Wiring substrate, positive photosensitive resin composition for forming light shielding layer, light shielding layer transfer film, and method for producing wiring substrate

Abstract

The present invention provides a wiring substrate having excellent design visibility, and a positive photosensitive resin composition for forming a light-shielding layer suitable for the wiring substrate. And a wiring substrate having, on a transparent substrate, a laminated pattern of an opaque wiring electrode and a light shielding layer containing a resin and a coloring component, the wiring substrate having an average value (R1) of internal diffuse reflectance at a wavelength of 540-570 nm as measured from the light shielding layer side of a laminated pattern forming portion of 0.03-0.11%.

Description

Technical Field

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

[0002] In recent years, the touch panel widely used as an input means is composed of a display unit such as a liquid crystal panel and a touch panel sensor for detecting information input to a specific position. As the wiring electrode used in the touch panel sensor, a transparent wiring electrode is usually used from the viewpoint that the wiring electrode is not easy to see, but in recent years, due to high sensitivity and large screens, opaque wiring electrodes using metal materials are becoming popular. There is a problem that the opaque wiring electrode using metal materials is easily visually recognized due to the metallic luster. As a method for making the opaque wiring electrode difficult to be visually recognized, the following wiring substrate (for example, see patent document 1) is proposed, which has a transparent substrate, an opaque wiring electrode patterned on at least one side of the aforementioned transparent substrate, and a transparent protective layer formed on the aforementioned transparent substrate and the aforementioned opaque wiring electrode, the internal reflectivity R1 of the aforementioned opaque wiring electrode forming portion measured from the aforementioned transparent protective layer side of the wiring substrate is less than 0.1%, the refractive index n1 of the aforementioned transparent substrate and the refractive index n2 of the aforementioned transparent protective layer satisfy a specific relationship, and in particular, a wiring substrate having a light shielding layer on the upper part of the opaque wiring electrode is proposed. In addition, as positive photosensitive compositions used in the light-shielding layer, there have been proposed: a photosensitive resin composition comprising a pigment, a Novolac resin, an acrylic resin having a carboxyl group, a photoacid generator, and an amine dispersant (for example, see Patent Document 2); and a positive photosensitive resin composition comprising an alkali-soluble resin (A) having an acrylic group and / or a methacrylic group in a side chain, a photosensitive agent (B), and a colorant (C) (for example, see Patent Document 3).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: International Publication No. 2022 / 130803

[0006] Patent Document 2: Japanese Patent Application Publication No. 2021-139971

[0007] Patent Document 3: International Publication No. 2021 / 149410 Summary of the invention

[0008] Problems to be solved by the invention

[0009] With the light-shielding layers disclosed in Patent Documents 1 to 3, it is possible to suppress the visual recognition ease caused by the metallic luster of the opaque wiring electrodes. However, especially in bright places such as in-vehicle applications, external light is likely to be reflected, and due to the light scattering on the surface of the wiring substrate, the portion where the laminated pattern is formed tends to look whitish and blurred compared to the portion where the laminated pattern is not formed and the decorative portion. In applications where a pitch-black appearance is required from a design perspective, it is necessary to suppress such whitening (Japanese: 白曇り), that is, to improve the design visual recognition.

[0010] Accordingly, an object of the present invention is to provide a wiring substrate with excellent design visual recognition and a positive photosensitive resin composition for forming a light-shielding layer suitable for use therewith.

[0011] Means for Solving the Problem

[0012] To solve the above problems, the present invention mainly has the following configurations.

[0013] <1> A wiring substrate having a laminated pattern of an opaque wiring electrode and a light-shielding layer containing a resin and a coloring component on a transparent substrate, wherein the average value R1 of the internal diffuse reflectance at a wavelength of 540 to 570 nm measured from the light-shielding layer side of the laminated pattern forming portion of the wiring substrate is 0.03 to 0.11%.

[0014] <2> The wiring substrate according to <1>, wherein the average value R1 [%] of the internal diffuse reflectance at a wavelength of 540 to 570 nm measured from the light-shielding layer side of the laminated pattern forming portion, the average value R2 [%] of the internal diffuse reflectance at a wavelength of 540 to 570 nm of the portion where the laminated pattern is not formed, the line width W [μm] of the laminated pattern, and the ratio (laminated pattern area / area of the laminated pattern forming portion) S of the laminated pattern area to the area of the laminated pattern forming portion satisfy the relationship of the following formula (1).

[0015] 0.0 ≤ ((R1 × W) - (R2 × (1 - S))) / S ≤ 7.0 (1)

[0016] <3> The wiring substrate according to <1> or <2>, wherein the thickness T1 [μm] of the light-shielding layer is 0.2 to 2.0.

[0017] <4> A positive photosensitive resin composition for forming a light-shielding layer, which contains (a) an alkali-soluble resin, (b) a quinonediazide compound, (c) metal nitride particles, and (d) a purple organic pigment.

[0018] <5> The positive photosensitive resin composition for forming a light-shielding layer according to <4>, wherein the content of the metal nitride particles (c) is 2.0 to 6.0% by volume.

[0019] <6> like <4> or <5> The positive photosensitive resin composition for forming a light-shielding layer further contains (e) a red organic pigment.

[0020] <7> like <6> In the positive photosensitive resin composition for forming a light-shielding layer, the total content of (c) metal nitride particles, (d) violet organic pigment and (e) red organic pigment is 5 to 15% by volume.

[0021] <8> A light shielding layer transfer film having a light shielding layer on a release film <4> ~ <7> A light-shielding layer formed from the positive photosensitive resin composition for light-shielding layer formation described in any one of the preceding claims.

[0022] <9> like <8> The light-shielding layer transfer film, wherein the thickness T1' [μm] of the light-shielding layer is 0.3-2.0.

[0023] <10> <1> ~ <3> The method for manufacturing a wiring substrate according to any one of the preceding claims, comprising:

[0024] The process of forming an opaque wiring electrode on a transparent substrate;

[0025] On the surface where the opaque wiring electrode is formed, a <4> ~ <7> A step of preparing a positive photosensitive resin composition for forming a light-shielding layer as described in any one of the preceding claims; and

[0026] The photosensitive resin composition coating film is exposed and developed from the surface opposite to the coating surface using the opaque wiring electrode as a mask, thereby patterning the photosensitive resin composition coating film to form a stacked pattern of the opaque wiring electrode and the light shielding layer.

[0027] <11> <1> ~ <3> The method for manufacturing a wiring substrate according to any one of the preceding claims, comprising:

[0028] The process of forming an opaque wiring electrode on a transparent substrate;

[0029] Will <8> or <9> A step of transferring the light-shielding layer of the light-shielding layer transfer film to the aforementioned opaque wiring electrode forming surface; and

[0030] The step of exposing and developing the light shielding layer from the surface opposite to the transfer surface using the opaque wiring electrode as a mask, thereby patterning the light shielding layer to form a stacked pattern of the opaque wiring electrode and the light shielding layer.

[0031] Effects of the Invention

[0032] The wiring substrate of the present invention is excellent in design visibility. According to the positive photosensitive resin composition for forming a light-shielding layer of the present invention, a wiring substrate excellent in design visibility can be obtained. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] [ Figure 1 ] is a schematic diagram showing an example of the structure of the wiring substrate of the present invention.

[0034] [ Figure 2 ] is a schematic diagram showing another example of the structure of the wiring substrate of the present invention.

[0035] [ Figure 3 ] is a schematic diagram showing an example of the structure of the substrate for evaluating the internal diffuse reflectance in the present invention.

[0036] [ Figure 4 ] is a schematic diagram showing the electrode pattern for visual recognition evaluation used in the embodiments and comparative examples.

[0037] [ Figure 5 ] is a schematic diagram of the grid pattern of the negative mask used in the embodiments and comparative examples. DETAILED DESCRIPTION

[0038] First, as a first embodiment of the present invention, a wiring substrate is 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 position corresponding to the opaque wiring electrode. That is, it has a stacked pattern of an opaque wiring electrode and a light shielding layer. A light shielding layer may be provided on the opaque wiring electrode, or an opaque wiring electrode may be provided on the light shielding layer. The light shielding layer has the following functions: suppressing light reflection and light scattering of the opaque wiring electrode, reproducing the jet black with high design, and improving the visual recognition of the design. In addition, a transparent protective layer may be provided on them, and by having a transparent protective layer, the surface of the opaque wiring electrode and the light shielding layer can be protected, and damage can be suppressed. Here, the so-called "transparent" means that the transmittance at a wavelength of 550nm is more than 50%, and "opaque" means that the transmittance at a wavelength of 550nm is less than 50%. It should be noted that the transmittance at a wavelength of 550nm can be measured using an ultraviolet visible spectrophotometer (U-3310: manufactured by Hitachi High-Technologies Corporation).

[0039] Figure 1 A schematic diagram showing an example of the structure of the wiring substrate of the present invention. The wiring substrate 4 has an opaque wiring electrode 2 on a transparent substrate 1 and a light shielding layer 3 on the opaque wiring electrode 2 . Figure 2 Another example of the structure of the wiring substrate of the present invention is shown. 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 .

[0040] The wiring substrate of the present invention has a stacked pattern of an opaque wiring electrode and a light-shielding layer containing a resin and a coloring component. Furthermore, in the present invention, the average value R1 of the internal diffuse reflectance at a wavelength of 540 to 570 nm measured from the light-shielding layer side of the stacked pattern forming portion is 0.03 to 0.11%. Here, the so-called stacked pattern forming portion refers to an area where a stacked pattern is formed, and in addition to a portion corresponding to the stacked pattern, it also includes a non-stacked pattern portion located between adjacent stacked patterns with a distance of less than 1 mm. More specifically, for example, in the case of a stacked pattern having a strip shape, a portion corresponding to the stacked pattern having a strip shape with a spacing of less than 1 mm and a non-stacked pattern portion sandwiched between these stacked patterns are collectively referred to as a stacked pattern forming portion. In addition, for example, in a case having Figure 5 In the case of the grid-shaped stacked pattern shown, the portion corresponding to the grid-shaped stacked pattern with a grid spacing less than 1 mm (stacked pattern portion 12) and the non-stacked pattern portion surrounded by these stacked patterns (non-stacked pattern portion 13) are collectively regarded as the stacked pattern forming portion. On the other hand, the non-stacked pattern portion whose distance between adjacent stacked patterns is more than 1 mm is regarded as the stacked pattern non-forming portion. As mentioned above, although the visual recognition ease caused by the metallic luster of the opaque wiring electrode can be suppressed by the previously known shading layer, there is a tendency for the stacked pattern forming portion to look whitish and blurred due to the light scattering on the surface of the wiring substrate, especially in bright places. According to the research of the inventors of the present application, by stacking the previously known shading layer on the opaque wiring electrode, although the total reflectivity (SCI) of the stacked pattern forming portion can be reduced, the diffuse reflectivity (SCE) is higher than that of transparent wiring electrodes such as ITO. Therefore, the inventors of the present application have studied the relationship between the design visual recognition problem caused by light scattering on the surface of the wiring substrate and the diffuse reflectance, focusing on the diffuse reflectance in the region of wavelengths of 540 to 570 nm with high visual perception. The average value R1 of the internal diffuse reflectance at a wavelength of 540 to 570 nm measured from the light shielding layer side of the stacked pattern forming part is an indicator of the diffuse reflectance in the wavelength region with high visual perception. By making R1 greater than 0.03, it is possible to suppress the visual recognition of the boundary between the stacked pattern forming part and the stacked pattern non-forming part due to the difference in diffuse reflectance between the stacked pattern forming part and the stacked pattern non-forming part. R1 is preferably greater than 0.04. On the other hand, by making R1 less than 0.11%, the white fogging of the stacked pattern forming part caused by light scattering on the surface of the wiring substrate can be suppressed, especially even in bright places, and the high-design black is reproduced, thereby improving the design visual recognition.

[0041] Here, the internal diffuse reflectance is equivalent to the diffuse reflectance after removing the reflection caused by the refractive index difference at the interface between the wiring base material surface and the air. Figure 3A schematic diagram showing an example of the construction of a substrate for evaluating the internal diffuse reflectance of a wiring substrate is shown. The wiring substrate 4 has a stacked pattern of an opaque wiring electrode 2 and a light-shielding layer 3 on a transparent substrate 1, and also has a transparent protective layer 6. An anti-reflection film 8 is adhered to the light-shielding layer forming surface of the wiring substrate (here, on the transparent protective layer 6) via an adhesive layer 7, and a black film 9 is adhered to the surface of the transparent substrate 1 on the side opposite to the light-shielding layer via an adhesive layer 7, thereby preparing a substrate 16 for evaluating the internal diffuse reflectance that reduces reflection at the interface between the wiring substrate and the air. It should be noted that, although not shown in the figure, when the wiring substrate is a stacked pattern of a light-shielding layer and an opaque wiring electrode on a transparent substrate and has a light-shielding layer on the transparent substrate side, an anti-reflection film is adhered to the transparent substrate via a transparent adhesive layer, and a black film is adhered to the transparent protective layer via an adhesive layer, thereby preparing a substrate for evaluating the internal diffuse reflectance that reduces reflection at the interface between the wiring substrate and the air. For the obtained stacked pattern forming portion of the substrate for evaluating the internal diffuse reflectance, from the light-shielding layer forming side, that is, on the Figure 3 In the case of the illustrated configuration, the diffuse reflectance at wavelengths of 540, 550, 560, and 570 nm is measured on the antireflection film 8 side using a colorimetric system or the like, and the average value thereof is obtained, thereby being able to calculate the average value R1 of the internal diffuse reflectance.

[0042] The diffuse reflectance is affected by the reflectance of the material forming the light-shielding layer itself, the line width, area, and concavo-convex shape of the light-shielding layer. For example, when the area of ​​the light-shielding layer is the same, the thinner the line width W, the closer the surface of the wiring substrate becomes to the state of the diffusion surface, and there is a tendency for the internal diffuse reflectance to become higher due to the concavo-convex shape of the light-shielding layer. As a method for making R1 0.03 to 0.11%, for example, there can be cited a method in which the ratio of the stacking pattern area to the area of ​​the stacking pattern forming part (stacked pattern area / stacked pattern forming part area, hereinafter referred to as "occupancy") S, the line width W of the stacking pattern, and the thickness T1 of the light-shielding layer are within the preferred range described later, and a method of forming a light-shielding layer by a positive photosensitive resin composition for forming a light-shielding layer of the present invention described later. Among them, from the aspect of less restrictions on the wiring pattern, a method of forming a light-shielding layer by a positive photosensitive resin composition for forming a light-shielding layer of the present invention described later is preferred.

[0043] In the wiring substrate of the present invention, the average internal diffuse reflectance R1 [%], the average internal diffuse reflectance R2 [%] of the non-stacked pattern forming portion at a wavelength of 540 to 570 nm, and the occupancy rate S preferably satisfy the relationship of the following formula (1).

[0044] 0.0≤((R1×W)-(R2×(1-S))) / S≤7.0 (1)

[0045] In the stacked pattern forming part, the reflection and scattering of the wiring surface in the area of ​​the area ratio S (stacked pattern part), and the reflection and scattering of the non-wiring surface in the area of ​​the area ratio (1-S) (non-stacked pattern part) affect the diffuse reflectance. In addition, as mentioned above, the diffuse reflectance is affected by the area of ​​the light shielding layer, the concave-convex shape, etc. The (R1×W) in the above formula (1) is an index of the diffuse reflection in the stacked pattern forming part after excluding the influence of the line width. On the other hand, in the non-stacked pattern part, the reflection and scattering of the non-wiring surface in the area of ​​the area ratio (1-S) affect the diffuse reflectance. The average value R2 of the internal diffuse reflectance of the non-stacked pattern forming part at a wavelength of 540 to 570nm is an index of the diffuse reflectance in the wavelength region with high visual perception, and the (R2×(1-S)) in the above formula (1) is an index of the diffuse reflection of the non-wiring surface in the stacked pattern forming part. Then, we focus on the diffuse reflection of the wiring surface per unit area obtained by dividing their difference (i.e., the diffuse reflection of the wiring surface in the stacked pattern forming portion) by the area ratio S. By making them satisfy the relationship of the above-mentioned formula (1), there are fewer restrictions on the wiring pattern, and the visual recognition of the design can be further improved. Here, with respect to the average value R2 of the internal diffuse reflectance of the stacked pattern non-forming portion at a wavelength of 540 to 570 nm, it can be calculated in the same way as the aforementioned R1 for the stacked pattern non-forming portion. The value of ((R1×W)-(R2×(1-S))) / S (hereinafter, sometimes described as "diffuse reflection per unit area") is more preferably less than 6.0. As a method satisfying the above-mentioned formula (1), for example, a method of forming a light-shielding layer using a positive photosensitive resin composition for forming a light-shielding layer of the present invention described later can be cited.

[0046] The light transmittance of the opaque wiring electrode at a wavelength of 550nm is preferably 25% or less. In addition, it is preferred to have light-shielding properties for the exposure light used in the method for forming a light-shielding layer described later. Specifically, the light transmittance at a wavelength of 365nm is preferably 15% or less. By making the light transmittance at a wavelength of 365nm less than 15%, the function as a mask in the method for forming a light-shielding layer described later is improved, and the desired light-shielding layer can be formed with better processability. It should be noted that the light transmittance of the opaque wiring electrode can be measured using a micro-surface spectrophotometer (VSS 400: manufactured by Nippon Denshoku Industries, Ltd.) for a square opaque wiring electrode with a side length of 0.1mm or more.

[0047] As materials constituting the opaque wiring electrodes, for example, conductive materials such as metals such as silver, gold, copper, platinum, lead, tin, nickel, aluminum, tungsten, molybdenum, chromium, titanium, and indium, and alloys thereof can be cited. Two or more of these can be used. Among them, silver, copper, and the like are preferably used from the viewpoint of conductivity.

[0048] As a raw material used in the formation of the opaque wiring electrode, conductive particles containing the aforementioned conductive material are preferably spherical in shape. From the viewpoint of improving the dispersibility of the conductive particles, the average particle size of the conductive particles is preferably 0.03 μm or more. On the other hand, from the viewpoint of making the end of the pattern of the opaque wiring electrode sharp, the average particle size of the conductive particles is preferably 1.0 μm or less. It should be noted that the average particle size of the conductive particles can be obtained by the following method: using a scanning electron microscope (SEM) or a transmission microscope (TEM), the conductive particles are magnified and observed at a magnification of 15,000 times, and for 100 randomly selected conductive particles, the length of each major axis is measured, and the number average is calculated.

[0049] The opaque wiring electrode may contain the aforementioned conductive material and an organic component. The opaque wiring electrode may be formed, for example, from a cured product of a photosensitive conductive composition containing conductive particles, an alkali-soluble resin, and a photopolymerization initiator. In this case, the opaque wiring electrode contains a photopolymerization initiator and / or a photodegradable product thereof. The photosensitive conductive composition may contain additives such as a thermosetting agent and a leveling agent as required.

[0050] As the pattern shape of the opaque wiring electrode, for example, a grid shape, a strip shape, etc. can be cited. As the grid shape, for example, a grid shape in which the unit shape is a triangle, a quadrilateral, a polygon, a circle, etc., or a grid shape formed by a combination of these unit shapes can be cited. Among them, from the viewpoint of making the conductivity of the pattern uniform, a grid shape is preferred. The opaque wiring electrode is more preferably a metal grid composed of the aforementioned metal and having a grid pattern. In the case where the opaque wiring electrode has a grid pattern, the occupancy rate S can be reduced by increasing the grid spacing.

[0051] From the viewpoint of improving conductivity, the thickness T2 [μm] of the opaque wiring electrode is preferably greater than 0.1, and more preferably greater than 0.3. On the other hand, from the viewpoint of forming finer wiring, the thickness T2 [μm] of the opaque wiring electrode is preferably less than 10, more preferably less than 5.0, and further preferably less than 3.0. In addition, in the case where the wiring substrate has a transparent protective layer, by making the thickness T2 [μm] of the opaque wiring electrode less than 10, the uneven step difference on the transparent substrate can be reduced, and the generation of bubbles caused by the step difference when the transparent protective layer is stacked can be suppressed. It should be noted that T2 can be measured using a stylus step difference meter.

[0052] From the viewpoint of improving conductivity, the line width of the pattern of the opaque wiring electrode is preferably 1 μm or more, more preferably 1.5 μm or more, and further preferably 2 μm or more. On the other hand, when the line width of the pattern of the opaque wiring electrode is the same pattern shape, from the viewpoint of further reducing the value of the internal diffuse reflectance R1 and further improving the visual recognition of the design, it is preferably 10 μm or less, and more preferably 8 μm or less. Here, the line width of the pattern of the opaque wiring electrode can be obtained by using an optical microscope to magnify and observe the stacked pattern forming portion, and measure the line width of the opaque wiring electrode at three randomly selected locations, and calculate the average value.

[0053] The wiring substrate of the present invention has a light-shielding layer containing a resin and a coloring component.

[0054] As the resin, an alkali-soluble resin is preferably used. Here, as the alkali-soluble resin, for example, a resin having a hydroxyl group and / or a carboxyl group can be cited. Among them, a resin having a phenolic hydroxyl group is preferably used. As the resin having a phenolic hydroxyl group, for example, Novolac resins such as phenol Novolac resin and cresol Novolac resin, polymers of monomers having a phenolic hydroxyl group, copolymers of monomers having a phenolic hydroxyl group and styrene, acrylonitrile, acrylic acid monomers, etc. can be cited. Two or more of these can be contained.

[0055] Examples of the coloring component include pigments such as inorganic pigments and organic pigments, and dyes. From the viewpoint of excellent weather resistance, pigments are preferred.

[0056] Examples of the organic pigment include soluble azo pigments, insoluble azo pigments, metal complex salt azo pigments, phthalocyanine pigments, condensed polycyclic pigments, black organic pigments such as CI Pigment Black 31 and 32, violet 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, 15:2. :2, 15:3, 15:4, 15:6, 16, 17, 60, 64, 65, 75, 79, 80 and other blue organic pigments, 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, 185, 192, 194, 199 and other yellow organic pigments, CI Pigment Green 7, 36, 37 and other green organic pigments, CI Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, 73 and other orange organic pigments, etc.

[0057] 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, chromium, lead, and metal composites thereof. Among these, metal nitride particles are preferred because of their high transmittance to exposure light.

[0058] From the viewpoint of making the average value R1 of the internal diffuse reflectance within the aforementioned range, the coloring component preferably absorbs light at a wavelength of 540 to 570 nm. As coloring components that absorb light at a wavelength of 540 to 570 nm, for example, metal nitride particles, red organic pigments, purple organic pigments, blue organic pigments, etc. can be cited. Two or more of them can be contained. Among them, when a high-pressure mercury lamp is used as an exposure light source when the light-shielding layer is formed, metal nitride particles, red organic pigments, purple organic pigments, and blue organic pigments are preferred. When an LED lamp (365 nm) is used, metal nitride particles, red organic pigments, and purple organic pigments are preferred. It is more preferred to include metal nitride particles and purple organic pigments, which can maintain the photosensitivity when an LED lamp (365 nm) is used as a light source when forming the light-shielding layer, and further improve the visual recognition after the light-shielding layer is formed.

[0059] The coloring component more preferably further includes a red organic pigment. By including a red organic pigment, the photosensitivity when an LED lamp (365 nm) is used as a light source when forming the light-shielding layer can be maintained, and the visibility after the light-shielding layer is formed can be further improved.

[0060] The thickness T1 [μm] of the light-shielding layer is preferably 0.2 to 2.0. By making T1 [μm] greater than 0.2, the increase in internal diffuse reflectance caused by the surface unevenness of the opaque wiring electrode can be further suppressed, and R1 can be more easily adjusted to the aforementioned range. On the other hand, by making T1 [μm] less than 2.0, the unevenness step difference on the transparent substrate can be reduced, and the generation of bubbles caused by the step difference when the transparent protective layer is stacked can be suppressed. It should be noted that T1 can be measured using a stylus step meter.

[0061] The line width of the shading layer is preferably equal to the line width of the aforementioned opaque wiring electrode. Therefore, from the viewpoint of improving conductivity, the line width W [μm] of the stacked pattern is preferably greater than 1, more preferably greater than 1.5, and further preferably greater than 2. On the other hand, with respect to the line width W [μm] of the stacked pattern, in the case of the same pattern shape, from the viewpoint of further reducing the value of the internal diffuse reflectance R1 and further improving the visual recognizability of the design, it is preferably less than 10, more preferably less than 8. Here, the line width W of the stacked pattern can be obtained by using an optical microscope to enlarge and observe the stacked pattern forming portion, and measuring the line width of the stacked pattern at three randomly selected locations, and calculating the average value thereof.

[0062] Next, the manufacturing method of the wiring substrate of the present invention is described. As the manufacturing method of the wiring substrate of the present invention, for example, in the case where a laminated pattern including an opaque wiring electrode and a light shielding layer in sequence is provided on a transparent substrate, it is preferable to have: a step of forming an opaque wiring electrode on the transparent substrate (hereinafter, sometimes described as an "opaque wiring electrode forming step"); and a step of forming a light shielding layer containing a resin and a coloring component on the opaque wiring electrode forming surface to form a laminated pattern (hereinafter, sometimes described as a "laminated pattern forming step").

[0063] In the opaque wiring electrode forming step, as a method for forming the opaque wiring electrode, for example, there can be mentioned: 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; a method of forming a film of metal, metal composite, composite of metal and metal compound, metal alloy, etc., by photolithography using a resist; etc. In the case of exhibiting conductivity by heat curing, the pattern formed by the photosensitive conductive composition is preferably heat cured at 140 to 500°C.

[0064] In the lamination pattern forming step, as a step of forming the light shielding layer, for example, there can be mentioned: a method of patterning the positive photosensitive resin composition for forming the light shielding layer of the second embodiment of the present invention described later, after coating the opaque wiring electrode, exposing the positive photosensitive resin composition coating film for forming the light shielding layer from the side opposite to the coating side using the opaque wiring electrode as a mask, and developing the positive photosensitive resin composition coating film for forming the light shielding layer; a method of patterning the light shielding layer after transferring the light shielding layer to the opaque wiring electrode through the light shielding layer transfer film of the present invention described later, exposing the light shielding layer from the side opposite to the transfer side using the opaque wiring electrode as a mask, and developing the light shielding layer; etc. Among them, the latter method using the light shielding layer transfer film is preferred. By transferring the light shielding layer with its shape maintained using a light shielding layer transfer film, it is possible to suppress the thickness of the non-formed portion of the opaque wiring electrode from becoming thicker due to the leveling of the light shielding layer during film formation, and to suppress the increase in the required exposure amount and development time. By forming a light shielding layer pattern on the opaque wiring electrode using the above method, a stacked pattern can be formed.

[0065] As the exposure light source, for example, a mercury lamp, a halogen lamp, a xenon lamp, an LED lamp (365nm, 405nm), a semiconductor laser, a KrF or ArF excimer laser, etc. can be cited. Among them, the i-line (wavelength 365nm) of the mercury lamp and the LED lamp (365nm, 405nm) are preferred, and from the perspective of high output, the LED lamp (365nm) is further preferred. The exposure light can be irradiated while the substrate is allowed to stand still, or it can be irradiated while the substrate is transported in the direction of irradiating the exposure light to the opposite side of the light shielding layer forming surface on the light source.

[0066] As the developer used in the development, a liquid that does not hinder the conductivity of the electrode pattern is preferably an alkaline developer. As the alkaline developer, for example, the liquid exemplified as the developer in International Publication No. 2018 / 168325 can be cited. As the development method, for example, there can be cited: a method of spraying the developer onto the surface of the resin layer while the substrate is allowed to stand or rotate; a method of immersing the resin layer in the developer; a method of applying ultrasonic waves while immersing the resin layer in the developer; and the like.

[0067] The light shielding layer pattern obtained by development can be subjected to a rinsing treatment based on a rinsing liquid. As the rinsing liquid, for example, the substances exemplified as rinsing liquids in International Publication No. 2018 / 168325 can be cited.

[0068] The obtained wiring substrate can be further heated at 100 to 300° C. By heating, the hardness of the resin layer can be increased, defects and peeling caused by contact with other components can be suppressed, and the adhesion with the substrate and wiring can be further improved. As a heating method, for example, heating using an oven, an inert oven, a heating plate, and heating using electromagnetic waves such as an infrared heater can be cited.

[0069] Next, as a second embodiment of the present invention, a positive photosensitive resin composition for forming a light-shielding layer is described. The positive photosensitive resin composition for forming a light-shielding layer of the present invention can be preferably used for forming a light-shielding layer in the wiring substrate of the first embodiment of the present invention, and by forming a light-shielding layer from the positive photosensitive resin composition for forming a light-shielding layer, the average value R1 of the internal diffuse reflectance can be easily adjusted to the aforementioned range.

[0070] The positive photosensitive resin composition for forming a light-shielding layer of the present invention comprises (a) an alkali-soluble resin, (b) a quinonediazide compound, (c) metal nitride particles, and (d) a violet organic pigment. Here, positive photosensitivity refers to the property that the light-irradiated part dissolves in the developer, while the unirradiated part does not dissolve in the developer.

[0071] As (a) alkali-soluble resin, the substances exemplified for the light-shielding layer in the wiring substrate of the first embodiment of the present invention can be cited. As (a) alkali-soluble resin, a resin having a phenolic hydroxyl group is preferred. Through the hydrogen bond between the phenolic hydroxyl group and the (b) quinonediazide compound, the occurrence of development film loss and development peeling in the unexposed part can be further suppressed, making the opaque wiring electrode pattern less visually recognizable. As a resin having a phenolic hydroxyl group, the resin described for the light-shielding layer in the wiring substrate of the first embodiment of the present invention can be cited. The content of the (a) alkali-soluble resin in the solid component of the positive photosensitive resin composition for forming the light-shielding layer is preferably 45 to 65% by mass.

[0072] (b) The quinonediazide compound includes compounds exemplified as quinonediazide compounds contained in the positive photosensitive composition in International Publication No. 2018 / 168325. The content of the quinonediazide compound in the solid content of the positive photosensitive resin composition is preferably 5 to 25% by mass.

[0073] The positive photosensitive resin composition for forming a light-shielding layer of the present invention contains (c) metal nitride particles and (d) violet organic pigments that absorb light in the region of 540 to 570 nm with high visual perception and absorb visible light in the region of 570 to 640 nm, thereby maintaining the photosensitivity when an LED lamp (365 nm) is used as a light source when forming the light-shielding layer, and further improving the visual recognition of the design after the light-shielding layer is formed. As the (c) metal nitride particles and (d) violet organic pigments, the substances described for the light-shielding layer in the wiring substrate of the first embodiment of the present invention can be cited.

[0074] From the viewpoint of further improving the visual recognition of the design, the content of the (c) metal nitride particles in the solid component of the positive photosensitive resin composition for forming the light-shielding layer is preferably 2.0 volume % or more, and more preferably 2.5 volume % or more. On the other hand, from the viewpoint of photosensitivity, the content of the metal nitride particles is preferably 6.0 volume % or less, and more preferably 5.0 volume % or less.

[0075] From the viewpoint of further improving the visual recognition of the design, the content of (d) violet organic pigment in the solid content of the positive photosensitive resin composition for forming a light-shielding layer is preferably 1.0 volume % or more. On the other hand, from the viewpoint of photosensitivity, the content of (d) violet organic pigment is preferably 8.0 volume % or less.

[0076] The positive photosensitive resin composition for forming a light-shielding layer of the present invention preferably further contains (e) a red organic pigment. The (e) red organic pigment absorbs light in the wavelength range of 460 to 540 nm and absorbs visible light in the wavelength range of 570 to 640 nm, thereby maintaining the photosensitivity when an LED lamp (365 nm) is used as a light source when forming the light-shielding layer, and further improving the design visual recognition of the light-shielding layer.

[0077] When the positive photosensitive resin composition for forming a light-shielding layer of the present invention contains (e) a red organic pigment, the total content of the (c) metal nitride particles, (d) violet organic pigment, and (e) red organic pigment in the solid component of the positive photosensitive resin composition is preferably 5.0% by volume or more from the viewpoint of making diffuse reflection per unit area within the aforementioned preferred range and further improving visual recognition. On the other hand, from the viewpoint of photosensitivity, the total content thereof is preferably 15.0% by volume or less.

[0078] The positive photosensitive resin composition for forming a light-shielding layer of the present invention may contain, as necessary, a monomer having an unsaturated double bond, a photopolymerization initiator, a photoacid generator, a thermal acid generator, a sensitizer, an adhesion improver, a surfactant, a thermosetting agent, a polymerization inhibitor, a rust inhibitor, a softener, a leveling agent, and the like.

[0079] The positive photosensitive resin composition for forming a light-shielding layer of the present invention can be obtained, for example, by mixing (a) an alkali-soluble resin, (b) a quinonediazide compound, (c) metal nitride particles, (d) a violet organic pigment, and other additives added as needed, and then dispersing the mixture using a disperser or a mixer. Examples of the disperser or mixer include a jet mill, a bead mill, a ball mill, a planetary ball mill, and the like.

[0080] The positive photosensitive resin composition for forming a light-shielding layer of the present invention can be preferably used for the light-shielding layer transfer film of the present invention, and the light-shielding layer transfer film can be preferably used for forming a light-shielding layer in the wiring substrate of the first aspect of the present invention.

[0081] The light-shielding layer transfer film of the present invention has a light-shielding layer formed from the positive photosensitive resin composition for forming a light-shielding layer of the second aspect of the present invention on a releasable film.

[0082] The releasable film is preferably a film having a release layer on the surface.

[0083] As the release agent for forming the release layer, for example, non-silicone release agents and silicone release agents can be cited. As the non-silicone release agent, for example, long-chain alkyl-based, fluorine-based release agents and the like can be cited. Two or more of them can be used. Among them, even if the release agent transfers during transfer, it is not easy to repel the developer in the subsequent steps, especially the development step, and it is possible to suppress the unevenness in the surface and form a fine pattern. Non-silicone release agents are preferred. From the viewpoint of suppressing the uneven transfer during transfer, the thickness of the release layer is preferably 50nm or more. On the other hand, from the viewpoint of suppressing the traces of the release agent during transfer, the thickness of the release layer is preferably 500nm or less.

[0084] From the viewpoint of suppressing the repulsion during the formation of the light-shielding layer, the peeling force of the release film is preferably 500mN / 20mm or more. On the other hand, from the viewpoint of expanding the process margin during the transfer of the light-shielding layer, the peeling force of the release film is preferably 5,000mN / 20mm or less. Here, the peeling force of the release film refers to the peeling force when the acrylic adhesive tape "31B" manufactured by Nitto Denko Co., Ltd. is adhered to the surface formed by the release layer using a 2kg roller, and after standing for 30 minutes, it is peeled off at a peeling angle of 180° and a peeling speed of 0.3m / min.

[0085] As the film used in the release film, for example, films containing resins such as polyethylene terephthalate (PET), cycloolefin polymers, polycarbonates, polyimides, aramids, fluororesins, acrylic resins, and polyurethane resins can be cited. Two or more of them can be used. Among these, a film having transmissivity to the exposure light used in the aforementioned stacked pattern forming process is preferred, preferably a film containing PET, cycloolefin polymers, and polycarbonates. By selecting a film having transmissivity to the exposure light, exposure can be performed across the release film in the aforementioned stacked pattern forming process, and by placing the release film between the light-shielding layer and the photomask, contamination of the photomask can be suppressed.

[0086] From the viewpoint of improving the handling stability during the formation of the light-shielding layer and suppressing the uneven thickness of the light-shielding layer, the thickness of the release film is preferably 5 μm or more, more preferably 10 μm or more. On the other hand, from the viewpoint of operability during peeling, the thickness of the release film is preferably 300 μm or less, more preferably 200 μm or less.

[0087] From the perspective of making the opaque wiring electrode less visually recognizable, the thickness T1' [μm] of the light-shielding layer of the light-shielding layer transfer film is preferably greater than 0.3, and more preferably greater than 0.5. On the other hand, from the perspective of reducing the development time and further improving the processability, the thickness T1' [μm] of the light-shielding layer is preferably less than 2.0. It should be noted that T1' can be measured using a stylus-type step difference meter. In addition, with respect to the thickness T1' of the light-shielding layer, when it is transferred to form a light-shielding layer in the wiring substrate, it corresponds to the thickness T1, but sometimes changes depending on the method of forming the light-shielding layer.

[0088] The light-shielding layer transfer film of the present invention is obtained by, for example, applying a positive photosensitive resin composition for forming a light-shielding layer onto a release film.

[0089] As a method for coating the positive photosensitive resin composition for forming a light-shielding layer on the release film, for example, spin coating using a spinner, spray coating, roll coating, screen printing, or coating using a slit coater, a knife coater, a die coater, a calender coater, a meniscus coater, or a rod coater, etc. The coating thickness of the positive photosensitive resin composition for forming a light-shielding layer is preferably set so that the thickness T1 of the light-shielding layer is within the above-mentioned preferred range.

[0090] When the positive photosensitive resin composition for forming a light-shielding layer contains a solvent, it is preferably dried by heating. The drying temperature is preferably 60 to 120° C., and the drying time is preferably 1 to 20 minutes. As a heating drying device, for example, an oven, a hot plate, etc. are preferred.

[0091] Example

[0092] 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.

[0093] [(a) Alkali-soluble resin]

[0094] · Phenol Novolac resin WR-104 (manufactured by DIC Corporation).

[0095] [(b) Quinonediazide compounds]

[0096] (Production Example 1: Quinonediazide compound)

[0097] Under a dry nitrogen stream, 21.22 g (0.05 mol) of α,α-bis(4-hydroxyphenyl)-4-(4-hydroxy-α,α-dimethylbenzylethylbenzene (trade name TrisP-PA, manufactured by Honshu Chemical Industry Co., Ltd.) and 33.58 g (0.125 mol) of naphthoquinonediazide-5-sulfonyl chloride were dissolved in 450 g of 1,4-dioxane and the mixture was brought to room temperature. 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise thereto so that the temperature in the system did not exceed 35°C. After the addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Then, the precipitate was collected by filtration. The precipitate was dried with a vacuum dryer to obtain a quinonediazide compound.

[0098] [Coloring ingredients]

[0099] (c) Metal nitride particles: titanium nitride particles (particle size 17 nm)

[0100] (d) Purple organic pigment: Pigment Violet 23 (particle size 50 nm)

[0101] (e) Red organic pigment: Pigment Red 254 (particle size 100 nm)

[0102] Blue organic pigment: Pigment blue 15:6 (particle size 100nm)

[0103] ·Carbon black: MA100 (manufactured by Mitsubishi Chemical Co., Ltd.).

[0104] [other]

[0105] (Production Example 2: Acrylic resin having a carboxyl group)

[0106] In a reaction container under nitrogen atmosphere, 150 g of diethylene glycol monoethyl ether acetate (hereinafter, referred to as "DMEA") was placed, and the temperature was raised to 80°C using an oil bath. A mixture containing 20 g of ethyl acrylate (hereinafter, referred to as "EA"), 40 g of 2-ethylhexyl methacrylate (hereinafter, referred to as "2-EHMA"), 20 g of styrene (hereinafter, referred to as "St"), 15 g of acrylic acid (hereinafter, referred to as "AA"), 0.8 g of 2,2'-azobisisobutyronitrile and 10 g of DMEA was added dropwise over 1 hour. After the addition was completed, the mixture was further stirred for 6 hours to perform a polymerization reaction. Then, 1 g of hydroquinone monomethyl ether was added to terminate the polymerization reaction. Next, a mixture containing 5 g of glycidyl methacrylate (hereinafter, referred to as "GMA"), 1 g of triethylbenzylammonium chloride and 10 g of DMEA was added dropwise over 0.5 hours. After the addition was completed, the mixture was further stirred for 2 hours to perform an addition reaction. The obtained reaction solution was purified with methanol to remove unreacted impurities, and then vacuum dried for 24 hours to obtain a carboxyl-containing acrylic resin having a copolymerization ratio (weight basis): EA / 2-EHMA / St / GMA / AA=20 / 40 / 20 / 5 / 15. The acid value of the obtained carboxyl-containing acrylic resin was measured according to JIS K 0070 (1992) and the result was 103 mgKOH / g. The weight average molecular weight of the obtained carboxyl-containing acrylic resin was 17,000.

[0107] (Production Example 3: Acrylic resin having phenolic hydroxyl groups and carboxyl groups)

[0108] In a reaction container under nitrogen atmosphere, 150 g of 2-methoxy-1-methylethyl acetate (hereinafter referred to as "PMA") was placed and the temperature was raised to 80°C using an oil bath. A mixture of 20 g of EA, 20 g of 2-EHMA, 20 g of 4-hydroxystyrene (hereinafter referred to as "HS"), 15 g of N-hydroxymethyl acrylamide (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 completed, the mixture was further heated and stirred at 80°C for 6 hours to perform a polymerization reaction. Then, 1 g of hydroquinone monomethyl ether was added to terminate the polymerization reaction. The obtained 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 groups and carboxyl groups with a copolymerization ratio (weight basis): EA / 2-EHMA / HS / MAA / AA=20 / 20 / 20 / 15 / 25. The acid value was measured in the same manner as in Preparation Example 2 and was 153 mgKOH / g. The weight average molecular weight of the obtained acrylic resin having phenolic hydroxyl groups and carboxyl groups was 10,000.

[0109] (Production Example 4: Photosensitive Conductive Paste)

[0110] In a 100 mL clean bottle, 3.0 g of the acrylic resin having a carboxyl group obtained in Production Example 2, 0.3 g of a photopolymerization initiator N-1919 (manufactured by ADEK Corporation), 1.2 g of a monomer "Light Acrylate (registered trademark)" BP-4EA, 0.5 g of a dispersant "BYK (registered trademark)"-LP21116 (manufactured by BYK-Chemie Co., Ltd.), 79.0 g of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA"), and 16.0 g of silver fine particles having an average surface carbon coating thickness of 1 nm and a particle diameter of 40 nm (manufactured by Nisshin Engineering Co., Ltd.) were added, and mixed using "Awatori Rentaro (registered trademark)" ARE-310 (manufactured by THINKY Corporation) to obtain 100.0 g of a photosensitive conductive paste. The viscosity of the obtained photosensitive conductive paste was measured using an E-type viscometer under the conditions of a temperature of 25° C. and a rotation speed of 100 rpm. The result was 3 mPa·s.

[0111] (Production Example 5: Photosensitive Insulating Paste)

[0112] In a 100 mL clean bottle, 15.5 g of the acrylic resin having a carboxyl group obtained in Preparation Example 2, 5.2 g of "Light Acrylate (registered trademark)" BP-4EAL, 0.3 g of photopolymerization initiator N-1919, and 79.0 g of PGMEA were added and mixed using a rotation-revolution vacuum mixer "Awatori Rentaro (registered trademark)" ARE-310 to obtain 100.0 g of a 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 (manufactured by Metricon, PC-2000). The result was 1.53.

[0113] Evaluations in each of Examples and Comparative Examples were performed by the following methods.

[0114] (1) Line width W of the stacked pattern

[0115] The laminate pattern-formed portion of the substrate obtained in each example and comparative example was magnified and observed using an optical microscope. The line width of the laminate pattern was measured at three randomly selected locations, and the average value was taken as the line width W of the laminate pattern.

[0116] (2) Internal diffuse reflectivity

[0117] An anti-reflection film MTAR-3 (manufactured by MeCan Imaging Co., Ltd.) with an adhesive layer 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, a black PET film Kukkiri Mieru (manufactured by Tomogawa Paper Co., Ltd.) with an adhesive layer was attached to the non-laminated pattern-forming surface of the wiring substrate using a rubber roller to produce a Figure 3 The internal diffuse reflectance evaluation substrate 16 shown in FIG. The diffuse reflectance SCE of the laminated pattern forming portion of the internal diffuse reflectance evaluation substrate at wavelengths of 540, 550, 560, and 570 nm was measured using a spectrophotometer (CM-2500d) manufactured by Konica Minolta Sensing (KG), and the average value thereof was taken as the average value R1 of the internal reflectance. Next, regarding the diffuse reflectance SCE, the diffuse reflectance SCE of the laminated pattern non-forming portion of the internal diffuse reflectance evaluation substrate at wavelengths of 540, 550, 560, and 570 nm was measured using a spectrophotometer (CM-2500d) manufactured by Konica Minolta Sensing (KG), and the average value thereof was taken as the average value R2 of the internal reflectance.

[0118] (3) Visual recognition difficulty

[0119] For the wiring substrate obtained in each embodiment and comparative example, a black sheet SuperBlackIR (manufactured by Systems Engineering) was placed on the side opposite to the surface where the opaque wiring electrode was formed, and then light was projected onto the surface where the opaque wiring electrode was formed using a floodlight. Ten people visually observed the surface from a distance of 30 cm, and the number of people who could visually recognize the grid-shaped opaque wiring electrode was used to evaluate the visual recognition difficulty.

[0120] (4) Design visual recognizability

[0121] In each of the Examples and Comparative Examples, light was projected onto the surface of the substrate for internal diffuse reflectance evaluation to which the antireflection film was attached using a floodlight, with respect to the substrate for internal diffuse reflectance evaluation prepared in (2) Internal diffuse reflectance. Ten people visually inspected the substrate from a distance of 100 cm, and the design visibility was evaluated based on the number of people who could clearly visually recognize the boundary between the stacked pattern forming portion 10 and the stacked pattern non-forming portion 11.

[0122] (5) Photosensitivity

[0123] In each of the Examples and Comparative Examples, the exposure device in the "Formation of Light Shielding Layer" was replaced with a 365 nm LED lamp (manufactured by CCS Corporation) at 500 mJ / cm 2 、800mJ / cm 2 、1500mJ / cm2 、3000mJ / cm 2 The exposure was performed at various exposure doses, and the minimum exposure dose at which the exposed part was dissolved in the developer within 30 seconds was taken as the necessary exposure dose to evaluate the photosensitivity. 2 If the exposure amount is such that the film cannot be dissolved within 30 seconds, it is evaluated as 3000<.

[0124] (Example 1)

[0125] <Opaque Wiring Electrode Forming Step>

[0126] The photosensitive conductive paste (D-1) obtained in Production Example 4 was applied to one side of an alkali-free glass "AN Wizus (registered trademark)" (AGC Co., Ltd., transmittance at a wavelength of 365 nm: 91%, transmittance at a wavelength of 550 nm: 92%) by spin coating so as to have a thickness of 1 μm after drying, and dried at 90° C. for 8 minutes. Figure 4 The exposure mask having the grid-shaped laminated pattern forming portion 10 and the laminated pattern non-forming portion 11 was used with an exposure device (PEM-6M; manufactured by Union Optical Co., Ltd.) at an exposure dose of 150 mJ / cm 2 (converted to a wavelength of 365nm) for exposure. Here, the grid-shaped pattern is Figure 5 The negative pattern shown has a grid pitch 14 of 400 μm, a grid angle 15 of 58°, a stacked pattern portion (mask opening portion) 12 with an opening width of 4 μm and a non-stacked pattern portion (mask light shielding portion) 13. Figure 5 In the process, black and white inversion was performed for the purpose of illustration. Then, a 0.1 mass % tetramethylammonium hydroxide aqueous solution was used as a developer, and development was performed for twice the time required for the exposure part to dissolve, and then rinsed with ultrapure water for 30 seconds, and then 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 difference meter "SURFCOM (registered trademark)" 1400 (manufactured by Tokyo Seimitsu Co., Ltd.), and the result was 0.5 μm.

[0127] <Laminate pattern forming step>

[0128] (Preparation of positive photosensitive resin composition for light shielding layer formation)

[0129] In a 100 mL clean bottle, 2.89 g of phenol Novolac resin WR-104 (manufactured by DIC Corporation) as (a) an alkali-soluble resin, 0.49 g of the quinonediazide compound obtained in Production Example 1 as (b) a quinonediazide compound, 0.22 g of carboxybenzotriazole "VERZONE (registered trademark)" C-BTA (manufactured by Yamato Chemical Industry Co., Ltd.), 0.01 g of a leveling agent "BYK (registered trademark)" -331 (manufactured by BYK-Chemie Co., Ltd.), and 44.45 g of PGMEA were added, and mixed using a rotation-revolution vacuum mixer "Awatori Rentaro (registered trademark)" ARE-310 (manufactured by THINKY Corporation) to obtain 48.07 g of a resin solution. 48.07 g of the obtained resin solution, 1.21 g of carbon black MA100 (manufactured by Mitsubishi Chemical Corporation) and 0.72 g of dispersant "BYK"-LP21116 (manufactured by BYK-Chemie) were mixed and the mixture was stirred at 70% by volume using a flask filled with 70% by volume of a flask. The mixture was kneaded with a centrifugal separator of zirconium oxide beads (manufactured by Toray Industries, Ltd.) and Ultra Apex Mill (manufactured by Kotobuki Industry Co., Ltd.) to obtain 50.0 g of a positive photosensitive resin composition 1 for light-shielding layer formation.

[0130] (Formation of Light-Shielding Layer)

[0131] The obtained positive photosensitive resin composition 1 for forming a light shielding layer was spin-coated on the surface of the opaque wiring electrode formed in the <opaque wiring electrode forming step> so that the film thickness after drying was 1.4 μm, and dried at 100° C. for 10 minutes. Then, using the opaque wiring electrode as a mask, an exposure device (PEM-6M) was used to expose the opaque wiring electrode from the opposite side of the surface formed with an exposure dose (converted at a wavelength of 365 nm) of 10,000 mJ / cm 2 The exposed film was exposed under the conditions of , and developed with 2.38 mass % tetramethylammonium hydroxide aqueous solution as a developer until the transparent substrate of the exposed part was exposed, and a light shielding layer pattern was formed on the opaque wiring electrode to form a stacked pattern. Further, it was heated in a box oven at 220°C for 60 minutes.

[0132] <Transparent protective layer forming step>

[0133] The photosensitive insulating paste obtained in (Manufacturing Example 5) was spin-coated on the substrate with the laminated pattern obtained in the <Laminated pattern forming step> so that the film thickness after drying was 3.0 μm, and dried at 80° C. for 5 minutes. An exposure device (PEM-6M) was used to expose the coated surface at an exposure dose (converted to a wavelength of 365 nm) of 100 mJ / cm 2The film was exposed under the conditions of , and developed for 60 seconds using a 0.1 mass % tetramethylammonium hydroxide aqueous solution as a developer. Furthermore, the film was heated in a box oven at 220° C. for 60 minutes. A wiring substrate having a transparent protective layer formed thereon was obtained.

[0134] (Example 2)

[0135] A wiring substrate was obtained in the same manner as in Example 1 except that the grid pitch and occupancy S of the exposure mask in the <Opaque wiring electrode forming step> and the composition in (preparation of a positive photosensitive resin composition for forming a light-shielding layer) were changed as shown in Table 1.

[0136] (Examples 3 to 9)

[0137] A wiring substrate was obtained in the same manner as in (Example 2) except that the composition in (Preparation of positive photosensitive resin composition for forming light-shielding layer) and the exposure amount in (Formation of light-shielding layer) were changed as described in Tables 1 and 2.

[0138] (Comparative Example 1)

[0139] A wiring substrate was obtained in the same manner as in (Example 3) except that (formation of the light shielding layer) was not performed.

[0140] (Comparative Examples 2 to 6)

[0141] A wiring substrate was obtained in the same manner as in (Example 2) except that the composition in (Preparation of positive photosensitive resin composition for forming light-shielding layer) and the exposure amount in (Formation of light-shielding layer) were changed as described in Table 3.

[0142] (Example 10)

[0143] <Formation of Opaque Wiring Electrode>

[0144] In the same manner as in (Example 2), a substrate with an opaque wiring electrode was obtained.

[0145] <Laminate pattern forming step>

[0146] (Preparation of positive photosensitive resin composition for light shielding layer formation)

[0147] In a 100 mL clean bottle, 0.77 g of phenol Novolac resin WR-104 (manufactured by DIC Corporation), 2.33 g of the acrylic resin having phenolic hydroxyl groups and carboxyl groups obtained in Preparation Example 2, 0.77 g of the quinonediazide compound obtained in Preparation Example 1, 0.19 g of carboxybenzotriazole "VERZONE (registered trademark)" C-BTA (manufactured by Yamato Chemical Industry Co., Ltd.), 0.01 g of leveling agent "BYK (registered trademark)" -331 (manufactured by BYK-Chemie Co., Ltd.), and 44.28 g of PGMEA were added, and mixed using a rotation-revolution vacuum mixer "Awatori Rentaro (registered trademark)" ARE-310 (manufactured by THINKY Corporation) to obtain 48.77 g of a resin solution. 48.77 g of the obtained resin solution, 0.79 g of titanium nitride particles, 0.32 g of a violet organic pigment, 0.11 g of a red organic pigment and 0.50 g of a dispersant "BYK (registered trademark)"-LP21116 (manufactured by BYK-Chemie) were mixed and a 70% by volume filled The mixture was kneaded with a centrifugal separator of zirconium oxide beads (manufactured by Toray Industries, Ltd.) and Ultra Apex Mill (manufactured by Kotobuki Industry Co., Ltd.) to obtain 50.0 g of a positive photosensitive resin composition 2 for light-shielding layer formation.

[0148] (Production of light-shielding layer transfer film)

[0149] A non-silicone release agent AL-5 (manufactured by Lintec Co., Ltd.) was applied to one side of a PET film "Lumirror (registered trademark)" FB40 (manufactured by Toray Industries, Ltd.) (thickness: 16 μm), and heat-treated and dried to form a release layer with a thickness of 100 nm on the surface of the substrate to obtain a release film. With respect to the obtained release film, an acrylic adhesive tape "31B" manufactured by Nitto Denko Co., Ltd. was attached to the release layer-forming surface using a 2 kg roller, and after standing for 30 minutes, the film was peeled off at a peeling angle of 180° and a peeling speed of 0.3 m / min. The peeling force at this time was measured and the result was 1,480 mN / 20 mm.

[0150] The obtained positive photosensitive resin composition 2 for forming a light-shielding layer was applied to the release layer of the obtained release film using a coater so that the thickness T1' after drying was 1.4 μm, and dried at 80° C. for 4 minutes to form a light-shielding layer and obtain a light-shielding layer transfer film.

[0151] (Formation of Light-Shielding Layer)

[0152] On the opaque wiring electrode formed in the <opaque wiring electrode forming step>, the light-shielding layer transfer film obtained in the <light-shielding layer transfer film preparation> was thermally pressed at 80°C and at a speed of 0.1 m / min, and the release film was peeled off. Then, using the opaque wiring electrode as a mask, an exposure device (PEM-6M) was used to expose the light-shielding layer from the opposite side of the opaque wiring electrode formation surface at an exposure amount (converted to a wavelength of 365 nm) of 100 mJ / cm 2 The film was exposed under the conditions of , and developed with a 1.00 mass % sodium carbonate aqueous solution as a developer until the transparent substrate of the exposed part was exposed, and a light shielding layer pattern was formed on the opaque wiring electrode to form a stacked pattern. Further, it was heated in a box oven at 220° C. for 60 minutes.

[0153] <Formation of Transparent Protective Layer>

[0154] A transparent protective layer was formed in the same manner as in (Example 1) to obtain a wiring substrate.

[0155] The main configurations and evaluation results of each example and comparative example are shown in Tables 1 to 4.

[0156]

[0157]

[0158]

[0159]

[0160] Description of Reference Numerals

[0161] 1: Transparent substrate

[0162] 2: Opaque wiring electrode

[0163] 3: Light-shielding layer

[0164] 4: Wiring substrate

[0165] 5: Cascading Patterns

[0166] 6: Transparent protective layer

[0167] 7: Adhesive layer

[0168] 8: Anti-reflective film

[0169] 9: Black film

[0170] 10: Lamination pattern forming part

[0171] 11: Layered pattern non-formed portion

[0172] 12: Lamination pattern part (mask opening part)

[0173] 13: Non-laminated pattern part (mask light shielding part)

[0174] 14: Grid Spacing

[0175] 15: Grid Angle

[0176] 16: Substrate for internal diffuse reflectance evaluation

Claims

1. A wiring substrate having a stacked pattern of an opaque wiring electrode and a light-shielding layer containing a resin and a coloring component on a transparent substrate, wherein the average value R1 of the internal diffuse reflectance of the wiring substrate at a wavelength of 540 to 570 nm measured from the light-shielding layer side of the stacked pattern forming portion is 0.03 to 0.11%.

2. The wiring substrate according to claim 1, wherein The average value R1 [%] of the internal diffuse reflectance, the average value R2 [%] of the internal diffuse reflectance of the non-stacked pattern forming portion at a wavelength of 540 to 570 nm, the line width W [μm] of the stacked pattern, and the ratio of the stacked pattern area to the area of ​​the stacked pattern forming portion (stacked pattern area / the area of ​​the stacked pattern forming portion) S satisfy the relationship of the following formula (1), 0.0≤((R1×W)-(R2×(1-S))) / S≤7.0 (1).

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

0.

4. A positive photosensitive resin composition for forming a light-shielding layer, comprising (a) an alkali-soluble resin, (b) a quinonediazide compound, (c) metal nitride particles, and (d) a violet organic pigment.

5. The positive photosensitive resin composition for forming a light-shielding layer according to claim 4, wherein The content of the (c) metal nitride particles is 2.0 to 6.0 volume %. 6 . The positive photosensitive resin composition for forming a light-shielding layer according to claim 4 , further comprising (e) a red organic pigment.

7. The positive photosensitive resin composition for forming a light-shielding layer according to claim 6, wherein The total content of the (c) metal nitride particles, the (d) violet organic pigment, and the (e) red organic pigment is 5.0 to 15.0% by volume. 8 . A light-shielding layer transfer film comprising a light-shielding layer formed from the positive-type photosensitive resin composition for forming a light-shielding layer according to claim 4 or 5 on a release film.

9. The light-shielding layer transfer film according to claim 8, wherein: The thickness T1' [μm] of the light shielding layer is 0.3 to 2.

0.

10. The method for producing a wiring substrate according to claim 1 or 2, comprising: The process of forming an opaque wiring electrode on a transparent substrate; A step of applying the positive photosensitive resin composition for forming a light shielding layer according to claim 4 or 5 to the surface where the opaque wiring electrode is formed; and The step of exposing and developing the photosensitive resin composition coating film from the surface opposite to the coating surface using the opaque wiring electrode as a mask to pattern the photosensitive resin composition coating film to form a stacked pattern of the opaque wiring electrode and the light shielding layer.

11. The method for producing a wiring substrate according to claim 1 or 2, comprising: The process of forming an opaque wiring electrode on a transparent substrate; a step of transferring the light-shielding layer of the light-shielding layer transfer film according to claim 8 to the surface on which the opaque wiring electrode is formed; and The step of exposing and developing the light shielding layer from the surface opposite to the transfer surface using the opaque wiring electrode as a mask, thereby patterning the light shielding layer to form a stacked pattern of the opaque wiring electrode and the light shielding layer.

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