymer, another example includes a polymer block including the structural unit (a1) and a block derived from CH ₂ = CH (OR) (wherein R is an alkyl group, an aryl group, or an aromatic group). Alkyl group or alkoxyalkyl group, a block polymer of a polymer block of structural units in which one or more hydrogen atoms may be substituted by fluorine atoms).

The block polymer may have a structural unit derived from a monomer other than the above. Examples of these monomers include unsaturated carboxylic acids or anhydrides thereof, esters of the unsaturated carboxylic acids, unsaturated nitriles, unsaturated amines, unsaturated amines, and unsaturated alcohols. Compounds, alicyclic skeleton compounds, nitrogen-containing vinyl compounds.

More specifically, for example:
(Meth) unsaturated carboxylic acids such as acrylic acid, maleic acid, fumaric acid, crotonic acid, mesaconic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride, or these anhydrides;
Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, cyclohexyl, 2- Hydroxyethyl ester, 2-hydroxypropyl ester, 3-hydroxypropyl ester, 4-hydroxybutyl ester, 2,2-dimethyl-3-hydroxypropyl ester, benzyl ester, isobornyl ester, tricyclodecyl ester, 1- Esters such as amantadine;
(Meth) acrylonitrile, maleonitrile, fumaric nitrile, Zhongcononitrile, citraconitrile, itaconitrile, and other unsaturated nitriles; (meth) acrylamid, crotylamine, maleimide, rich Unsaturated ammonium amines such as malamidine, mesalamine, citraconam, itacamide; maleimide, N-phenylmaleimide, N-cyclohexylmaleimide Unsaturated fluorene imines; (meth) allyl alcohols and other unsaturated alcohols;
Bicyclo [2.2.1] hept-2-ene (norbornene), tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] twelve-3-ene, cyclobutene, cyclopentene, cyclooctene Compounds having an alicyclic skeleton, such as dicyclopentadiene, tricyclo [5.2.1.0 ^2,6 ] decene;
Nitrogen-containing vinyl compounds such as N-vinylaniline, vinylpyridines, N-vinyl-ε-caprolactam, N-vinylpyrrolidone, N-vinylimidazole, and N-vinyloxazole.

The polymer (A) may further have a structural unit (m1) containing a crosslinkable functional group different from the alkali-soluble group. This improves the heat resistance and insulation of the cured film 10.

The structural unit (m1) includes, for example, a material represented by a structural unit (hereinafter referred to as a “structural unit (a2)”) represented by the following formula (a2).

[Chemical 2]

In formula (a2), a plurality of R ³ each independently represent a group having a cationic polymerizable group or a hydrogen atom. Among them, at least one of the plurality of R ³ is a group having a cationic polymerizable group. Particularly preferably, R ³ at the p-position is a group having a cationic polymerizable group, and the other R ³ is a hydrogen atom. R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom or a methyl group.

In the present specification, examples of the cationically polymerizable group include an oxetanyl group, an oxetanyl group, a methylol group, an alkoxymethylol group, a dioxolane group, and a trioxanyl group. , Vinyl ether group, styryl group. Among these, a group having a cyclic ether structure is preferred in terms of forming a cured film having excellent elongation properties. Among these, an oxetanyl group or an oxetanyl group is preferred, and an oxetan group is particularly preferred. Propyl.

In the present specification, examples of the group having a cationically polymerizable group include hydrogen of an cationically polymerizable group itself, an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms). A group in which an atom (usually one or more, preferably one hydrogen atom) is substituted with a cationically polymerizable group and a group represented by the following formulae (A) to (C).

[Chemical 3]

In the formulae (A) to (C), Y ¹ to Y ³ each independently represent a direct bond, a methylene group, or an alkylene group having 2 to 10 carbon atoms. Y ⁴ to Y ⁶ each independently represent a direct bond, a methylene group, or an alkylene group having 2 to 10 carbon atoms. Y ⁷ to Y ⁹ each independently represent a cationically polymerizable group, and are preferably an oxetanyl group or an oxetanyl group, and particularly preferably an oxetanyl group. In formula (a2), it is particularly preferred that R ³ at the p position is a group represented by formulas (A) to (C), and the other R ³ is a hydrogen atom.

When the polymer (A) has a structural unit (m1) containing a crosslinkable functional group, the polymer (A) may include a structural unit having an alkali-soluble group and a structural unit having a crosslinkable functional group. The polymer chain (m1) may be a polymer chain including a structural unit having an alkali-soluble group and a polymer chain including a structural unit (m1) having a crosslinkable functional group.

Furthermore, the polymer (A) may have the following structural units (for example, a structural unit (a1), a structural unit (m2)) having a base-soluble group, and a structural unit (m1) having a crosslinkable functional group. The structural unit (hereinafter also referred to as "structural unit (a3)") represented by the formula (a3) may include a polymer different from the polymer (A) containing the structural unit (a3). When a polymer different from the polymer (A) containing the structural unit (a3) is contained, the cured film may have increased flexibility or fracture strength.

[Chemical 4]

In formula (a3), a plurality of R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. R ⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom or a methyl group. By having such a structural unit (a3), the moldability of the cured film at the time of a development process can be adjusted.

Regarding the cured film 10, by using a composition containing a polymer (A), the elongation characteristics of the cured film 10 are improved. As a reason therefor, it is presumed that: (1) a sea-island structure is formed by microphase separation, so that portions that are prone to elongation are gathered; and / or (2) the entanglement of the polymer main chain is increased.

With respect to the cured film 10, if the composition containing the polymer (A) is used, in addition to excellent elongation properties, the cured film 10 can also be formed with excellent properties such as electrical insulation properties. When the photosensitive film containing the polymer (A) and the radiation-sensitive compound (B) described later is used for the cured film 10, the cured film 10 having excellent properties such as resolution and residual film properties can be formed. In particular, when the polymer (A) contains an acyclic structural unit, the acyclic structural unit has lower rigidity and less steric hindrance than the cyclic structural unit, so that high flexibility can be obtained. Therefore, the elongation physical properties of the composition constituting the cured film 10 can be improved.

In the polymer (A), a structural unit (for example, a structural unit (a1), a structural unit (m2)) containing an alkali-soluble group, and a structural unit (m1) containing a crosslinkable functional group and / or as required The arrangement of the structural units (a3) is not particularly limited, and the polymer (A) may be any of a random copolymer and a block copolymer.

In the polymer (A), with respect to 100 mol% of all the structural units, the structural unit (for example, the structural unit (a1), the structural unit (m2)) containing an alkali-soluble group and the structural unit containing a crosslinkable functional group ( The total content ratio of m1) is preferably 60 mol% to 95 mol%, and more preferably 70 mol% to 90 mol%. When the total content ratio of these is within the above-mentioned range, the polymer (A) becomes a polymer mainly composed of a styrene-based skeleton, and there is a tendency that properties such as heat resistance and electrical insulation of the cured film 10 are improved. The content of the structural unit of the polymer (A) can be measured by ¹ H-Nuclear Magnetic Resonance (NMR) and ¹³ C-NMR analysis.

Regarding the weight average molecular weight (Mw) of the polymer (A) measured by a gel permeation chromatography (GPC) method, from the viewpoint of the thermal shock resistance and heat resistance of the cured film 10 and the resolution of the composition, In other words, it is usually 4,000 to 100,000 in terms of polystyrene, preferably 6,000 to 80,000, and even more preferably 8,000 to 30,000. When Mw is above the lower limit, the heat resistance or elongation properties of the cured film 10 tend to be improved. When Mw is below the upper limit, the compatibility of the polymer (A) with other components is improved. Furthermore, the patterning characteristics of the photosensitive composition tend to be improved. The details of the Mw measurement method will be described in the examples.

In addition, the cured film 10 may include the above-mentioned material and may be a mixture of a plurality of types of polymers (A) having an alkali-soluble group.

Hereinafter, the manufacturing method of a polymer (A) is demonstrated. When the structural unit containing an alkali-soluble group is a structural unit (a1), as a monomer which can form the said structural unit (a1), the monomer represented by Formula (a1 ') (henceforth the following is also called) "Monomer (a1 ')"), etc. Moreover, when the structural unit (m1) containing a crosslinkable functional group is made into the structural unit (a2), as a monomer which can form the said structural unit (a2), the formula (a2 ') is mentioned. Monomer (hereinafter also referred to as "monomer (a2 ')") and the like. Moreover, as a monomer which can form a structural unit (a3), the monomer (henceforth a "monomer (a3 ')") etc. which are represented by Formula (a3') are mentioned. In addition, in this specification, "a structural unit derived from a monomer" is also abbreviated as "a monomer unit."

[Chemical 5]

In addition, in formula (a1 '), R ¹ and R ² have the same meanings as R ¹ and R ² in formula (a1), and in formula (a2'), R ³ and R ⁴ have the same meaning as in formula (a2). the R ³ and R ⁴ are the same meanings of formula (a3 '), R ⁵ is and R is R ⁵ and R ⁶ respectively of formula (a3) ⁶ is the same meaning.

Examples of the monomer (a1 ') include aromatics having phenolic hydroxyl groups such as p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, and o-isopropenylphenol. Among these vinyl compounds, p-hydroxystyrene and p-isopropenylphenol are preferred.

A monomer in which the hydroxyl group of the monomer (a1 ′) is protected by, for example, a tert-butyl group or an ethylfluorenyl group may also be used. A structural unit derived from a hydroxyl-protected monomer is converted into a structural unit containing a phenolic hydroxyl group by a known method (for example, in a solvent and under an acid catalyst such as hydrochloric acid or sulfuric acid, at a temperature of 50 ° C to The reaction is performed at 150 ° C for 1 hour to 30 hours.) The obtained polymer is deprotected. A monomer (a1 ') may be used individually by 1 type, and may use 2 or more types together.

Examples of the monomer (a2 ′) include p-vinylbenzyl glycidyl ether and p-vinylbenzyloxetane. A monomer (a2 ') may be used individually by 1 type, and may use 2 or more types together.

Examples of the monomer (a3 ') include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-methoxystyrene, and m-methoxy Aromatic vinyl compounds such as styrene and p-methoxystyrene. A monomer (a3 ') may be used individually by 1 type, and may use 2 or more types together.

The polymer (A) is, for example, a copolymer of a monomer (a1 '), a monomer (a2'), and an optional monomer (a3 '), and may include only the structural unit (a1) and the structural unit (a2) and The required structural unit (a3) may include an acyclic structural unit.

When the polymer (A) is obtained, for example, as long as the monomer (a1 ') and / or the compound that has protected its hydroxyl group and the monomer (a2'), and optionally the monomer (a3 ') or other monomer are used in the initiator, Polymerization may be carried out in the presence of ions and in a solvent. The polymerization method is not particularly limited, and in order to obtain a polymer having the above-mentioned molecular weight, it is preferably carried out by radical polymerization, anionic polymerization, or the like.

<Radiation-sensitive compound (B)>
The composition constituting the cured film 10 may contain a radiation-sensitive compound (B) to impart radiation sensitivity (photosensitivity). The radiation-sensitive compound in this case may be any of a positive type and a negative type. The radiation-sensitive compound (B) can be appropriately selected according to a positive radiation-sensitive compound or a negative radiation-sensitive compound. As the radiation-sensitive compound (B), in the case of a positive type, a compound having a quinonediazide group (hereinafter also referred to as "quinonediazide compound (B1)") and the like are used. Examples include photo-sensitive acid generators (hereinafter also referred to as "acid generators (B2)").

"Quinone Diazide Compound (B1)"
Quinonediazide compound (B1) is an ester of a compound having one or more phenolic hydroxyl groups and 1,2-naphthoquinonediazide-4-sulfonic acid or 1,2-naphthoquinonediazide-5-sulfonic acid Compound.

The coating film obtained from the photosensitive composition containing a quinonediazide compound (B1) is a coating film which is hardly soluble with respect to an alkaline developing solution. The quinonediazide compound (B1) is a compound that decomposes a quinonediazide group and generates a carboxyl group by light irradiation. Therefore, a positive pattern can be formed by using the following characteristics: the coating film is made alkaline by light irradiation The insoluble state is changed to an alkali-soluble state.

Examples of the compound having one or more phenolic hydroxyl groups include compounds represented by the following formulae (B1-1) to (B1-5). These compounds may be used individually by 1 type, and may use 2 or more types together.

[Chemical 6]

In the formula (B1-1), X ¹ to X ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. At least one of X ¹ to X ⁵ is a hydroxyl group. A is a direct bond, -O-, -S-, -CH _2- , -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , carbonyl (-C (= O)-) or sulfonyl (-S (= O) _2- ).

[Chemical 7]

In the formula (B1-2), X ¹¹ to X ²⁴ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. At least one of X ¹¹ to X ¹⁵ is a hydroxyl group. Y ¹ to Y ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[Chemical 8]

In the formula (B1-3), X ²⁵ to X ³⁹ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. At least one of X ²⁵ to X ²⁹ is a hydroxyl group, and at least one of X ³⁰ to X ³⁴ is a hydroxyl group. Y ⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[Chemical 9]

In the formula (B1-4), X ⁴⁰ to X ⁵⁸ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. At least one of X ⁴⁰ to X ⁴⁴ is a hydroxyl group, at least one of X ⁴⁵ to X ⁴⁹ is a hydroxyl group, and at least one of X ⁵⁰ to X ⁵⁴ is a hydroxyl group. Y ⁶ to Y ⁸ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[Chemical 10]

In the formula (B1-5), X ⁵⁹ to X ⁷² are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. At least one of X ⁵⁹ to X ⁶² is a hydroxyl group, and at least one of X ⁶³ to X ⁶⁷ is a hydroxyl group.

Examples of the quinonediazide compound (B1) include 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, and 2,3,4-trihydroxybenzophenone. , 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,2 ', 4'-pentahydroxybenzophenone, tris (4-hydroxyphenyl) methane, tris (4- Hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl] Benzene, 1,4-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene, 1,1-bis (4-hydroxyphenyl) -1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethane Ester compounds with 1,2-naphthoquinonediazide-4-sulfonic acid or 1,2-naphthoquinonediazide-5-sulfonic acid.

The quinonediazide compound (B1) may be used singly or in combination of two or more kinds. When the quinonediazide compound (B1) is used as the radiation-sensitive compound (B), the content of the quinonediazide compound (B1) is usually 5 to 50 parts by mass based on 100 parts by mass of the polymer (A). The mass part is preferably 10 to 30 parts by mass, and more preferably 15 to 30 parts by mass. When the content of the quinonediazide compound (B1) is equal to or more than the lower limit value, the residual film rate of the unexposed portion is increased, and an image faithful to the mask pattern is easily obtained. When the content of the quinonediazide compound (B1) is at most the above-mentioned upper limit value, a cured film having an excellent pattern shape is easily obtained, and foaming at the time of curing can be prevented.

"Acid generator (B2)"
The acid generator (B2) is a compound that forms an acid by light irradiation. The acid acts on the cationically polymerizable group of the polymer (A) to form a crosslinked structure. A negative pattern can be formed by utilizing a characteristic that the coating film obtained from the radiation-sensitive compound (B) containing the acid generator (B2) is changed from an alkali-soluble state to an alkali by the formation of a crosslinked structure. Insoluble state.

Examples of the acid generator (B2) include an onium salt compound, a halogen-containing compound, a sulfonium compound, a sulfonic acid compound, a sulfonylimine compound, and a diazomethane compound. Among these, an onium salt compound is preferred because a cured film having excellent elongation properties can be formed.

Examples of onium salt compounds include sulfonium salts, sulfonium salts, sulfonium salts, diazonium salts, and pyridinium salts. Specific examples of preferred onium salts include diphenylsulfonium trifluoromethanesulfonate, diphenylsulfonium p-toluenesulfonate, diphenylsulfonium hexafluoroantimonate, and diphenylsulfonium hexafluorophosphoric acid. Salt, diphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, 4-tert-butylphenyl × Diphenylsulfonium triflate, 4-tert-butylphenyl × diphenylsulfonium p-toluenesulfonate, 4,7-di-n-butoxynaphthyltetrahydrothienium trifluoromethanesulfonate Salt, 4- (phenylthio) phenyldiphenylphosphonium tris (pentafluoroethyl) trifluorophosphate, 4- (phenylthio) phenyldiphenylphosphonium hexafluorophosphate.

Examples of the halogen-containing compound include a halogenated alkyl-containing hydrocarbon compound and a halogenated alkyl-containing heterocyclic compound. Specific examples of preferred halogen-containing compounds include 1,10-dibromo-n-decane, 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, and benzene. -Bis (trichloromethyl) -mesytriazine, 4-methoxyphenyl-bis (trichloromethyl) -mesitytriazine, styryl-bis (trichloromethyl) -mesitytriazine, Mesazine derivatives such as naphthyl-bis (trichloromethyl) -mesatriazine.

Examples of the fluorene compound include β-ketofluorene compounds, β-sulfofluorene fluorene compounds, and α-diazo compounds of these compounds. Specific examples of the preferred sulfonium compound include 4-tribenzylhydrazone methylsulfonium, mesitylbenzylhydrazone methylsulfonium, and bis (benzylhydrazone methylsulfonyl) methane.

Examples of the sulfonic acid compound include alkylsulfonic acid esters, halogenated alkylsulfonic acid esters, arylsulfonic acid esters, and iminosulfonic acid esters. Specific examples of preferred sulfonic acid compounds include benzoin tosylate, pyrogallol tri-trifluoromethanesulfonate, o-nitrobenzyl trifluoromethanesulfonate, and o-nitrobenzyl Tosylate.

Examples of the sulfonimine compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N -(Trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyl Fluorenimine, N- (trifluoromethylsulfonyloxy) naphthylfluorenimine.

Examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, and bis (phenylsulfonyl) diazomethane.

The acid generator (B2) may be used singly or in combination of two or more kinds. When the acid generator (B2) is used as the radiation-sensitive compound (B), the content of the acid generator (B2) is usually 0.1 to 10 parts by mass based on 100 parts by mass of the polymer (A). It is 0.3 to 5 parts by mass, and more preferably 0.5 to 5 parts by mass. When content of an acid generator (B2) is more than the said lower limit, hardening of an exposure part will become sufficient and heat resistance will become easy to improve. When content of an acid generator (B2) exceeds the said upper limit, transparency with respect to exposure light may fall and resolution may fall.

<Solvent (C)>
The composition constituting the cured film 10 contains a solvent (C). By using the solvent (C), operability, viscosity adjustment, and storage stability can be improved.

Examples of the solvent (C) include:
Alcohols such as methanol, ethanol, ethylene glycol, diethylene glycol, and propylene glycol;
Cyclic ethers such as tetrahydrofuran and dioxane;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol Alkyl ethers of polyhydric alcohols such as ethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether;
Alkyl ether acetates of polyhydric alcohols such as ethylene glycol monoethyl ether acetate, diethylene glycol ethyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate;
Aromatic hydrocarbons such as toluene and xylene;
Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methylpentyl ketone, 4-hydroxy-4-methyl-2-pentanone, diacetone alcohol;
Ethyl acetate, butyl acetate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutane Methyl ester, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, ethyl lactate, etc. Wait. Among these, tetrahydrofuran, propylene glycol monomethyl ether acetate, diethylene glycol ethyl methyl ether, ethyl lactate, methylpentyl ketone, and propylene glycol monomethyl ether are preferred.

The solvent (C) may be used singly or in combination of two or more kinds. In the composition constituting the cured film 10, the content of the solvent (C) is usually 40 parts by mass to 900 parts by mass, and preferably 60 parts by mass with respect to 100 parts by mass of a total of components other than the solvent (C) in the composition. ~ 400 parts by mass.

<Crosslinkable compound (D)>
The composition constituting the cured film 10 may further include a crosslinkable compound (D) in order to improve the curability and increase the breaking strength. The crosslinkable compound (D) functions as a crosslinkable component (hardening component) that reacts with the polymer (A).

Examples of the crosslinkable compound (D) include compounds having two or more alkyl etherified amine groups (hereinafter also referred to as "amine group-containing compounds"), and compounds containing an oxeane ring. , A compound containing an oxetane ring, a compound containing an isocyanate group (including a blocker), a phenol compound containing an aldehyde group, and a phenol compound containing a methylol group. Among them, compounds corresponding to the polymer (A) are excluded from the self-crosslinkable compound (D). Moreover, the silane coupling agent which has an oxetanyl group is excluded from the compound containing an oxepan ring, and the silane coupling agent which has an isocyanate group is excluded from the compound which contains an isocyanate group.

Examples of the alkyl-etherified amine group include a group represented by the following formula. In the formula, R ¹¹ represents a methylene group or an alkylene group, and R ¹² represents an alkyl group.

[Chemical 11]

Examples of the amine group-containing compound include nitrogen such as (poly) methylolated melamine, (poly) methylolated glycoluril, (poly) methylolated benzomelamine, and (poly) methylolated urea. Compounds in which all or part (at least two) of the active methylol groups (CH ₂ OH groups) in the compound are alkyl etherified. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group. These may be the same as or different from each other. In addition, the methylol group which is not alkyl etherified may be self-condensed in one molecule or may be condensed between two molecules. As a result, an oligomer component can be formed. Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycol urea, tetrabutoxymethylglycol urea, and the like can be used.

The compound containing an oxetane ring is not particularly limited as long as it contains an oxetane ring (also referred to as an oxetanyl group) in the molecule, and examples thereof include phenol novolac epoxy resins, Cresol novolac epoxy resin, bisphenol epoxy resin, triphenol epoxy resin, tetraphenol epoxy resin, phenol-xylylene epoxy resin, naphthol-xylylene ring Oxygen resin, phenol-naphthol type epoxy resin, phenol-dicyclopentadiene type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin.

Specific examples of the oxetane-containing compound include resorcinol diglycidyl ether, pentaerythritol glycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, and phenyl glycidyl. Glyceryl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether / polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether / polypropylene glycol diglycidyl ether, 1,6-hexanediol di Glycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane triglycidyl ether.

The oxetane ring-containing compound is not particularly limited as long as it contains an oxetane ring (also referred to as an oxetanyl ring) in the molecule, and examples thereof include the general formula (d-1) ~ A compound represented by general formula (d-3).

[Chemical 12]

In formulas (d-1) to (d-3), A represents a direct bond or an alkylene group such as methylene, ethylene, or propylene; R represents an alkyl group such as methyl, ethyl, or propyl; R ¹ represents an alkylene group such as methylene, ethylene, or propylene; R ² represents an alkyl group such as methyl, ethyl, propyl, or hexyl; aryl group such as phenyl or xylyl;

[Chemical 13]

A group (wherein R and R ^{1 have} the same meanings as R and R ¹ in formula (d-1) to formula (d-3), respectively), and a dimethyl group represented by the following formula (i) Siloxane residues; alkylene groups such as methylene, ethylene, and propylene; phenylene groups; groups represented by the following formulae (ii) to (vi); i and R ^{2 have} the same valence Is an integer from 1 to 4. In addition, "*" in the following formulas (i) to (vi) represents a bonding site.

[Chemical 14]

In Formula (i) and Formula (ii), x and y are each independently an integer of 0-50. In formula (iii), Z is a direct bond or two represented by -O-, -CH _2- , -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -CO- or -SO _2- Price base.

Specific examples of the compounds represented by the general formulae (d-1) to (d-3) include 1,4-bis {[(3-ethyloxetane-3-yl) Methoxy] methyl} benzene (trade name "OXT-121", manufactured by Toa Sangyo Co., Ltd.), 3-ethyl-3-{[((3-ethyloxetane-3-yl) methyl Oxy] methyl} oxetane (trade name "OXT-221", manufactured by Toa Kosei Co., Ltd.), 4,4'-bis [(3-ethyl-3-oxetanyl) methyl Oxymethyl] biphenyl (manufactured by Ube Kosan Co., Ltd., trade name "ETERNACOLL OXBP"), bis [(3-ethyl-3-oxetanylmethoxy) methyl- Phenyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] propane, bis [(3-ethyl-3-oxetanylmethoxy) methyl- Phenyl] fluorene, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] one, bis [(3-ethyl-3-oxetanylmethoxy) methyl- Phenyl] hexafluoropropane, tris [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, tetra [(3-ethyl-3-oxetanylmethoxy) methyl] benzene A compound represented by the following formulae (da) to (dd).

[Chemical 15]

In addition to these compounds, high molecular weight compounds having a polyvalent oxetane ring can also be used. For example, an oxetane oligomer (brand name "Oligo-OXT", manufactured by Toa Sangyo Co., Ltd.), and a compound represented by the following formula (d-e) to formula (d-g) are mentioned.

[Chemical 16]

In the formulae (de) to (dg), p, q, and s are each independently an integer of 0 to 10,000, and preferably an integer of 1 to 10. In formula (df), Y is a group represented by an alkylene group such as ethylene or propylene, or -CH ₂ -Ph-CH _2- (in the formula, Ph represents a phenylene group).

The crosslinkable compound (D) may be used singly or in combination of two or more kinds. The content of the crosslinkable compound (D) is usually 1 to 60 parts by mass, preferably 5 to 50 parts by mass, and more preferably 5 to 40 parts by mass based on 100 parts by mass of the polymer (A). Serving. When the content of the crosslinkable compound (D) is within the above range, the curing reaction proceeds sufficiently. When a photosensitive composition is used, the formed cured film has a good pattern shape, and has excellent elongation properties and heat resistance. Excellent electrical insulation.

<Adhesion aid (E)>
The composition constituting the cured film 10 may further include an adhesion promoter (E) in order to improve adhesion to the lower layer. The adhesion assistant (E) is preferably a functional silane coupling agent, and examples thereof include a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryl group, a vinyl group, an isocyanate group, or an oxetanyl group. Specifically, Specific examples include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, and γ-isocyanate. Propyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 1,3,5-N-tris (Trimethoxysilylpropyl) isocyanurate.

The content of the composition constituting the cured film 10 is preferably 0.5 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass based on 100 parts by mass of the polymer (A). When the content of the adhesion assistant (E) is within the above range, the adhesion of the cured film 10 to the lower layer (for example, the substrate 1) is further improved.

<Surfactant (F)>
The composition constituting the cured film 10 may further contain a surfactant (F) in order to improve the film formability. Examples of the surfactant (F) include a fluorine-based surfactant, a silicone-based surfactant, and other surfactants.

〈Other additives〉
The composition constituting the cured film 10 may include various additives such as a leveling agent, a sensitizer, an inorganic filler, and a quencher within a range that does not impair the object and characteristics of the present invention.

In addition, the composition constituting the cured film 10 may further contain crosslinked fine particles in order to improve insulation and thermal shock resistance. Examples of the crosslinked fine particles include crosslinked fine particles of a copolymer of a monomer having a hydroxyl group and / or a carboxyl group and a crosslinkable monomer having two or more polymerizable unsaturated groups. In addition, crosslinked fine particles in which copolymers of other monomers are further copolymerized may also be used. The content of the composition constituting the cured film 10 is preferably 0 to 200 parts by mass, more preferably 0.1 to 150 parts by mass, and more preferably 100 parts by mass of the polymer (A). It is 0.5 to 100 parts by mass.

[Production method]
The composition constituting the cured film 10 can be prepared by uniformly mixing the components. In addition, in order to remove waste residue, after the components are uniformly mixed, the obtained mixture may be filtered by a screening program or the like. The production method of each polymer is as described above.

The cured film 10 is formed by performing the following steps as described above: a step of applying a composition constituting the cured film 10 to a support (for example, the substrate 1) to form a coating film (coating step); A step of exposing the coating film with a mask pattern (exposure step); and developing the coating film with an alkaline developer to dissolve an exposed portion (in the case of a positive type) or a non-exposed portion (in the case of a negative type) The step of removing (the developing step) by which a desired pattern is formed on the support.
[Example]

Hereinafter, the present invention will be described in detail through examples, but the present invention is not limited to these examples.

<Method for measuring weight average molecular weight (Mw) of polymer (A) and other polymers>
Mw was measured by gel permeation chromatography (GPC) under the following conditions.
Tubular column: TSK-M and TSK2500 serially connected to Tosoh's column. Solvent: Tetrahydrofuran (THF)
Temperature: 40 ° C
Detection method: refractive index standard material: polystyrene

<Method for measuring content of structural unit of polymer (A)>
The content of the structural unit of the polymer (A) was measured by ¹ H-NMR and ¹³ C-NMR analysis.

<1. Synthesis of Polymer (A)>

[Synthesis Example 1] Synthesis of Polymer (A-1) In a flask, 85 parts by mass of p-hydroxystyrene, 18 parts by mass of p-vinylbenzyl glycidyl ether, 21 parts by mass of styrene, and azobisisobutyl were prepared. A mixed solution in which 4 parts by mass of nitrile was dissolved in 150 parts by mass of propylene glycol dimethyl ether. The mixture was heated at 70 ° C for 10 hours. The heated mixed solution was put into a solution containing toluene and hexane, and the precipitate was washed with hexane to obtain a p-hydroxystyrene / p-vinylbenzyl glycidyl ether / styrene copolymer ( Hereinafter, it is also referred to as "polymer (A-1)").

The weight average molecular weight (Mw) of the polymer (A-1) was 8,800. The polymer (A-1) is a polymer having 70 mol% p-hydroxystyrene units, 10 mol% p-vinylbenzyl glycidyl ether units, and 20 mol% styrene units. The p-vinylbenzyl glycidyl ether is represented by the following formula.

[Chemical 17]

[Synthesis Example 2] Synthesis of Polymer (A-2) A total of 100 parts by mass of p-tert-butoxystyrene and styrene was dissolved in 150 parts by mass of propylene glycol monomethyl ether in a molar ratio of 80:20. The reaction temperature was maintained at 70 ° C. under a nitrogen atmosphere, and polymerization was performed for 10 hours using 4 parts by mass of azobisisobutyronitrile. Thereafter, sulfuric acid was added to the reaction solution, the reaction temperature was maintained at 90 ° C. and the reaction was performed for 10 hours, and p-tert-butoxystyrene was deprotected and converted into hydroxystyrene. Ethyl acetate was added to the obtained copolymer, followed by washing with water five times, the ethyl acetate phase was separated, and the solvent was removed to obtain a p-hydroxystyrene / styrene copolymer (hereinafter referred to as "polymer (A- 2)").

The molecular weight of the polymer (A-2) was measured by gel permeation chromatography (GPC). As a result, the weight average molecular weight (Mw) in terms of polystyrene was 10,000, and the weight average molecular weight (Mw) and number average molecular weight ( The ratio (Mw / Mn) of Mn) was 3.5. As a result of ¹³ C-NMR analysis, the molar ratio of copolymerized p-hydroxystyrene and styrene was 80:20.

[Synthesis Example 3] Synthesis of Polymer (A-4) A flask equipped with a cooling tube and a stirrer was charged with 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and diethyl ether. 220 parts by mass of glycol ethyl methyl ether. Next, 15 parts by mass of methacrylic acid, 25 parts by mass of glycidyl methacrylate, 10 parts by mass of p-isopropenylphenol, 25 parts by mass of methyl methacrylate, 5 parts by mass of lauryl methacrylate, and N- (Cyclohexyl) 20 parts by mass of maleimidine, after nitrogen substitution, stirring was started slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution (hereinafter referred to as "polymer (A-4)").

The solid content concentration of the polymer (A-4) was 31.0% by mass. The molecular weight of the polymer (A-4) was measured by gel permeation chromatography (GPC). As a result, the weight average molecular weight (Mw) in terms of polystyrene was 10,000, the weight average molecular weight (Mw) and the number average molecular weight (Mn). The ratio (Mw / Mn) is 2.1.

[Synthesis Example 4] Synthesis of Polymer (A-5) m-cresol and p-cresol were mixed at a weight ratio of 60:40, an aqueous formaldehyde solution was added thereto, an oxalic acid catalyst was used, and condensation was performed by a conventional method Cresol novolac resin. The resin was subjected to a classification treatment, and a low-molecular region was cut to obtain a novolak resin (hereinafter referred to as "polymer (A-5)") having a weight average molecular weight of 15,000.

[Synthesis Example 5] Synthesis of Polymer (A-6) A flask equipped with a thermometer, a cooling tube, a fractionating tube, and a stirrer was charged with 144.2 g (1.0 mol) of 1-naphthol and methyl isobutyl ketone. 400 g, 96 g of water, and 32.6 g of 92% by mass paraformaldehyde (1.0 mol in terms of formaldehyde conversion). Then, 3.4 g of p-toluenesulfonic acid was added while stirring. Then, it reacted at 100 degreeC for 8 hours. After the reaction, 200 g of pure water was added, and the solution in the system was transferred to a separating funnel, and the water layer was separated and removed from the organic layer. Then, water washing was performed until the washing water showed neutrality, and then the solvent was removed from the organic layer under heating and reduced pressure to obtain a novolak resin (hereinafter referred to as a weight average molecular weight (Mw) of the structural unit represented by the following formula: 2,000) It is called "polymer (A-6)").
[Chemical 18]

[Synthesis Example 6] Synthesis of Polymer (A-7) A flask equipped with a cooling tube and a stirrer was charged with 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and diethyl ether. 220 parts by mass of glycol ethyl methyl ether. Next, 15 parts by mass of methacrylic acid, 40 parts by mass of glycidyl methacrylate, 10 parts by mass of p-isopropenylphenol, 10 parts by mass of methyl methacrylate, 5 parts by mass of lauryl methacrylate, and N- (Cyclohexyl) 20 parts by mass of maleimidine, after nitrogen substitution, stirring was started slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution (hereinafter referred to as "polymer (A-7)"). The solid content concentration of the obtained polymer solution was 31.0% by weight.

[Synthesis Example 7] Synthesis of Polymer (A-8) In 1000 mL of tetrahydrofuran, 0.05 g of n-butyllithium as an anionic polymerization initiator was dissolved, and then cooled to -70 ° C. 45 g of 2-methyl-1,3-butadiene (isoprene) was added to the solution, and polymerization was performed for 3 hours. Next, 55 g of p-tert-butoxystyrene was added, and polymerization was further performed for 2 hours. Polymerization was stopped by adding methanol, and a polymer produced by mixing with a large amount of methanol was solidified.

Next, the obtained copolymer was dissolved in 500 g of tetrahydrofuran, 5 g of p-toluenesulfonic acid monohydrate and 10 g of distilled water were added, and a deprotection reaction was performed under heating and refluxing for 12 hours. Thereafter, the reaction solution was poured into a large amount of distilled water, the copolymer was coagulated and recovered, and dried under reduced pressure to obtain a white copolymer (A-8). The copolymer (A-8) is an AB-type ([isoprene]-[p-hydroxystyrene]) block copolymer, and Mw is 35,000. As a result of ¹³ C-NMR measurement, the mass ratio in the copolymer including the structural units of isoprene and p-hydroxystyrene was 55/45.

[Synthesis Example 8] In addition to synthesis of polymer (A-9), instead of using 2-methyl-1,3-butadiene (isoprene), 1,3-butadiene was used. Example 7 was synthesized in the same manner to obtain a copolymer (A-9). The copolymer (A-9) is an AB-type ([1,3-butadiene]-[p-hydroxystyrene]) block copolymer, and Mw is 30,000. As a result of ¹³ C-NMR measurement, the mass ratio in the copolymer including 1,3-butadiene and the constituent unit of p-hydroxystyrene was 30/70.

[Synthesis Example 9] Synthesis of Polymer (A-10) An aqueous solution prepared by dissolving 5 parts by mass of sodium dodecylbenzenesulfonate in 200 parts by mass of distilled water, 46 parts by mass of butadiene as a raw material monomer, 31 parts by mass of styrene, 10 parts by mass of 2-hydroxybutyl methacrylate, 9 parts by mass of methacrylic acid, 4 parts by mass of divinylbenzene, and a redox catalyst were charged into an autoclave, and the temperature was adjusted to 10 ° C. 0.01 parts by mass of cumene hydroxide was added as a polymerization initiator to perform emulsion polymerization until the polymerization conversion rate was 85%.

Then, N, N-diethylhydroxylamine was added as a reaction stopper to synthesize a copolymer emulsion. Thereafter, water vapor was blown into the solution to remove unreacted raw material monomers, and then the solution was added to a 5% calcium chloride aqueous solution, and the precipitated copolymer was copolymerized with a blower dryer set at 80 ° C. The copolymer was dried to isolate the copolymer (A-10). Regarding the copolymer (A-10), the glass transition temperature (Tg) was measured by a differential scanning calorimetry (DSC) method, and it was -27 ° C. (Morbi 63/22/5/8/2)

<3. Preparation of composition>

[Example 1]
40 parts by mass of the polymer (A-1), 60 parts by mass of the polymer (A-9), 25 parts by mass of the radiation-sensitive compound (B-1), 10 parts by mass of the crosslinkable compound (D-3), and closely adhere 7 parts by mass of the auxiliary agent (E-1) and 0.05 parts by mass of the surfactant (F-2) were dissolved in 260 parts by mass of the solvent (C-1) and 180 parts by mass of the solvent (C-5) to prepare a composition. A predetermined evaluation was performed using the obtained composition.

[Example 2 to Example 13, Comparative Example 1 to Comparative Example 2]
A composition was prepared in the same manner as in Example 1 except that the types and amounts of the blending components were changed as shown in Table 1. A predetermined evaluation was performed using the obtained composition.

The details of each component in Table 1 are as follows.

(Polymer (A))
A-1: Polymer (A-1) obtained in Synthesis Example 1
A-2: Polymer (A-2) obtained in Synthesis Example 2
A-3: Trade name "MARUKA LYNCUR M2PH" (manufactured by Maruzan Petrochemical Co., Ltd.)
A-4: Polymer (A-4) obtained in Synthesis Example 3
A-5: Polymer (A-5) obtained in Synthesis Example 4
A-6: Polymer (A-6) obtained in Synthesis Example 5
A-7: Polymer (A-7) obtained in Synthesis Example 6
A-8: Polymer obtained in Synthesis Example 7 (A-8)
A-9: Polymer (A-9) obtained in Synthesis Example 8
A-10: Polymer (A-10) obtained in Synthesis Example 9

(Radioactive compound (B))
B-1: 1,1-bis (4-hydroxyphenyl) -1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethane and 1,2- Condensate of naphthoquinonediazide-5-sulfonic acid (Molar ratio = 1.0: 2.0)
B-2: Condensate of 1,1,1-tris (p-hydroxyphenyl) ethane and 1,2-naphthoquinonediazide-5-sulfonyl chloride (Molar ratio = 1.0: 2.0)

(Solvent (C))
C-1: Propylene Glycol Monomethyl Ether Acetate (PGMEA)
C-2: methylpentyl ketone
C-3: ethyl lactate
C-4: Diethylene glycol ethyl methyl ether
C-5: Diacetone alcohol

(Crosslinkable compound (D))
D-1: Hexamethoxymethylol melamine, trade name "NIKALACK MW-390" (manufactured by Sanwa Chemical Co., Ltd.)
D-2: Trimethylolpropane triglycidyl ether, trade name "Denacol EX-321L" (manufactured by NAGASE ChemteX)
D-3: Compound represented by the following formula (D3)
D-4: Trade name "XD-1000" (manufactured by Nippon Kayaku Co., Ltd.)
D-5: trimellitic anhydride

[Chemical 19]

(Adhesion aid (E))
E-1: Tris (3- (trimethoxysilyl) propyl) isocyanurate, manufactured by GE Toshiba Silicone
E-2: 3-Glycidoxypropyltrimethoxysilane, manufactured by JNC

(Surfactant (F))
F-1: Fluorine-based surfactant, trade name "Ftergent FTX-218", manufactured by NEOS
F-2: Silicone surfactant, trade name "SH8400 FLUID", manufactured by Toray Dow Corning Co., Ltd.

(Other additives (G))
G-1: 4,4 '-[1- [4- [2- (4-hydroxyphenyl) -2-propyl] phenyl] ethylene] bisphenol

<4. Evaluation>
Each composition of an Example and a comparative example was evaluated as follows. The results are shown in Table 1.

(4-1 elongation)
Each composition was applied to a substrate with a release material, and then heated at 90 ° C. for 2 minutes using a hot plate to produce a uniform coating film having a thickness of 10 μm. Next, the entire surface of the coating film was irradiated with an alignment exposure machine (manufactured by Suss Microtec, model "MA-100") so that the exposure amount at a wavelength of 365 nm became 300 mJ / cm ² Ultraviolet light from a high-pressure mercury lamp. Next, the coating film was heated at 120 ° C for 5 minutes using a hot plate, and further heated at 230 ° C for 30 minutes using an oven.

The heated coating film was peeled from the substrate with a release material, and cut into a strip shape of 2.5 cm × 0.5 cm. The tensile breaking elongation (%) of the coating film was measured with a tensile compression tester (SDWS-0201 type, manufactured by Ida Manufacturing Co., Ltd.) (condition: chuck distance = 1.0 cm, tensile speed = 5 mm / min (Measurement temperature = 23 ℃). The result is an average of 5 measured values.

(4-2 breaking strength)
In the evaluation of the elongation, the stress when the coating film was broken was taken as the breaking strength. The breaking strength is a value calculated by the following formula.

(Break strength) = (Tensile force at break) / (Cross-sectional area of the sample)

(4-3 bending characteristics)
According to Japanese Industrial Standards (JIS) K 5600-5-1 (buckling resistance, cylindrical mandrel method), under the environment of a temperature of 25 ° C and a relative humidity of 50%, it will be used as 4-1 The coating film subjected to the heat treatment was bent 180 degrees (crimped) along a mandrel with an outer diameter of 0.5 mm, and the coating film was visually observed for cracking and peeling. A case where cracking and peeling did not occur was evaluated as A, and a case where cracking and peeling had occurred was evaluated as B.

(4-4 insulation)
Each composition is coated on a substrate 52 for evaluating the electrical insulation properties of the substrate 50 and the patterned copper foil 51 formed on the substrate 50 as shown in FIG. 6, and thereafter, a hot plate is used at 90 ° C. Under heating for 2 minutes, a base material having a coating film having a thickness of 10 μm on the copper foil 51 was produced. Thereafter, the coating film was cured by heating at 230 ° C. for 30 minutes using a convection oven to obtain a cured film. The obtained test substrate was put into a migration evaluation system (AEI, EHS-221MD, manufactured by Tabai Espec Co., Ltd.) at a temperature of 121 ° C, a humidity of 85%, a pressure of 1.2 atmospheres, and an application of Processed at a voltage of 10 V for 100 hours. Thereafter, the resistance value (Ω) of the test substrate was measured to confirm the electrical insulation properties. When the insulation property was confirmed, it was set to A evaluation.

(4-5 warping)
The coating film after the heat treatment by the same method as 4-1 was cut into 5 cm squares, and the case where the floating height at the end was within 10 mm was evaluated as A, and the floating height was 10 mm or more. The evaluation was set to B.

(4-6 shape after baking)
The resin composition was spin-coated on a 6-inch silicon wafer, and heated at 90 ° C. for 2 minutes using a hot plate to prepare a uniform coating film having a thickness of 3 μm. Thereafter, a mask using a registration exposure machine (manufactured by Suss Microtec Co., Ltd., model "MA-100") was arranged at intervals of 6 μm, and a plurality of masks with a square pattern of 2 μm on one side were removed. The ultraviolet rays from the high-pressure mercury lamp were exposed so that the exposure amount at a wavelength of 365 nm became 300 mJ / cm ² .

Then, it was immersed and developed at 23 ° C. for 60 seconds using a 2.38 mass% tetramethylammonium hydroxide aqueous solution. Thereafter, the entire surface of the coating film was irradiated with ultra pure water for 60 seconds and air-dried using the alignment exposure machine so that the exposure amount at a wavelength of 365 nm became 300 mJ / cm ² . Ultraviolet light from a high pressure mercury lamp.

Next, the coating film was heated at 120 ° C. for 5 minutes using a hot plate, and further heated at 230 ° C. for 30 minutes in an oven to harden the resin coating film to obtain a cured film. The cross-sectional shape was observed at a magnification of 1500 times using a scanning electron microscope (manufactured by Hitachi, Ltd., S-4200) with respect to the pattern obtained by removing a square having a side of 2 μm in this manner, and the cross-sectional shape was evaluated. A case where a pattern is not deformed to the extent that adjacent patterns are in contact with each other and a pattern opening is not buried (a case where an opening is maintained) is evaluated as A. The pattern opening is filled with the adjacent patterns in contact with each other to fill the pattern opening. In the case of B evaluation.

[Table 1]

1‧‧‧ Flexible printed circuit board

1a‧‧‧Organic EL element

1b‧‧‧Touch screen

2‧‧‧ flexible substrate

3‧‧‧ conductive layer

4‧‧‧ conductive layer

8‧‧‧ Coating

9‧‧‧ Opening area (opening / contact hole)

10, 10a, 10b, 10c‧‧‧Insulated hardened film

21‧‧‧Wiring layer

22‧‧‧Display electrode

23‧‧‧Wiring pattern

24‧‧‧Organic light emitting layer

25‧‧‧Sealing layer

26‧‧‧Polarizing film

27‧‧‧control chip

31‧‧‧detection electrode

32‧‧‧Wiring electrode

33‧‧‧Bridge electrode layer

50‧‧‧ Substrates for base materials for insulation evaluation

51‧‧‧copper foil

52‧‧‧Substrate for insulation evaluation

A1‧‧‧active area

A2‧‧‧ inactive area

FIG. 1 is a cross-sectional view schematically showing a configuration example of a flexible printed circuit board as an embodiment of a wiring member of the present invention.

FIG. 2A is a step sectional view of the flexible printed substrate shown in FIG. 1.

FIG. 2B is a step cross-sectional view of the flexible printed substrate shown in FIG. 1.

FIG. 2C is a step cross-sectional view of the flexible printed substrate shown in FIG. 1.

FIG. 2D is a step cross-sectional view of the flexible printed substrate shown in FIG. 1.

FIG. 2E is a step sectional view of the flexible printed substrate shown in FIG. 1.

3 is a cross-sectional view schematically showing a configuration example of an organic electroluminescence (EL) element as an embodiment of a wiring member of the present invention.

FIG. 4A is a step sectional view of the organic EL element shown in FIG. 3.

FIG. 4B is a step sectional view of the organic EL element shown in FIG. 3.

FIG. 4C is a step sectional view of the organic EL element shown in FIG. 3.

FIG. 4D is a step sectional view of the organic EL element shown in FIG. 3.

FIG. 4E is a step sectional view of the organic EL element shown in FIG. 3.

FIG. 4F is a step sectional view of the organic EL element shown in FIG. 3.

FIG. 4G is a step sectional view of the organic EL element shown in FIG. 3.

FIG. 5 is a cross-sectional view schematically showing a configuration example of a touch screen as an embodiment of a wiring member of the present invention.

FIG. 6 is a plan view schematically showing a substrate used in the insulation evaluation.

Claims (15)

A wiring member includes a substrate and a cured film disposed on an upper layer of the substrate, and the wiring member is characterized by: When the substrate surface of the wiring member on the side opposite to the cured film was bent 180 ° along a mandrel with an outer diameter of 0.5 mm, the cured film did not crack or peel. The wiring member according to item 1 of the scope of patent application, wherein the film thickness of the thickest portion of the cured film is 0.3 μm to 20 μm. The wiring member according to item 1 of the scope of patent application, wherein the cured film is converted to an elongation at break of 7% or more expressed by the following formula when the film thickness is 10 μm; the elongation at break (%) = {( L ₁ -L ₀ ) / L ₀ } × (10 / T) × 100 where T is the thickness of the cured film [μm], L ₀ is the initial length of the test piece, and L ₁ is the test piece when it is broken length. The wiring member according to claim 1 or claim 2, wherein a portion of the wiring member has a buckled portion. The wiring member according to item 1 or 2 of the scope of patent application, which can be used as a display substrate or a touch panel having an active area and an inactive area adjacent to the active area in a direction parallel to the substrate surface. Controlled screen substrate. The wiring member according to item 5 of the scope of patent application, wherein the inactive area is bent from a main surface side of the display substrate or the touch screen substrate toward a rear surface side opposite to the main surface . The wiring member according to item 6 of the scope of patent application, wherein the non-active area is bent by 180 ° so that a back surface of the non-active area faces a back surface of the active area. The wiring member according to item 5 of the scope of patent application, wherein the cured film located in the inactive region has a pattern formed by a photolithography method with respect to the positive-type photosensitive film. The wiring member according to item 8 of the scope of patent application, wherein the pattern is at least one of a hole pattern and a circuit pattern. The wiring member according to any one of claims 1 to 3, wherein the cured film is a coating film of a composition for forming a photosensitive film, and The composition for forming a photosensitive film includes: (A) a polymer having an alkali-soluble group, (B) radiation-sensitive compounds, and (C) Solvent. The wiring member according to claim 10, wherein the (A) polymer has a structural unit (m1) containing a crosslinkable functional group different from the alkali-soluble group. The wiring member according to claim 10, wherein the composition for forming a photosensitive film further contains (D) a crosslinkable compound. The wiring member according to item 9 of the scope of patent application, wherein the (A) polymer contains a structure derived from at least one of (meth) acrylate, butadiene, isoprene, and chloroprene Unit (m2). The wiring member according to item 9 of the scope of patent application, wherein the (A) polymer or a polymer different from the (A) polymer and contained in the photosensitive film-forming composition includes the following The structural unit (a3) represented by the formula; In formula (a3), a plurality of R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; R ⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms . The wiring member according to item 13 of the scope of patent application, wherein the content of the polymer including the structural unit (m2) is 10% by mass or more of the total mass of components other than the solvent in the photosensitive film forming composition. And 90% by mass or less.