Wiring board, positive-type photosensitive resin composition for forming a light-shielding layer, light-shielding layer transfer film, and method for manufacturing a wiring board

Abstract

Provided are a wiring base material having excellent design visibility, and a positive photosensitive resin composition for forming a light-blocking layer suitable for the wiring base material. The wiring base material has, on a transparent base material, a multilayer pattern of an opaque wiring electrode and a light-blocking layer containing a resin and a colored component. An average value R1 of internal diffuse reflectance at a wavelength of 540-570 nm measured from the light-blocking layer side of a multilayer pattern forming portion is 0.03-0.11%.

Description

[Technical Field]

[0001] The present invention relates to a wiring substrate, a positive-type photosensitive resin composition for forming a light-shielding layer, a light-shielding layer transfer film, and a method for manufacturing a wiring substrate. [Background technology]

[0002] Touch panels, which have become widely used as input devices in recent years, consist of a display unit such as a liquid crystal panel and a touch panel sensor that detects information input at a specific location. Transparent wiring electrodes have generally been used in touch panel sensors to make them less visible, but in recent years, opaque wiring electrodes made of metal materials have become widespread due to increased sensitivity and larger screen sizes. Opaque wiring electrodes made of metal materials have the problem of being easily visible due to their metallic luster. As a method to make opaque wiring electrodes less visible, a wiring board has been proposed having a transparent substrate, opaque wiring electrodes patterned on at least one side of the transparent substrate, and a transparent protective layer formed on the transparent substrate and the opaque wiring electrodes, wherein the internal reflectance R1 of the opaque wiring electrode formation portion measured from the transparent protective layer side of the wiring board is 0.1% or less, and the refractive index n1 of the transparent substrate and the refractive index n2 of the transparent protective layer satisfy a specific relationship, in particular a wiring board having a light-shielding layer on top of the opaque wiring electrodes (see, for example, Patent Document 1). Furthermore, as positive-type photosensitive compositions used in light-shielding layers, photosensitive resin compositions containing a pigment, a novolac resin, an acrylic resin having a carboxyl group, a photoacid generator, and an amine-based dispersant (see, for example, Patent Document 2), and positive-type photosensitive resin compositions containing an alkali-soluble resin (A) having an acrylic group and / or a methacrylic group in its side chain, a photosensitive agent (B), and a colorant (C) (see, for example, Patent Document 3) have been proposed. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International Publication No. 2022 / 130803 [Patent Document 2] Japanese Patent Publication No. 2021-139971 [Patent Document 3] International Publication No. 2021 / 149410 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] While the light-shielding layers disclosed in Patent Documents 1 to 3 can suppress the visibility of opaque wiring electrodes due to their metallic luster, ambient light is easily reflected, especially in bright locations such as automotive applications. Due to light scattering on the surface of the wiring substrate, the laminated pattern area tends to appear whiter and cloudier compared to the non-laminated or decorated areas. In applications where jet black is required from an aesthetic standpoint, there is a need to suppress this white cloudiness, i.e., to improve the visibility of the design.

[0005] Therefore, the present invention aims to provide a wiring substrate with excellent design visibility and a positive-type photosensitive resin composition suitable for forming a light-shielding layer. [Means for solving the problem]

[0006] To solve the above problems, the present invention mainly has the following configuration. <1> A wiring substrate having a laminated pattern of opaque wiring electrodes and a light-shielding layer containing resin and coloring components on a transparent substrate, wherein the average value R1 of the internal diffuse reflectance at wavelengths of 540 to 570 nm, measured from the light-shielding layer side of the laminated pattern formation portion, is 0.03 to 0.11%. <2> The following equation (1) satisfies the relationship between the following conditions: the average value R1[%] of the internal diffuse reflectance at wavelengths of 540-570 nm measured from the light-shielding layer side of the laminated pattern formation area, the average value R2[%] of the internal diffuse reflectance at wavelengths of 540-570 nm in the non-laminated pattern area, the line width W[μm] of the laminated pattern, and the ratio S of the laminated pattern area to the area of ​​the laminated pattern formation area (laminated pattern area / area of ​​the laminated pattern formation area). <1> Wiring substrate as described above. 0.0≦((R1×W)-(R2×(1-S))) / S≦7.0 (1) <3> The thickness T1 [μm] of the light-shielding layer is 0.2 to 2.0. <1> or <2> Wiring substrate as described above. <4> A positive-type photosensitive resin composition for forming a light-shielding layer, comprising (a) an alkali-soluble resin, (b) a quinone diazide compound, (c) metal nitride particles, and (d) a purple organic pigment. <5> The above (c) contains 2.0 to 6.0 volume percent of metal nitride particles. <4> A positive-type photosensitive resin composition for forming a light-shielding layer as described above. <6> Furthermore, (e) contains a red organic pigment <4> or <5> A positive-type photosensitive resin composition for forming a light-shielding layer as described above. <7> (c) Metal nitride particles, (d) purple organic pigment, and (e) red organic pigment have a total content of 5-15% by volume. <6> A positive-type photosensitive resin composition for forming a light-shielding layer as described above. <8> On the release film, <4> ~ <7> A light-shielding layer transfer film having a light-shielding layer formed from a positive-type photosensitive resin composition for light-shielding layer formation described in any of the above. <9> The thickness T1' [μm] of the light-shielding layer is 0.3 to 2.0. <8> The light-shielding layer transfer film described above. <10> A process of forming opaque wiring electrodes on a transparent substrate, On the opaque wiring electrode forming surface <4> ~ <7> A step of applying a positive-type photosensitive resin composition for forming a light-shielding layer as described in any of the above, and Using the opaque wiring electrode as a mask, the photosensitive resin composition coating film is exposed to light from the side opposite to the coating surface and developed to pattern-process the photosensitive resin composition coating film and form a laminated pattern of the opaque wiring electrode and the light-shielding layer. has <1> ~ <3> A method for manufacturing a wiring substrate as described in any of the following. <11> A process of forming opaque wiring electrodes on a transparent substrate, On the opaque wiring electrode forming surface <8> or <9> The process of transferring the light-shielding layer of the light-shielding layer transfer film described above, and Using the opaque wiring electrode as a mask, the light-shielding layer is exposed to light from the side opposite to the transfer surface and developed to pattern the light-shielding layer and form a laminated pattern of the opaque wiring electrode and the light-shielding layer. has <1> ~ <3> A method for manufacturing a wiring substrate as described in any of the following. [Effects of the Invention]

[0007] The wiring substrate of the present invention has excellent design visibility. According to the positive-type photosensitive resin composition for forming a light-shielding layer of the present invention, a wiring substrate with excellent design visibility can be obtained. [Brief explanation of the drawing]

[0008] [Figure 1] This is a schematic diagram showing an example of the configuration of the wiring substrate of the present invention. [Figure 2] This is a schematic diagram showing another example of the configuration of the wiring substrate of the present invention. [Figure 3] This is a schematic diagram showing an example of the configuration of a substrate for evaluating internal diffuse reflectance in the present invention. [Figure 4] This is a schematic diagram showing the electrode patterns used for visibility evaluation in the examples and comparative examples. [Figure 5] This is a schematic diagram of the mesh pattern of the negative-type mask used in the examples and comparative examples. [Modes for carrying out the invention]

[0009] First, as the first aspect of the present invention, the wiring substrate will be described. The wiring substrate of the present invention has an opaque wiring electrode on a transparent substrate and has a light-shielding layer at a portion corresponding to the opaque wiring electrode. That is, it has a laminated pattern of the opaque wiring electrode and the light-shielding layer. The light-shielding layer may be provided on the opaque wiring electrode, or the opaque wiring electrode may be provided on the light-shielding layer. The light-shielding layer has the effect of suppressing light reflection and light scattering of the opaque wiring electrode to reproduce highly artistic pitch-black and improving design visibility. Further, a transparent protective layer may be provided thereon, and by having the transparent protective layer, the surface of the opaque wiring electrode and the light-shielding layer can be protected, and scratches and the like can be suppressed. Here, "transparent" means that the light transmittance at a wavelength of 550 nm is 50% or more, and "opaque" means that the light transmittance at a wavelength of 550 nm is less than 50%. The light transmittance at a wavelength of 550 nm can be measured using an ultraviolet-visible spectrophotometer (U-3310: manufactured by Hitachi High-Technologies Corporation).

[0010] FIG. 1 shows a schematic diagram of an example of the configuration of the wiring substrate of the present invention. The wiring substrate 4 has an opaque wiring electrode 2 on a transparent substrate 1 and has a light-shielding layer 3 on the opaque wiring electrode 2. FIG. 2 shows another example of the configuration of the wiring substrate of the present invention. The wiring substrate 4 has a light-shielding layer 3 on a transparent substrate 1 and has an opaque wiring electrode 2 on the light-shielding layer 3.

[0011] The wiring substrate of the present invention has a laminated pattern of opaque wiring electrodes and a light-shielding layer containing resin and coloring components. In the present invention, the average value R1 of the internal diffuse reflectance at wavelengths of 540 to 570 nm, measured from the light-shielding layer side of the laminated pattern forming portion, is 0.03 to 0.11%. Here, the laminated pattern forming portion refers to the region where the laminated pattern is formed, and includes not only the portion corresponding to the laminated pattern but also the non-laminated pattern portion located between adjacent laminated patterns with a distance of less than 1 mm. More specifically, for example, in the case of a stripe-shaped laminated pattern, the portion corresponding to the stripe-shaped laminated pattern with a pitch of less than 1 mm and the non-laminated pattern portion sandwiched between those laminated patterns are collectively considered the laminated pattern forming portion. Also, for example, in the case of a mesh-shaped laminated pattern as shown in Figure 5, the portion corresponding to the mesh-shaped laminated pattern with a mesh pitch of less than 1 mm (laminated pattern portion 12) and the non-laminated pattern portion surrounded by those laminated patterns (non-laminated pattern portion 13) are collectively considered the laminated pattern forming portion. On the other hand, non-laminated pattern portions where the distance between adjacent laminated patterns is 1 mm or more are considered non-laminated pattern portions. As mentioned above, while conventionally known light-shielding layers can suppress the visibility of opaque wiring electrodes due to their metallic luster, the laminated pattern formation area tended to appear cloudy and whitish due to light scattering on the wiring substrate surface, especially in bright locations. Our investigations revealed that while laminating a conventionally known light-shielding layer onto opaque wiring electrodes can lower the total reflectance (SCI) of the laminated pattern formation area, it resulted in a higher diffuse reflectance (SCE) compared to transparent wiring electrodes such as ITO. Therefore, we investigated the relationship between the design visibility issue due to light scattering on the wiring substrate surface and the diffuse reflectance, focusing on the diffuse reflectance in the wavelength range of 540-570 nm, where luminosity is high. The average value R1 of the internal diffuse reflectance in the wavelength range of 540-570 nm, measured from the light-shielding layer side of the laminated pattern formation area, is an indicator of the diffuse reflectance in the wavelength range where luminosity is high. By setting R1 to 0.03 or higher, the difference in diffuse reflectance between the laminated pattern formation area and the non-laminated area can suppress the visibility of the boundary between the laminated pattern formation area and the non-laminated area. R1 is preferably 0.04 or higher.On the one hand, by setting R1 to 0.11% or less, it is possible to suppress the clouding of the laminated pattern forming portion due to light scattering on the surface of the wiring substrate even in particularly bright places, reproduce a highly decorative deep black, and improve the design visibility.

[0012] Here, the internal diffuse reflectance corresponds to the diffuse reflectance obtained by removing the reflection caused by the refractive index difference at the interface between the surface of the wiring substrate and air. FIG. 3 shows a schematic diagram of an example of the configuration of a substrate for evaluating the internal diffuse reflectance for evaluating the internal diffuse reflectance of the wiring substrate. The wiring substrate 4 has a laminated pattern of an opaque wiring electrode 2 and a light shielding layer 3 on a transparent substrate 1, and further has a transparent protective layer 6. An antireflection film 8 is attached via an adhesive layer 7 to the light shielding layer forming surface of the wiring substrate (here, on the transparent protective layer 6), and a black film 9 is attached via an adhesive layer 7 to the surface of the transparent substrate 1 on the side opposite to the light shielding layer, to prepare a substrate 16 for evaluating the internal diffuse reflectance with reduced reflection at the interface between the wiring substrate and air. Although not shown, when the laminated pattern of the light shielding layer and the opaque wiring electrode on the transparent substrate has a light shielding layer on the transparent substrate side, an antireflection film is attached to the transparent substrate via a transparent adhesive layer, and a black film is attached to the transparent protective layer via an adhesive layer, to prepare a substrate for evaluating the internal diffuse reflectance with reduced reflection at the interface between the wiring substrate and air. Regarding the laminated pattern forming portion of the obtained substrate for evaluating the internal diffuse reflectance, from the side of the antireflection film 8 in the case of the configuration shown in FIG. 3, i.e., the light shielding layer forming side, the diffuse reflectances at wavelengths of 540, 550, 560, and 570 nm are measured respectively using a colorimetric system or the like, and the average value of the internal diffuse reflectance R1 can be calculated by obtaining the average value thereof.

[0013] The diffuse reflectance is affected by the reflectance of the material forming the light-shielding layer itself, as well as the line width, area, and uneven shape of the light-shielding layer. For example, if the area of ​​the light-shielding layer is the same, a narrower line width W results in the wiring substrate surface being closer to the diffusion surface, and the internal diffuse reflectance tends to be higher due to the uneven shape of the light-shielding layer. Methods for setting R1 to 0.03-0.11% include, for example, the ratio of the laminated pattern area to the area of ​​the laminated pattern formation area (laminated pattern area / area of ​​the laminated pattern formation area, hereinafter referred to as "occupancy rate") S, methods for setting the line width W of the laminated pattern and the thickness T1 of the light-shielding layer to a preferred range described later, and methods for forming the light-shielding layer using the positive-type photosensitive resin composition for light-shielding layer formation of the present invention, described later. Among these, the method of forming the light-shielding layer using the positive-type photosensitive resin composition for light-shielding layer formation of the present invention, described later, is preferred because it has fewer constraints on the wiring pattern.

[0014] In the present invention, it is preferable that the average value R1[%] of the internal diffuse reflectance, the average value R2[%] of the internal diffuse reflectance at wavelengths of 540-570 nm in the non-layered pattern area, and the occupancy rate S satisfy the relationship given by the following formula (1). 0.0≦((R1×W)-(R2×(1-S))) / S≦7.0 (1) In the laminated pattern formation area, the reflection and scattering of the wiring surface in the area ratio S region (laminated pattern area) and the reflection and scattering of the non-wiring surface in the area ratio (1-S) region (non-laminated pattern area) affect the diffuse reflectance. Furthermore, as mentioned above, the diffuse reflectance is affected by the area and uneven shape of the light-shielding layer. In equation (1) above, (R1 × W) is an index of the diffuse reflectance in the laminated pattern formation area, excluding the effect of line width. On the other hand, in the non-laminated pattern area, the reflection and scattering of the non-wiring surface in the area ratio (1-S) region affects the diffuse reflectance. The average value R2 of the internal diffuse reflectance at wavelengths of 540-570 nm in the non-laminated pattern area is an index of the diffuse reflectance in the wavelength region with high luminous sensitivity, and (R2 × (1-S)) in equation (1) above is an index of the diffuse reflectance of the non-wiring surface in the laminated pattern formation area. Then, we focused on the diffuse reflectance of the wiring surface per unit area, obtained by dividing these differences (i.e., the diffuse reflectance of the wiring surface in the laminated pattern formation area) by the area ratio S. When these satisfy the relationship in equation (1) above, the constraints on the wiring pattern are reduced and the design visibility can be further improved. Here, the average value R2 of the internal diffuse reflectance at wavelengths of 540 to 570 nm in the area where the laminated pattern is not formed can be calculated for the area where the laminated pattern is not formed in the same way as R1 above. The value of ((R1 × W) - (R2 × (1 - S))) / S (hereinafter sometimes referred to as "diffuse reflectance per unit area") is more preferably 6.0 or less. As a method that satisfies the above equation (1), for example, there is a method of forming a light-shielding layer using the positive-type photosensitive resin composition for light-shielding layer formation of the present invention, which will be described later.

[0015] The opaque wiring electrode preferably has a light transmittance of 25% or less at a wavelength of 550 nm. Furthermore, it is preferable that it has light-shielding properties against the exposure light used in the method for forming the light-shielding layer described later. Specifically, the light transmittance at a wavelength of 365 nm is preferably 15% or less. By setting the light transmittance at 365 nm to 15% or less, the mask function in the method for forming the light-shielding layer described later is improved, and the desired light-shielding layer can be formed with better processability. The light transmittance of the opaque wiring electrode can be measured for a square opaque wiring electrode with a side length of 0.1 mm or more using a micro-surface spectrophotometer (VSS 400: manufactured by Nippon Denshoku Industries Ltd.).

[0016] Examples of materials that make up opaque wiring electrodes include conductive materials such as metals like silver, gold, copper, platinum, lead, tin, nickel, aluminum, tungsten, molybdenum, chromium, titanium, and indium, as well as alloys thereof. Two or more of these may be used. Among these, silver and copper are preferred from the viewpoint of conductivity.

[0017] The raw material used to form opaque wiring electrodes is preferably conductive particles containing the aforementioned conductive substance, and the shape is preferably spherical. The average particle size of the conductive particles is preferably 0.03 μm or larger from the viewpoint of improving the dispersibility of the conductive particles. On the other hand, the average particle size of the conductive particles is preferably 1.0 μm or smaller from the viewpoint of sharpening the edges of the pattern of the opaque wiring electrodes. The average particle size of the conductive particles can be determined by observing the conductive particles at a magnification of 15,000 times using a scanning electron microscope (SEM) or transmission microscope (TEM), measuring the long axis length of 100 randomly selected conductive particles, and calculating the number average value.

[0018] The opaque wiring electrode may contain organic components along with the conductive material described above. The opaque wiring electrode may be formed from a cured product of a photosensitive conductive composition containing, for example, conductive particles, an alkali-soluble resin, and a photopolymerization initiator, in which case the opaque wiring electrode contains the photopolymerization initiator and / or its photodegraded products. The photosensitive conductive composition may optionally contain additives such as thermosetting agents and leveling agents.

[0019] Examples of pattern shapes for opaque wiring electrodes include mesh and stripe patterns. Examples of mesh patterns include grids where the unit shape is a triangle, square, polygon, or circle, or a grid consisting of a combination of these unit shapes. Among these, a mesh pattern is preferred from the viewpoint of making the conductivity of the pattern uniform. Opaque wiring electrodes are more preferably made of the aforementioned metal and have a mesh pattern. When opaque wiring electrodes have a mesh pattern, the occupancy rate S can be reduced by increasing the mesh pitch.

[0020] The thickness T2 [μm] of the opaque wiring electrode is preferably 0.1 or greater, and more preferably 0.3 or greater, from the viewpoint of improving conductivity. On the other hand, the thickness T2 [μm] of the opaque wiring electrode is preferably 10 or less, more preferably 5.0 or less, and even more preferably 3.0 or less, from the viewpoint of forming finer wiring. Furthermore, when the wiring substrate has a transparent protective layer, setting the thickness T2 [μm] of the opaque wiring electrode to 10 or less reduces unevenness and steps on the transparent substrate, thereby suppressing the generation of air bubbles caused by steps when the transparent protective layer is laminated. Note that T2 can be measured using a stylus-type step meter.

[0021] From the viewpoint of improving conductivity, the line width of the opaque wiring electrode pattern is preferably 1 μm or more, more preferably 1.5 μm or more, and even more preferably 2 μm or more. On the other hand, when the pattern shape is the same, the line width of the opaque wiring electrode pattern is preferably 10 μm or less, and more preferably 8 μm or less, from the viewpoint of further reducing the value of the internal diffuse reflectance R1 and further improving the design visibility. Here, the line width of the opaque wiring electrode pattern can be determined by using an optical microscope to magnify and observe the laminated pattern formation area, measuring the line width of the opaque wiring electrode at three randomly selected locations, and calculating the average value.

[0022] The wiring substrate of the present invention has a light-shielding layer containing a resin and a coloring component.

[0023] As the resin, an alkali-soluble resin is preferred. Here, examples of alkali-soluble resins include resins having hydroxyl groups and / or carboxyl groups. Among these, resins having phenolic hydroxyl groups are preferred. Examples of resins having phenolic hydroxyl groups include novolac resins such as phenol novolac resins and cresol novolac resins, polymers of monomers having phenolic hydroxyl groups, and copolymers of monomers having phenolic hydroxyl groups with styrene, acrylonitrile, acrylic monomers, etc. Two or more of these may be included.

[0024] Examples of coloring components include pigments such as inorganic pigments and organic pigments, as well as dyes. Pigments are preferred because they have excellent weather resistance.

[0025] Organic pigments include soluble azo pigments, insoluble azo pigments, metal complex azo pigments, phthalocyanine pigments, condensed polycyclic pigments, black organic pigments such as CI Pigment Black 31 and 32, purple organic pigments such as CI Pigment Violet 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, and 50, red organic pigments such as CI Pigment Red 9, 48, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 190, 192, 196, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254, 255, 264, and 265, and CI Pigment Blue 15, 15:1, and 1 Blue organic pigments such as 5:2, 15:3, 15:4, 15:6, 16, 17, 60, 64, 65, 75, 79, 80, CI Pigment Yellow 12, 13, 17, 20, 24, 74, 83, 86, 93, 95, 109, 110, 117, 120, 125, 129, 138, 139, 150, 151, 175, 180, 181 Examples include yellow organic pigments such as 185, 192, 194, and 199; green organic pigments such as CI Pigment Green 7, 36, and 37; and orange organic pigments such as CI Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, and 73.

[0026] Examples of inorganic pigments include carbon black, graphite, metal nitride particles such as titanium nitride and zirconium nitride, pine soot, or iron oxides such as iron black, hematite, goethite, and magnetite, as well as chromium, lead, and metal composites thereof. Among these, metal nitride particles are preferred due to their high transmittance of exposure light.

[0027] From the viewpoint of setting the average value R1 of the internal diffuse reflectance within the aforementioned range, the coloring component preferably absorbs light at wavelengths of 540 to 570 nm. Examples of coloring components that absorb light at wavelengths of 540 to 570 nm include metal nitride particles, red organic pigments, purple organic pigments, and blue organic pigments. Two or more of these may be included. Among these, when a high-pressure mercury lamp is used as the exposure light source during the formation of the light-shielding layer, metal nitride particles, red organic pigments, purple organic pigments, and blue organic pigments are preferred, and when an LED lamp (365 nm) is used, metal nitride particles, red organic pigments, and purple organic pigments are preferred. It is more preferable to include metal nitride particles and purple organic pigments, as this can further improve visibility after the formation of the light-shielding layer while maintaining photosensitivity when an LED lamp (365 nm) is used as the light source during the formation of the light-shielding layer.

[0028] The coloring component more preferably includes a red organic pigment. By including a red organic pigment, it is possible to maintain photosensitivity when using an LED lamp (365 nm) as a light source during the formation of the light-shielding layer, while further improving visibility after the formation of the light-shielding layer.

[0029] The thickness T1 [μm] of the light-shielding layer is preferably 0.2 to 2.0. By setting T1 [μm] to 0.2 or more, the increase in internal diffuse reflectance due to surface irregularities of the opaque wiring electrodes can be further suppressed, and R1 can be easily adjusted within the aforementioned range. On the other hand, by setting T1 [μm] to 2.0 or less, the unevenness and steps on the transparent substrate can be reduced, and the generation of air bubbles caused by steps can be suppressed when laminating the transparent protective layer. Note that T1 can be measured using a stylus-type step meter.

[0030] The line width of the light-shielding layer is preferably equal to the line width of the opaque wiring electrode mentioned above. Therefore, the line width W [μm] of the laminated pattern is preferably 1 or more, more preferably 1.5 or more, and even more preferably 2 or more, from the viewpoint of improving conductivity. On the other hand, when the pattern shape is the same, the line width W [μm] of the laminated pattern is preferably 10 or less, and more preferably 8 or less, from the viewpoint of further reducing the value of the internal diffuse reflectance R1 and further improving the visibility of the design. Here, the line width W of the laminated pattern can be determined by using an optical microscope to magnify and observe the laminated pattern formation area, measuring the line width of the laminated pattern at three randomly selected locations, and calculating the average value.

[0031] Next, a method for manufacturing the wiring substrate of the present invention will be described. As a method for manufacturing the wiring substrate of the present invention, for example, if the laminated pattern having an opaque wiring electrode and a light-shielding layer in that order on a transparent substrate is preferable, it is preferable to have a step of forming an opaque wiring electrode on the transparent substrate (hereinafter sometimes referred to as the "opaque wiring electrode formation step") and a step of forming a laminated pattern by forming a light-shielding layer containing a resin and a coloring component on the opaque wiring electrode formation surface (hereinafter sometimes referred to as the "laminated pattern formation step").

[0032] In the opaque wiring electrode formation process, methods for forming opaque wiring electrodes include, for example, a method of forming a pattern by photolithography using the aforementioned photosensitive conductive composition; a method of forming a pattern by screen printing, gravure printing, inkjet, etc., using a conductive composition; and a method of forming a film of metal, metal composite, composite of metal and metal compound, metal alloy, etc., and then forming it by photolithography using a resist. When the pattern formed from the photosensitive conductive composition exhibits conductivity upon heat curing, it is preferable to heat cure it at 140 to 500°C.

[0033] In the lamination pattern formation process, the process for forming the light-shielding layer includes, for example, a method of patterning the coating film of the positive-type photosensitive resin composition for forming the light-shielding layer, which is a second embodiment of the present invention described later, by applying it to an opaque wiring electrode, and then, using the opaque wiring electrode as a mask, exposing the coating film of the positive-type photosensitive resin composition for forming the light-shielding layer from the side opposite to the coating surface and developing it; or a method of patterning the light-shielding layer by transferring the light-shielding layer to the opaque wiring electrode using a light-shielding layer transfer film of the present invention described later, and then, using the opaque wiring electrode as a mask, exposing the light-shielding layer from the side opposite to the transfer surface and developing it. Among these, the latter method using a light-shielding layer transfer film is preferred. By transferring a light-shielding layer that maintains its shape using a light-shielding layer transfer film, it is possible to suppress the increase in the required exposure amount and development time due to the thickening of the film thickness in the non-formed areas of the opaque wiring electrode caused by the leveling of the light-shielding layer during film formation. By patterning the light-shielding layer on the opaque wiring electrode using these methods, a laminated pattern can be formed.

[0034] Examples of exposure light sources include mercury lamps, halogen lamps, xenon lamps, LED lamps (365nm, 405nm), semiconductor lasers, and KrF or ArF excimer lasers. Among these, the i-line of mercury lamps (wavelength 365nm) and LED lamps (365nm, 405nm) are preferred, and LED lamps (365nm) are even more preferred due to their high output. The exposure light may be irradiated while the substrate is stationary, or it may be irradiated while the substrate is transported on the light source in a direction that irradiates the opposite side of the light-shielding layer formation surface.

[0035] The developer used for development is preferably one that does not hinder the conductivity of the electrode pattern, and an alkaline developer is preferred. Examples of alkaline developers include those exemplified as developers in International Publication No. 2018 / 168325. Examples of development methods include spraying the developer onto the surface of the resin layer while the substrate is standing or rotating, immersing the resin layer in the developer, and applying ultrasound while the resin layer is immersed in the developer.

[0036] The light-shielding layer pattern obtained by development may be rinsed with a rinsing solution. Examples of rinsing solutions include those exemplified in International Publication No. 2018 / 168325.

[0037] The resulting wiring substrate may be further heated to 100-300°C. Heating increases the hardness of the resin layer, suppresses chipping and peeling due to contact with other components, and further improves adhesion to the substrate and wiring. Examples of heating methods include heating with an oven, inert oven, hot plate, or electromagnetic wave heating such as an infrared heater.

[0038] Next, a second aspect of the present invention will be described, which is a positive-type photosensitive resin composition for forming a light-shielding layer. The positive-type photosensitive resin composition for forming a light-shielding layer of the present invention can be preferably used to form a light-shielding layer in the wiring substrate of the first aspect of the present invention described above, and by forming a light-shielding layer from such a positive-type photosensitive resin composition for forming a light-shielding layer, the average value R1 of the internal diffuse reflectance can be easily adjusted to the range described above.

[0039] The positive-type photosensitive resin composition for forming a light-shielding layer of the present invention comprises (a) an alkali-soluble resin, (b) a quinone diazide compound, (c) metal nitride particles, and (d) a purple organic pigment. Here, positive-type photosensitivity refers to the property that the light-irradiated area dissolves in the developer, while the unirradiated area does not dissolve in the developer.

[0040] (a) Examples of alkali-soluble resins include those used for the light-shielding layer in the wiring substrate of the first embodiment of the present invention. (a) Preferably, the alkali-soluble resin is a resin having phenolic hydroxyl groups, and the hydrogen bonding between the phenolic hydroxyl groups and (b) the quinone diazide compound further suppresses the reduction of the developed film in unexposed areas and the occurrence of peeling off the developed film, making the opaque wiring electrode pattern less visible. Examples of resins having phenolic hydroxyl groups include those used for the light-shielding layer in the wiring substrate of the first embodiment of the present invention. The content of (a) alkali-soluble resin in the solid content of the positive-type photosensitive resin composition for forming the light-shielding layer is preferably 45 to 65% by mass.

[0041] (b) Examples of quinone diazide compounds include those exemplified in International Publication No. 2018 / 168325 as quinone diazide compounds included in positive-type photosensitive compositions. The content of the quinone diazide compound in the solid content of the positive-type photosensitive resin composition is preferably 5 to 25% by mass.

[0042] The positive-type photosensitive resin composition for forming a light-shielding layer of the present invention contains (c) metal nitride particles and (d) a purple organic pigment that absorb light in the wavelength region of 540 to 570 nm, which has high visual sensitivity, and also absorb visible light in the wavelength region of 570 to 640 nm. This allows for improved design visibility after the formation of the light-shielding layer while maintaining photosensitivity when an LED lamp (365 nm) is used as the light source during light-shielding layer formation. Examples of (c) metal nitride particles and (d) purple organic pigment include those described in the description of the light-shielding layer in the wiring substrate of the first embodiment of the present invention.

[0043] The content of (c) metal nitride particles in the solid content of the positive-type photosensitive resin composition for forming a light-shielding layer is preferably 2.0 volume% or more, and more preferably 2.5 volume% or more, from the viewpoint of further improving the visibility of the design. On the other hand, the content of metal nitride particles is preferably 6.0 volume% or less, and more preferably 5.0 volume% or less, from the viewpoint of photosensitivity.

[0044] The content of (d) purple organic pigment in the solid content of the positive-type photosensitive resin composition for forming a light-shielding layer is preferably 1.0 volume% or more from the viewpoint of further improving the visibility of the design. On the other hand, the content of (d) purple organic pigment is preferably 8.0 volume% or less from the viewpoint of photosensitivity.

[0045] The positive-type photosensitive resin composition for forming a light-shielding layer of the present invention preferably further contains (e) a red organic pigment. Since the (e) red organic pigment absorbs light in the wavelength range of 460 to 540 nm and visible light in the wavelength range of 570 to 640 nm, it is possible to further improve the design visibility of the light-shielding layer while maintaining photosensitivity when an LED lamp (365 nm) is used as the light source during the formation of the light-shielding layer.

[0046] When the positive-type photosensitive resin composition for forming a light-shielding layer of the present invention contains (e) a red organic pigment, the total content of (c) metal nitride particles, (d) purple organic pigment, and (e) red organic pigment in the solid content of the positive-type photosensitive resin composition is preferably 5.0 volume% or more from the viewpoint of bringing the diffuse reflectance per unit area to the aforementioned preferred range and further improving visibility. On the other hand, from the viewpoint of photosensitivity, the total content of these is preferably 15.0 volume% or less.

[0047] The positive-type photosensitive resin composition for forming a light-shielding layer of the present invention may optionally contain monomers having unsaturated double bonds, photopolymerization initiators, photoacid generators, thermoacid generators, sensitizers, adhesion improvers, surfactants, thermosetting agents, polymerization inhibitors, rust inhibitors, softeners, leveling agents, and the like.

[0048] The positive-type photosensitive resin composition for forming a light-shielding layer of the present invention can be obtained by mixing, for example, (a) an alkali-soluble resin, (b) a quinone diazide compound, (c) metal nitride particles, (d) a purple organic pigment, and other additives as needed, and then dispersing the mixture using a disperser or kneader. Examples of dispersers and kneaders include jet mills, bead mills, ball mills, and planetary ball mills.

[0049] The positive-type photosensitive resin composition for forming a light-shielding layer of the present invention can be preferably used in the light-shielding layer transfer film of the present invention, and such light-shielding layer transfer film can be preferably used for forming a light-shielding layer in the wiring substrate of the first embodiment of the present invention described above.

[0050] The light-shielding layer transfer film of the present invention has a light-shielding layer formed on a release film from the positive-type photosensitive resin composition for forming a light-shielding layer according to the second embodiment of the present invention described above.

[0051] The release film is preferably a film having a release layer on its surface.

[0052] Examples of release agents for forming the release layer include non-silicone release agents and silicone release agents. Examples of non-silicone release agents include long-chain alkyl and fluorine-based release agents. Two or more of these may be used. Among these, non-silicone release agents are preferred because, even if release agent transfer occurs during transfer, they are less likely to cause phenomena such as developer repelling in the subsequent process, especially the development process, and can suppress in-plane unevenness and form fine patterns. From the viewpoint of suppressing transfer unevenness during transfer, the thickness of the release layer is preferably 50 nm or more. On the other hand, from the viewpoint of suppressing release agent transfer during transfer, the thickness of the release layer is preferably 500 nm or less.

[0053] The release force of the release film is preferably 500 mN / 20 mm or more from the viewpoint of suppressing repulsion during the formation of the light-shielding layer. On the other hand, the release force of the release film is preferably 5,000 mN / 20 mm or less from the viewpoint of widening the process margin during the transfer of the light-shielding layer. Here, the release force of the release film refers to the release force obtained when Nitto Denko Corporation's acrylic adhesive tape "31B" is applied to the release layer formation surface using a 2 kg roller, left to stand for 30 minutes, and then peeled off under the conditions of a peeling angle of 180° and a peeling speed of 0.3 m / min.

[0054] Examples of films used as release films include films containing resins such as polyethylene terephthalate (PET), cycloolefin polymer, polycarbonate, polyimide, aramid, fluororesin, acrylic resin, and polyurethane resin. Two or more of these may be used. Among these, films that are transparent to the exposure light used in the aforementioned laminated pattern formation process are preferred, and films containing PET, cycloolefin polymer, and polycarbonate are preferred. By selecting a film that is transparent to the exposure light, exposure can be performed through the release film in the aforementioned laminated pattern formation process, and contamination of the photomask can be suppressed by interposing the release film between the light-shielding layer and the photomask.

[0055] The thickness of the release film is preferably 5 μm or more, and more preferably 10 μm or more, from the viewpoint of improving transport stability during the formation of the light-shielding layer and suppressing thickness unevenness of the light-shielding layer. On the other hand, from the viewpoint of handling during peeling, the thickness of the release film is preferably 300 μm or less, and more preferably 200 μm or less.

[0056] The thickness T1' [μm] of the light-shielding layer in the light-shielding layer transfer film is preferably 0.3 or greater, and more preferably 0.5 or greater, from the viewpoint of making opaque wiring electrodes less visible. On the other hand, the thickness T1' [μm] of the light-shielding layer is preferably 2.0 or less from the viewpoint of reducing development time and further improving processability. T1' can be measured using a stylus-type step meter. Furthermore, when the thickness T1' of the light-shielding layer is transferred to form a light-shielding layer on the wiring substrate, it corresponds to the thickness T1, but it may change depending on the method of forming the light-shielding layer.

[0057] The light-shielding layer transfer film of the present invention can be obtained, for example, by applying a positive-type photosensitive resin composition for light-shielding layer formation onto a release film.

[0058] Methods for applying a positive-type photosensitive resin composition for forming a light-shielding layer onto a release film include, for example, rotational coating using a spinner, spray coating, roll coating, screen printing, or coating using a slit coater, blade coater, die coater, calender coater, meniscus coater, or bar coater. The coating thickness of the positive-type photosensitive resin composition for forming a light-shielding layer is preferably set so that the thickness T1 of the light-shielding layer falls within the aforementioned preferred range.

[0059] If the positive-type photosensitive resin composition for forming the light-shielding layer contains a solvent, it is preferable to heat-dry it. The drying temperature is preferably 60 to 120°C, and the drying time is preferably 1 to 20 minutes. Suitable heating and drying equipment includes, for example, an oven or a hot plate. [Examples]

[0060] The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. The materials used in each example are as follows.

[0061] [(a) Alkali-soluble resins] • Phenolic novolac resin WR-104 (manufactured by DIC Corporation).

[0062] [(b) Quinone diazide compounds] (Manufacturing Example 1: Quinone diazide compound) Under a stream of dry nitrogen, 21.22 g (0.05 mol) of α,α,-bis(4-hydroxyphenyl)-4-(4-hydroxy-α,α-dimethyldimethylbenzylethylbenzene (trade name TrisP-PA, manufactured by Honshu Chemical Industry Co., Ltd.) and 33.58 g (0.125 mol) of 5-naphthoquinone diazidosulfonylic acid chloride were dissolved in 450 g of 1,4-dioxane and allowed to rise to room temperature. To this, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise, ensuring that the temperature in the system did not exceed 35°C. After addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was added to water. The precipitated material was then collected by filtration. This precipitate was dried in a vacuum dryer to obtain the quinone diazide compound.

[0063] [Coloring ingredients] (c) Metal nitride particles: Titanium nitride particles (particle size 17 nm) • (d) Purple organic pigment: Pigment Violet 23 (particle size 50 nm) • (e) Red organic pigment: Pigment Red 254 (particle size 100 nm) • Blue organic pigment: Pigment Blue 15:6 (particle size 100nm) • Carbon black: MA100 (manufactured by Mitsubishi Chemical Corporation).

[0064] [others] (Manufacturing example 2: Acrylic resin containing carboxyl groups) 150 g of diethylene glycol monoethyl ether acetate (hereinafter, "DMEA") was charged into a reaction vessel under a nitrogen atmosphere, and the temperature was raised to 80°C using an oil bath. A mixture consisting of 20 g of ethyl acrylate (hereinafter, "EA"), 40 g of 2-ethylhexyl methacrylate (hereinafter, "2-EHMA"), 20 g of styrene (hereinafter, "St"), 15 g of acrylic acid (hereinafter, "AA"), 0.8 g of 2,2'-azobisisobutyronitrile, and 10 g of DMEA was added dropwise over 1 hour. After the addition was complete, the mixture was stirred for a further 6 hours to carry out the polymerization reaction. Subsequently, 1 g of hydroquinone monomethyl ether was added to stop the polymerization reaction. Subsequently, a mixture consisting of 5 g of glycidyl methacrylate (hereinafter, "GMA"), 1 g of triethylbenzylammonium chloride, and 10 g of DMEA was added dropwise over 0.5 hours. After the dropwise addition was complete, the mixture was stirred for a further 2 hours to carry out the addition reaction. The resulting reaction solution was purified with methanol to remove unreacted impurities, and then vacuum-dried for 24 hours to obtain an acrylic resin having carboxyl groups with a copolymerization ratio (by mass): EA / 2-EHMA / St / GMA / AA = 20 / 40 / 20 / 5 / 15. The acid value of the obtained acrylic resin having carboxyl groups was measured according to JIS K 0070 (1992) and was found to be 103 mg KOH / g. The weight-average molecular weight of the obtained acrylic resin having carboxyl groups was 17,000.

[0065] (Manufacturing Example 3: Acrylic resin having phenolic hydroxyl groups and carboxyl groups) 150 g of 2-methoxy-1-methylethyl acetate (hereinafter referred to as "PMA") was charged into a reaction vessel under a nitrogen atmosphere, and the temperature was raised to 80°C using an oil bath. A mixture consisting of 20 g of EA, 20 g of 2-EHMA, 20 g of 4-hydroxystyrene (hereinafter referred to as "HS"), 15 g of N-methylolacrylamide (hereinafter referred to as "MAA"), 25 g of AA, 0.8 g of 2,2'-azobisisobutyronitrile, and 10 g of PMA was added dropwise over 1 hour. After the addition was complete, the mixture was heated and stirred at 80°C for 6 hours to carry out the polymerization reaction. Subsequently, 1 g of hydroquinone monomethyl ether was added to stop the polymerization reaction. The resulting reaction solution was purified with methanol to remove unreacted impurities, and then vacuum-dried for 24 hours to obtain an acrylic resin having phenolic hydroxyl and carboxyl groups with a copolymerization ratio (by mass): EA / 2-EHMA / HS / MAA / AA = 20 / 20 / 20 / 15 / 25. The acid value was measured in the same manner as in Production Example 2 and was found to be 153 mg KOH / g. The weight-average molecular weight of the obtained acrylic resin having phenolic hydroxyl and carboxyl groups was 10,000.

[0066] (Manufacturing Example 4: Photosensitive conductive paste) In a 100 mL clean bottle, 3.0 g of carboxyl-containing acrylic resin obtained according to Production Example 2, 0.3 g of photopolymerization initiator N-1919 (manufactured by ADEK Corporation), 1.2 g of monomer "Light Acrylate" (registered trademark) BP-4EA, 0.5 g of dispersant "BYK" (registered trademark)-LP21116 (manufactured by BYK Chemie Co., Ltd.), and 79.0 g of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA"), and 16.0 g of silver nanoparticles with an average surface carbon coating layer thickness of 1 nm and a particle size of 40 nm (manufactured by Nisshin Engineering Co., Ltd.) were placed and mixed using "Awatori Rentaro" (registered trademark) ARE-310 (manufactured by Thinky Co., Ltd.) to obtain 100.0 g of photosensitive conductive paste. The viscosity of the obtained photosensitive conductive paste was measured using an E-type viscometer under conditions of a temperature of 25 °C and a rotation speed of 100 rpm, and was found to be 3 mPa·s.

[0067] (Manufacturing example 5: Photosensitive insulating paste) In a 100 mL clean bottle, 15.5 g of carboxyl-containing acrylic resin obtained according to Production Example 2, 5.2 g of "Light Acrylate®" BP-4EAL, 0.3 g of photopolymerization initiator N-1919, and 79.0 g of PGMEA were placed and mixed using a rotation-orbit vacuum mixer "Awatori Rentaro®" ARE-310 to obtain 100.0 g of photosensitive insulating paste. The obtained photosensitive insulating paste was applied to a 4-inch silicone wafer, and the refractive index at a wavelength of 550 nm was measured at room temperature of 23°C using a prism coupler (Metricon, PC-2000), and the result was 1.53.

[0068] The evaluations for each example and comparative example were performed using the following method.

[0069] (1) Line width W of the layered pattern For each example and comparative example, the substrates after the formation of the laminated pattern were observed under magnification using an optical microscope. The line width of the laminated pattern was measured at three randomly selected locations, and the average value was defined as the line width W of the laminated pattern.

[0070] (2) Internal diffuse reflectance An anti-reflective film MTAR-3 with an adhesive layer (manufactured by Mikan Imaging Co., Ltd.) was attached to the transparent protective layer-forming surface of the wiring substrate obtained in each example and comparative example using a rubber roller. Furthermore, an adhesive black PET film Kukkiri Mieru (manufactured by Tomoegawa Paper Co., Ltd.) was attached to the non-laminated surface of the wiring substrate using a rubber roller to prepare the substrate 16 for internal diffuse reflectance evaluation shown in Figure 3. The diffuse reflectance SCE at wavelengths of 540, 550, 560, and 570 nm of the laminated pattern-forming area of ​​the substrate for internal diffuse reflectance evaluation was measured using a spectrophotometer (CM-2500d) manufactured by Konica Minolta Sensing, Inc., and the average value was taken as the average value R1 of the internal reflectance. Next, the diffuse reflectance SCE was measured at wavelengths of 540, 550, 560, and 570 nm in the unlayered patterned areas of the substrate used for evaluating the internal diffuse reflectance, using a Konica Minolta Sensing, Inc. spectrophotometer (CM-2500d). The average value of these measurements was defined as the average internal reflectance R2.

[0071] (3) Difficulty in being seen For each example and comparative example, a black sheet SuperBlackIR (manufactured by Systems Engineering Co., Ltd.) was placed on the side opposite to the opaque wiring electrode formation surface of the wiring substrate. Then, light was projected onto the opaque wiring electrode formation surface using a floodlight. Ten people each visually inspected the substrate from a distance of 30 cm, and the degree of visibility was evaluated based on the number of people who could see the mesh-like opaque wiring electrodes.

[0072] (4) Design visibility In each example and comparative example, (2) light was projected onto the anti-reflective film-attached surface of the substrate prepared for internal diffuse reflectance evaluation using a floodlight. Ten people observed the substrate from a distance of 100 cm, and the design visibility was evaluated based on the number of people who could clearly see the boundary between the laminated pattern-forming portion 10 and the non-laminated pattern-forming portion 11.

[0073] (5) Photosensitivity In each example and comparative example, the exposure apparatus in the <formation of the light-shielding layer> was replaced with a 365nm LED lamp (manufactured by CCS Corporation), and the exposure was 500mJ / cm². 2 800 mJ / cm² 2 , 1500 mJ / cm 2 3000 mJ / cm² 2 Exposure was performed at each exposure level, and the minimum exposure level at which the exposed area dissolved in the developer within 30 seconds was defined as the required exposure level to evaluate photosensitivity. Note: 3000 mJ / cm² 2 If it did not dissolve within 30 seconds, it was evaluated as <3000.

[0074] (Example 1) <Opaque wiring electrode formation process> A photosensitive conductive paste (D-1) obtained in Manufacturing Example 4 was applied to one side of alkali-free glass "AN Wizus®" (manufactured by AGC Inc., transmittance at 365 nm: 91%, transmittance at 550 nm: 92%) by spin coating to a thickness of 1 μm after drying, and dried at 90°C for 8 minutes. Using an exposure mask having a mesh-shaped layered pattern forming area 10 and a non-layered pattern forming area 11 as shown in Figure 4, an exposure apparatus (PEM-6M; manufactured by Union Optical Co., Ltd.) was used with an exposure dose of 150 mJ / cm². 2 Exposure was performed at a wavelength of 365 nm. The mesh pattern is a negative type pattern with a mesh pitch 14 of 400 μm and a mesh angle 15 of 58°, and an aperture width of 4 μm, consisting of a stacked pattern section (mask opening) 12 and a non-stacked pattern section (mask light-shielding section) 13. Note that in Figure 5, the colors are inverted for illustrative purposes. Subsequently, development was performed using a 0.1 mass% tetramethylammonium hydroxide aqueous solution as the developer for twice the time it took for the exposed area to dissolve. After rinsing with ultrapure water for 30 seconds, the material was heated and cured in a box oven at 220°C for 60 minutes to form an opaque wiring electrode. The thickness of the opaque wiring electrode was measured using a stylus-type step meter "Surfcom (registered trademark)" 1400 (manufactured by Tokyo Seimitsu Co., Ltd.) and was found to be 0.5 μm.

[0075] <Layer pattern formation process> (Preparation of positive-type photosensitive resin composition for light-shielding layer formation) In a 100 mL clean bottle, (a) 2.89 g of Fernovolac resin WR-104 (manufactured by DIC Corporation) as an alkali-soluble resin, (b) 0.49 g of the quinone diazide compound obtained in Production Example 1, 0.22 g of carboxybenzotriazole "VERZONE®" C-BTA (manufactured by Yamato Kasei Co., Ltd.), 0.01 g of leveling agent "BYK®"-331 (manufactured by Bic Chemie Co., Ltd.), and 44.45 g of PGMEA were added and mixed using a rotation-revolution vacuum mixer "Awatori Rentaro®" ARE-310 (manufactured by Thinky Co., Ltd.) to obtain 48.07 g of resin solution. The obtained 48.07 g of resin solution, 1.21 g of carbon black MA100 (manufactured by Mitsubishi Chemical Corporation), and 0.72 g of dispersant "BYK"-LP21116 (manufactured by Bic Chemie) were mixed and kneaded using an Ultra Apex Mill (manufactured by Kotobuki Kogyo Co., Ltd.) equipped with a centrifugation separator filled with 0.10 mmφ zirconia beads (manufactured by Toray Industries, Inc.) at a rate of 70 volume%, to obtain 50.0 g of positive-type photosensitive resin composition 1 for light-shielding layer formation.

[0076] (Formation of a light-shielding layer) In the <Opaque Wiring Electrode Formation Process>, the obtained positive-type photosensitive resin composition 1 for light-shielding layer formation was spin-coated onto the opaque wiring electrode surface to a thickness of 1.4 μm after drying, and dried at 100°C for 10 minutes. Subsequently, using the opaque wiring electrode as a mask, an exposure apparatus (PEM-6M) was used to expose the surface of the opaque wiring electrode formation surface from the opposite side, with an exposure dose (calculated at a wavelength of 365 nm) of 10,000 mJ / cm². 2 The material was exposed under the specified conditions, and developed using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide as the developer until the transparent substrate in the exposed area was exposed. A light-shielding layer pattern was formed on the opaque wiring electrode, creating a laminated pattern. Furthermore, it was heated in a box oven at 220°C for 60 minutes.

[0077] <Transparent protective layer formation process> On the laminated pattern substrate obtained in the <Laminated Pattern Formation Process>, the photosensitive insulating paste obtained in (Manufacturing Example 5) was spin-coated to a film thickness of 3.0 μm after drying, and dried at 80°C for 5 minutes. Using an exposure apparatus (PEM-6M), an exposure dose (calculated at a wavelength of 365 nm) of 100 mJ / cm was applied from the coated surface. 2 The substrate was exposed to light under the specified conditions and developed for 60 seconds using a 0.1% by mass aqueous solution of tetramethylammonium hydroxide as the developer. Furthermore, it was heated in a box oven at 220°C for 60 minutes to obtain a wiring substrate with a transparent protective layer formed on it.

[0078] (Example 2) A wiring substrate was obtained in the same manner as in Example 1, except that the mesh pitch and occupancy rate S of the exposure mask in the <Opaque Wiring Electrode Formation Process> and the composition in (Preparation of the positive-type photosensitive resin composition for light-shielding layer formation) were changed as shown in Table 1.

[0079] (Examples 3-9) A wiring substrate was obtained in the same manner as in Example 2, except that the composition in (Preparation of positive-type photosensitive resin composition for light-shielding layer formation) and the exposure amount in (Formation of light-shielding layer) were changed as shown in Tables 1 and 2.

[0080] (Comparative Example 1) A wiring substrate was obtained in the same manner as in Example 3, except that (formation of a light-shielding layer) was not performed.

[0081] (Comparative Examples 2-6) A wiring substrate was obtained in the same manner as in Example 2, except that the composition in (Preparation of positive-type photosensitive resin composition for light-shielding layer formation) and the exposure amount in (Formation of light-shielding layer) were changed as shown in Table 3.

[0082] (Example 10) <Formation of opaque wiring electrodes> A substrate with opaque wiring electrodes was obtained in the same manner as in (Example 2).

[0083] <Layer pattern formation process> (Preparation of positive-type photosensitive resin composition for light-shielding layer formation) In a 100 mL clean bottle, 0.77 g of phenol novolac resin WR-104 (manufactured by DIC Corporation), 2.33 g of acrylic resin having phenolic hydroxyl and carboxyl groups obtained in Production Example 2, 0.77 g of quinone diazide compound obtained in Production Example 1, 0.19 g of carboxybenzotriazole "VERZONE®" C-BTA (manufactured by Yamato Kasei Co., Ltd.), 0.01 g of leveling agent "BYK®"-331 (manufactured by Bic Chemie Co., Ltd.), and 44.28 g of PGMEA were placed and mixed using a rotation-revolution vacuum mixer "Awatori Rentaro®" ARE-310 (manufactured by Thinky Co., Ltd.) to obtain 48.77 g of resin solution. The obtained 48.77 g of resin solution, 0.79 g of titanium nitride particles, 0.32 g of purple organic pigment, 0.11 g of red organic pigment, and 0.50 g of dispersant "BYK(registered trademark)"-LP21116 (manufactured by Bic Chemie) were mixed together and kneaded using an Ultra Apex Mill (manufactured by Kotobuki Kogyo Co., Ltd.) equipped with a centrifugal separator filled with 70 volume% of 0.10 mmφ zirconia beads (manufactured by Toray Industries, Inc.) to obtain 50.0 g of positive-type photosensitive resin composition 2 for light-shielding layer formation.

[0084] (Preparation of light-shielding transfer film) A non-silicone release agent AL-5 (Lintec Corporation) was applied to one side of a PET film "Lumirror®" FB40 (manufactured by Toray Industries, Inc.) (thickness: 16 μm), and then heat-treated and dried to form a 100 nm thick release layer on the substrate surface, thereby obtaining a release film. For the obtained release film, Nitto Denko Corporation's acrylic adhesive tape "31B" was applied to the release layer-formed surface using a 2 kg roller, and after standing for 30 minutes, the peeling force was measured when peeled at a peeling angle of 180° and a peeling speed of 0.3 m / min, and the result was 1,480 mN / 20 mm.

[0085] The obtained release layer surface of the release film was coated with the obtained positive-type photosensitive resin composition 2 for light-shielding layer formation using a coater so that the thickness T1' after drying was 1.4 μm, and the film was dried at 80°C for 4 minutes to form a light-shielding layer and obtain a light-shielding layer transfer film.

[0086] (Formation of light-shielding layer) On the opaque wiring electrode formed in the <Opaque wiring electrode forming step>, the light-shielding layer of the light-shielding layer transfer film obtained by <Production of light-shielding layer transfer film> was thermocompression-bonded at a speed of 80 °C and 0.1 m / min so that they were in contact with each other, and the release film was peeled off. Then, using the exposure apparatus (PEM-6M) with the opaque wiring electrode as a mask, from the opposite side of the surface on which the opaque wiring electrode was formed, the exposure amount (converted to a wavelength of 365 nm) was 100 mJ / cm 2 . The substrate was exposed under the conditions of, and developed using an aqueous sodium carbonate solution of 1.00 mass% as a developer until the transparent substrate of the exposed portion was exposed, to form a light-shielding layer pattern on the opaque wiring electrode and form a laminated pattern. Further, it was heated in a box oven at 220 °C for 60 minutes.

[0087] (Formation of transparent protective layer) A transparent protective layer was formed in the same manner as in (Example 1) to obtain a wiring substrate.

[0088] The main configurations and evaluation results of each example and comparative example are shown in Tables 1 to 4.

[0089] [Table 1]

[0090] [Table 2]

[0091] [Table 3]

[0092] [Table 4] [Explanation of reference numerals]

[0093] 1: Transparent substrate 2: Opaque wiring electrode 3: Light blocking layer 4: Wiring base material 5: Lamination Pattern 6:Transparent protective layer 7: Adhesive layer 8: Anti-reflective film 9: Black film 10: Lamination pattern forming section 11: Area where the laminated pattern is not formed 12: Lamination pattern section (mask opening) 13: Non-layered pattern section (mask light-shielding section) 14: Mesh pitch 15: Mesh angle 16: Substrate for evaluating internal diffuse reflectance

Claims

1. A wiring substrate having a laminated pattern of opaque wiring electrodes and a light-shielding layer containing resin and coloring components on a transparent substrate, wherein the average value R1 of the internal diffuse reflectance at wavelengths of 540 to 570 nm, measured from the light-shielding layer side of the laminated pattern formation portion, is 0.03 to 0.11%. A wiring substrate that satisfies the following relationship (1): the average value R1 [%] of the internal diffuse reflectance, the average value R2 [%] of the internal diffuse reflectance at wavelengths of 540 to 570 nm in the non-layered pattern area, the line width W [μm] of the layered pattern, and the ratio of the layered pattern area to the area of ​​the layered pattern formation area (layered pattern area / area of ​​the layered pattern formation area) S. 0.0≦((R1×W)-(R2×(1-S))) / S≦7.0 (1)

2. The wiring substrate according to claim 1, wherein the thickness T1 [μm] of the light-shielding layer is 0.2 to 2.

0.

3. (a) an alkali-soluble resin, (b) a quinone diazide compound, (c) metal nitride particles, and (d) a purple organic pigment. (c) A positive-type photosensitive resin composition for forming a light-shielding layer, wherein the content of metal nitride particles is 2.0 to 6.0 volume percent.

4. Furthermore, (e) the positive-type photosensitive resin composition for forming a light-shielding layer according to claim 3, which also contains a red organic pigment.

5. The positive-type photosensitive resin composition for forming a light-shielding layer according to claim 4, wherein the total content of (c) metal nitride particles, (d) purple organic pigment, and (e) red organic pigment is 5.0 to 15.0% by volume.

6. A light-shielding layer transfer film having a light-shielding layer formed on a release film from the positive-type photosensitive resin composition for light-shielding layer formation described in claim 3.

7. The light-shielding layer transfer film according to claim 6, wherein the thickness T1' [μm] of the light-shielding layer is 0.3 to 2.

0.

8. A method for manufacturing a wiring substrate according to claim 1, A process of forming opaque wiring electrodes on a transparent substrate, The steps include applying the light-shielding layer-forming positive-type photosensitive resin composition described in claim 3 to the opaque wiring electrode forming surface, and Using the opaque wiring electrode as a mask, the photosensitive resin composition coating film is exposed to light from the side opposite to the coating surface and developed to pattern-process the photosensitive resin composition coating film and form a laminated pattern of the opaque wiring electrode and the light-shielding layer. A method for manufacturing a wiring substrate having

9. A method for manufacturing a wiring substrate according to claim 1, A process of forming opaque wiring electrodes on a transparent substrate, A step of transferring the light-shielding layer of the light-shielding layer transfer film described in claim 6 to the opaque wiring electrode forming surface, and Using the opaque wiring electrode as a mask, the light-shielding layer is exposed to light from the side opposite to the transfer surface and developed to pattern the light-shielding layer and form a laminated pattern of the opaque wiring electrode and the light-shielding layer. A method for manufacturing a wiring substrate having

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