Method for manufacturing substrate with wiring electrode

Abstract

The purpose of the present invention is to provide a method for manufacturing a substrate with a wiring electrode, wherein an opaque wiring electrode pattern is not easily visible, and processability is excellent. The present invention relates to a method for manufacturing a substrate with a wiring electrode, the method comprising: a step for forming an opaque wiring electrode pattern on at least one surface of a transparent substrate; a step for forming a light-shielding layer on the opaque wiring electrode pattern-formed surface of the transparent substrate by transferring a positive photosensitive resin layer that contains light-shielding components; and a step for forming a light-shielding pattern on a region corresponding to the opaque wiring electrode pattern by exposing and developing the light-shielding layer by using the opaque wiring electrode pattern as a mask.

Description

Method for manufacturing substrate with wiring electrodes

[0001] The present invention relates to a method for producing a substrate with wiring electrodes, which has an opaque wiring electrode pattern and a light-shielding pattern on at least one surface of a transparent substrate.

[0002] Touch panels, which have become widely used as input devices in recent years, are composed of a display unit such as a liquid crystal panel and a touch panel sensor that detects information input at a specific position. Transparent wiring electrodes have generally been used as wiring electrodes for touch panel sensors to make the wiring electrodes less visible. However, in recent years, due to increased sensitivity and larger screen sizes, opaque wiring electrodes made of metallic materials have become more common. Opaque wiring electrodes made of metallic materials have a problem of being visible due to their metallic luster. Therefore, as a method for making the opaque wiring electrodes less visible, a method for manufacturing a substrate with wiring electrodes has been proposed, which includes the steps of forming an opaque wiring electrode on at least one surface of a transparent substrate, applying a positive-type photosensitive light-blocking composition to one surface of the transparent substrate, and exposing and developing the positive-type photosensitive composition using the opaque wiring electrode as a mask to form a light-blocking layer in the area corresponding to the opaque wiring electrode (see, for example, Patent Document 1).

[0003] International Publication No. 2018 / 168325

[0004] The manufacturing method described in Patent Document 1 makes it possible to obtain a substrate with wiring electrodes having a fine pattern, excellent conductivity, and opaque wiring electrodes and wiring electrodes that are difficult to see. However, when a positive-type photosensitive light-shielding composition is applied to the opaque wiring electrodes to form a light-shielding layer, a positive-type photosensitive light-shielding composition layer is formed in areas where there are no opaque wiring electrodes due to leveling. As a result, the thickness of the areas removed by the photolithography process is greater than the thickness of the light-shielding layer formed on the opaque wiring electrodes. This has led to processability issues, such as an increased exposure dose required to form a pattern of the light-shielding layer and a longer development time. Furthermore, the longer development time is likely to cause thinning of the developed film and peeling during development, making the opaque wiring electrodes more visible.

[0005] Therefore, an object of the present invention is to provide a method for manufacturing a substrate with wiring electrodes, which has an opaque wiring electrode pattern that is difficult to see and has excellent processability.

[0006] In order to solve the above problems, the present invention mainly comprises the following components: <1> A method for manufacturing a substrate with wiring electrodes, comprising the steps of: forming an opaque wiring electrode pattern on at least one surface of a transparent substrate; forming a light-shielding layer by transferring a positive photosensitive resin layer containing a light-shielding component onto the surface of the transparent substrate on which the opaque wiring electrode pattern is formed; and exposing and developing the light-shielding layer using the opaque wiring electrode pattern as a mask to form a light-shielding pattern in a portion corresponding to the opaque wiring electrode pattern. <2> A method for manufacturing a substrate with wiring electrodes according to <1>, wherein the positive photosensitive resin layer has a thickness T1 [μm] of 0.3 to 2.0 μm. <3> A method for manufacturing a substrate with wiring electrodes according to <1> or <2>, wherein the sum of the thickness T1 [μm] of the positive photosensitive resin layer and the thickness T2 [μm] of the opaque wiring electrode pattern is 1.5 to 10.0 μm, and T1 and T2 satisfy the following formula (1): 0.1<T1 / (T1+T2)<0.5 (1) <4> The method for producing a substrate with wiring electrodes according to any one of <1> to <3>, wherein the thickness T2 [μm] of the opaque wiring electrode pattern is 1.0 to 5.0. <5> The method for producing a substrate with wiring electrodes according to any one of <1> to <4>, wherein the positive photosensitive resin layer contains (b-1) an acrylic resin having a phenolic hydroxyl group and a carboxyl group. <6> The method for producing a substrate with wiring electrodes according to <5>, wherein the positive photosensitive resin layer further contains (b-2) a phenol novolac resin. <7> The method for producing a substrate with wiring electrodes according to <6>, wherein the mass ratio ((b-1) / (b-2)) of the content of the acrylic resin having a phenolic hydroxyl group and a carboxyl group (b-1) to the content of the phenol novolac resin (b-2) in the positive photosensitive resin layer is 1.0 to 3.0. <8> The method for producing a substrate with wiring electrodes according to any one of <1> to <7>, wherein the line width of the opaque wiring electrode pattern is 1 to 10 μm. <9> The method for producing a substrate with wiring electrodes according to any one of <1> to <8>, wherein the substrate with wiring electrodes has at least a fine line pattern portion, and in the fine line pattern portion, the proportion of an area where the opaque wiring electrode pattern is formed relative to the entire transparent substrate is 20 area % or less.<10> The method for producing a substrate with wiring electrodes according to any one of <1> to <9>, wherein the opaque wiring electrode pattern has a light transmittance of 15% or less at a wavelength of 365 nm. <11> The method for producing a substrate with wiring electrodes according to any one of <1> to <10>, wherein the opaque wiring electrode pattern contains silver and / or copper.

[0007] According to the present invention, a substrate with wiring electrodes, in which the opaque wiring electrode pattern is hardly visible, can be obtained with good processability.

[0008] Fig. 1 is a schematic diagram showing an example of the configuration of a substrate with wiring electrodes in the present invention. Fig. 2 is a schematic diagram showing another example of the configuration of a substrate with wiring electrodes in the present invention. Fig. 3 is a schematic diagram showing a part of an example of a method for manufacturing a substrate with wiring electrodes of the present invention. Fig. 4 is a schematic diagram showing an electrode pattern for evaluating visibility and conductivity used in Examples and Comparative Examples. Fig. 5 is a schematic diagram of a mesh pattern of a negative-type mask used in Examples and Comparative Examples. Fig. 6 is a schematic diagram of a mesh pattern of a positive-type mask used in Examples and Comparative Examples.

[0009] The substrate with wiring electrodes of the present invention has an opaque wiring electrode pattern on at least one surface of a transparent substrate, and a light-shielding pattern in a region corresponding to the opaque wiring electrode pattern. The light-shielding pattern has the effect of making the opaque wiring electrode pattern less visible. Furthermore, an overcoat layer may be formed thereon, which protects the surface of the opaque wiring electrode pattern and the light-shielding pattern and prevents scratches and the like. Note that in the present invention, a light-shielding pattern may be formed in a portion of a region corresponding to the opaque wiring electrode pattern. For example, in the case of a substrate with wiring electrodes used in a touch panel sensor, it is required to make the opaque wiring electrode pattern less visible in the display section of a liquid crystal panel or the like, so it is preferable to have a light-shielding pattern in the display section.

[0010] Fig. 1 shows a schematic diagram of one example of the configuration of a substrate with wiring electrodes in the present invention. An opaque wiring electrode pattern 2 is provided on a transparent substrate 1, and a light-shielding pattern 3 is provided on the opaque wiring electrode pattern 2. Fig. 2 shows another example of the configuration of a substrate with wiring electrodes in the present invention. An opaque wiring electrode pattern 2 (first opaque wiring electrode pattern) and an insulating layer 4 are provided on the transparent substrate 1, an opaque wiring electrode pattern 2 (second opaque wiring electrode pattern) is provided on the insulating layer 4, and a light-shielding pattern 3 is provided in a position corresponding to the opaque wiring electrode pattern 2 (first opaque wiring electrode pattern and second opaque wiring electrode pattern).

[0011] The method for producing a substrate with wiring electrodes of the present invention includes a step of forming an opaque wiring electrode pattern on at least one surface of a transparent substrate (hereinafter sometimes abbreviated as the "opaque wiring electrode pattern forming step"), a step of forming a light-shielding layer by transferring a positive photosensitive resin layer containing a light-shielding component to the surface of the transparent substrate on which the opaque wiring electrode pattern has been formed (hereinafter sometimes abbreviated as the "light-shielding layer forming step"), and a step of exposing and developing the light-shielding layer using the opaque wiring electrode pattern as a mask to form a light-shielding pattern in a portion corresponding to the opaque wiring electrode pattern (hereinafter sometimes abbreviated as the "light-shielding pattern forming step"). By forming a light-shielding layer on the surface on which the opaque wiring electrode pattern has been formed in the opaque wiring electrode pattern forming step, and then exposing and developing the light-shielding layer using the opaque wiring electrode pattern as a mask, the light-shielding pattern can be formed in the portion corresponding to the opaque wiring electrode pattern. Here, in the light-shielding layer-forming step, when a positive-type photosensitive light-shielding composition is applied to the uneven surface of a transparent substrate on which an opaque wiring electrode pattern has been formed, as described above, the positive-type photosensitive light-shielding composition is applied not only to the convex portions but also to the concave portions due to leveling, resulting in the formation of a light-shielding layer in areas where there is no opaque wiring electrode pattern. In such areas, in addition to the originally intended thickness of the light-shielding layer, a light-shielding layer corresponding to the thickness of the opaque wiring electrode pattern is also formed. This tends to increase the exposure dose and development time required for pattern formation, resulting in processability issues. Longer development times are likely to cause development film thinning and peeling, reducing the effectiveness of the light-shielding layer and making the opaque wiring electrode pattern more visible. From the perspective of electrical conductivity, this issue becomes more pronounced as the thickness of the opaque wiring electrode pattern is increased. In contrast, the present invention is characterized in that a shape-retaining positive-type photosensitive resin layer is transferred in the light-shielding layer-forming step. By forming a light-shielding layer by transferring a positive photosensitive resin layer, the above-mentioned problems caused by leveling can be solved, a light-shielding layer of a desired thickness can be formed with good processability, and the opaque wiring electrode pattern can be made less visible.

[0012] 3 shows a schematic diagram of the light-shielding layer exposure step in the light-shielding pattern formation step as part of an example of the method for manufacturing a substrate with wiring electrode of the present invention. An opaque wiring electrode pattern 2 is formed on one side of a transparent substrate 1, and a positive photosensitive resin layer containing a light-shielding component is transferred onto the opaque wiring electrode pattern 2 to form a light-shielding layer 5. By exposing the transparent substrate 1 from the side opposite to the side on which the opaque wiring electrode pattern 2 is formed, the light-shielding layer 5 can be exposed using the opaque wiring electrode pattern 2 as a mask.

[0013] Each step will be explained.

[0014] First, in the opaque wiring electrode pattern forming step, an opaque wiring electrode pattern is formed on at least one surface of a transparent substrate. Opaque wiring electrode patterns may be formed on both surfaces of the transparent substrate. Here, "transparent" refers to a light transmittance of 50% or more at a wavelength of 550 nm, and "opaque" refers to a light transmittance of less than 50% at a wavelength of 550 nm. 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).

[0015] The opaque wiring electrode pattern preferably has a fine line pattern consisting of a pattern with a line width of 20 μm or less. It is more preferable that the thin line pattern and a pad portion are included. Here, the pad portion refers to a portion electrically connected to an external element and is generally formed in a portion that is not visible. For example, in the case of a substrate with wiring electrodes used in a touch panel sensor, the opaque wiring electrode pattern preferably has a fine line pattern in a position corresponding to a display portion such as a liquid crystal panel to detect a touch position, and a pad portion outside the display portion to electrically connect to an external element. Furthermore, wiring may be included outside the display portion to connect these fine line patterns to the pad portion. In the present invention, as described above, it is preferable to have a light-shielding pattern in the display portion, and therefore it is preferable that the light-shielding pattern be included in a portion corresponding to the fine line pattern, and the light-shielding pattern may not be included in portions corresponding to the opaque wiring electrode pattern in the non-display portion, such as the pad portion or wiring.

[0016] The transparent substrate preferably has transparency to the exposure light used in the light-shielding pattern formation step described below. Specifically, the light transmittance at a wavelength of 365 nm is preferably 50% or more, and more preferably 70% or more. By ensuring that the light transmittance at a wavelength of 365 nm is 50% or more, the positive photosensitive composition can be efficiently exposed in the light-shielding pattern formation step described below. The light transmittance at a wavelength of 365 nm of the transparent substrate can be measured using an ultraviolet-visible spectrophotometer (U-3310: manufactured by Hitachi High-Technologies Corporation).

[0017] The transparent substrate may or may not be flexible. Examples of non-flexible transparent substrates include quartz glass substrates, soda glass substrates, alkali-free glass substrates, chemically strengthened glass substrates, Pyrex (registered trademark) glass substrates, synthetic quartz plates, epoxy resin substrates, polyetherimide resin substrates, polyether ketone resin substrates, and polysulfone resin substrates. Examples of flexible transparent substrates include resin films such as polyethylene terephthalate films (hereinafter referred to as "PET films"), cycloolefin polymer films, polyimide films, polyester films, and aramid films, as well as optical resin plates. A plurality of these may be stacked and used; for example, multiple transparent substrates may be bonded together with an adhesive layer. Furthermore, an insulating layer may be formed on the surface of these transparent substrates.

[0018] The thickness of the transparent substrate is appropriately selected depending on the material within a range that can stably support the opaque wiring electrode pattern and has the aforementioned transparency. For example, from the viewpoint of more stably supporting the opaque wiring electrode pattern, the thickness of the transparent substrate is preferably 0.3 mm or more in the case of a non-flexible transparent substrate, and preferably 25 μm or more in the case of a flexible transparent substrate. On the other hand, from the viewpoint of further improving the transparency of exposure light, the thickness of the transparent substrate is preferably 1.5 mm or less in the case of a non-flexible transparent substrate, and preferably 300 μm or less in the case of a flexible transparent substrate.

[0019] The opaque wiring electrode pattern preferably has a light transmittance of 25% or less at a wavelength of 550 nm. Furthermore, the opaque wiring electrode pattern preferably has light-shielding properties against the exposure light used in the light-shielding pattern formation process described below. Specifically, the opaque wiring electrode pattern preferably has a light transmittance of 15% or less at a wavelength of 365 nm. By setting the light transmittance at a wavelength of 365 nm to 15% or less, the mask function can be improved in the light-shielding pattern formation process described below, and the desired light-shielding pattern can be formed with greater ease of processing. The opaque wiring electrode pattern preferably has a light transmittance of 5% or less at a wavelength of 365 nm, and even more preferably has a light transmittance of 3% or less. When a light-shielding pattern is formed in a portion corresponding to the opaque wiring electrode pattern, the light transmittance of the opaque wiring electrode pattern in the portion where the light-shielding pattern is formed is preferably within the above-mentioned range, and the light transmittance of the thin line pattern of the opaque wiring electrode pattern is preferably within the above-mentioned range. The light transmittance of the opaque wiring electrode pattern can be measured for an opaque wiring electrode pattern of 0.1 mm square or larger using a microsurface spectrophotometer (VSS 400: manufactured by Nippon Denshoku Industries Co., Ltd.).

[0020] Examples of materials constituting the opaque wiring electrode pattern include metals such as silver, gold, copper, platinum, lead, tin, nickel, aluminum, tungsten, molybdenum, chromium, titanium, and indium, and conductive materials such as alloys of these. Two or more of these may be used. Among these, silver, copper, and the like are preferred from the viewpoint of conductivity.

[0021] The raw material used to form the opaque wiring electrode pattern is preferably conductive particles containing the above-mentioned conductive material, and the shape thereof is preferably spherical. The average particle size of the conductive particles is preferably 0.03 μm or more 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 less from the viewpoint of sharpening the edges of the opaque wiring electrode pattern. 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 a transmission electron microscope (TEM), measuring the major axis length of each of 100 randomly selected conductive particles, and calculating the number average value.

[0022] The opaque wiring electrode pattern may contain an organic component in addition to the aforementioned conductive substance. The opaque wiring electrode pattern 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 pattern contains the photopolymerization initiator and / or its photodecomposition product. The photosensitive conductive composition may contain additives such as a heat curing agent and a leveling agent, as necessary.

[0023] Among the opaque wiring electrode patterns, examples of the shape of the thin line pattern include a mesh shape and a stripe shape. Examples of the mesh shape include a lattice shape whose unit shapes are triangles, squares, polygons, circles, etc., or a lattice shape consisting of a combination of these unit shapes. Among these, the mesh shape is preferred from the viewpoint of achieving uniform conductivity of the pattern. Among the opaque wiring electrode patterns, the thin line pattern is more preferably a metal mesh made of the above-mentioned metal and having a mesh-like pattern.

[0024] The thickness T2 [μm] of the opaque wiring electrode pattern is preferably 0.5 or more, more preferably 1.0 or more, and even more preferably 1.5 or more, from the viewpoint of improving conductivity. On the other hand, the thickness T2 [μm] of the opaque wiring electrode pattern 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 substrate with wiring electrode has an overcoat layer, by setting the thickness T2 [μm] of the opaque wiring electrode pattern to 10 or less, unevenness on the transparent substrate can be reduced and the generation of bubbles due to the unevenness when the overcoat layer is laminated can be suppressed. Of the opaque wiring electrode pattern, the thickness of the fine line pattern is preferably within the above range. The thickness T2 [μm] of the opaque wiring electrode pattern can be determined by measuring the thickness at five randomly selected locations using a stylus-type profilometer "Surfcom" (registered trademark) 1400 (manufactured by Tokyo Seimitsu Co., Ltd.) and calculating the average value.

[0025] 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 even more preferably 2 μm or more, from the viewpoint of improving conductivity. On the other hand, the line width of the pattern of the opaque wiring electrode is preferably 10 μm or less, more preferably 8 μm or less, from the viewpoint of making the wiring electrode less visible. Of the opaque wiring electrode patterns, it is preferable that the line width of the thin line pattern is within the above range. The line width of the pattern of the opaque wiring electrode can be determined by measuring five randomly selected locations using an optical microscope and calculating the average value.

[0026] When the opaque wiring electrode pattern has a fine line pattern, from the viewpoint of making the opaque wiring electrode pattern less visible, in the portion of the wiring electrode substrate where the fine line pattern is formed (fine line pattern portion), the proportion of the area where the opaque wiring electrode pattern is formed relative to the entire transparent substrate is preferably 20 area % or less, more preferably 15 area % or less. The opaque wiring electrode pattern may be laminated in two or more layers via a transparent protective layer. In particular, by laminating the fine line pattern, the proportion of the area where the fine line pattern is formed can be reduced while maintaining conductivity, making it less visible. The area where the fine line pattern is formed can be calculated by measuring the length and width of the fine line pattern using an optical microscope.

[0027] The opaque wiring electrode pattern forming process may include a step of forming a first opaque wiring electrode pattern on one side of a transparent substrate, a step of forming an insulating layer on the first opaque wiring electrode, and a step of forming a second opaque wiring electrode pattern on the insulating layer.

[0028] Examples of methods for forming an opaque wiring electrode pattern include a method of forming a pattern by photolithography using the above-mentioned photosensitive conductive composition, a method of forming a pattern by screen printing, gravure printing, inkjet printing, or the like using a conductive composition (conductive paste), and a method of forming a film of a metal, a metal composite, a composite of a metal and a metal compound, a metal alloy, or the like, and then forming a pattern by photolithography using a resist. When forming an opaque wiring electrode pattern on both sides of a transparent substrate, when forming two or more layers of opaque wiring electrode patterns via an insulating layer, or when forming a thin line pattern and other layers in separate processes, each opaque wiring electrode pattern may be formed by the same method, or different methods may be combined. An insulating layer may be formed on the opaque wiring electrode pattern of the obtained substrate with an opaque wiring electrode pattern. Examples of insulating layers and methods for forming them include the insulating layers and methods for forming them exemplified in International Publication No. WO 2018 / 168325.

[0029] Next, in the light-shielding layer formation step, a positive-type photosensitive resin layer containing a light-shielding component is transferred onto the surface of the transparent substrate on which the opaque wiring electrode pattern is formed, thereby forming a light-shielding layer. As the positive-type photosensitive resin layer, for example, a so-called dry film can be used, which is obtained by applying a positive-type photosensitive resin composition containing a light-shielding component onto a release film and drying it as necessary. By transferring a positive-type photosensitive resin layer having shape retention properties such as a dry film, the above-mentioned problems caused by leveling can be solved, a light-shielding layer of the desired thickness can be formed with good processability, and the opaque wiring electrode pattern can be made less visible. It is preferable to use a black transfer film, which will be described later, as the dry film. Below, the light-shielding layer formation step using a dry film will be described as an example.

[0030] First, a dry film is prepared. A positive photosensitive resin composition containing a light-shielding component may be applied onto a release film and then dried to produce a dry film having a positive photosensitive resin layer containing a light-shielding component.

[0031] The release film refers to a film having a release layer on the surface.

[0032] Examples of release agents that form the release layer include non-silicone release agents and silicone release agents. Examples of non-silicone release agents include long-chain alkyl release agents 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 repellency in subsequent processes, particularly the development process, and can form fine patterns while suppressing in-plane unevenness. The thickness of the release layer is preferably 50 nm or more from the viewpoint of suppressing transfer unevenness during transfer. On the other hand, the thickness of the release layer is preferably 500 nm or less from the viewpoint of suppressing release agent transfer during transfer.

[0033] The peeling strength of the release film is preferably 500 mN / 20 mm or more from the viewpoint of suppressing repelling during the formation of the positive photosensitive resin layer. On the other hand, the peeling strength 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 positive photosensitive resin layer. Here, the peeling strength of the release film refers to the peeling strength measured when an acrylic adhesive tape "31B" manufactured by Nitto Denko Corporation is applied to the surface on which the release layer is formed using a 2 kg roller, allowed to stand for 30 minutes, and then peeled at a peel angle of 180° and a peeling speed of 0.3 m / min.

[0034] Examples of films used for the release film 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, those that are transparent to the exposure light used in the light-shielding pattern formation step described below 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 light-shielding pattern formation step described below. In this case, by placing a release film between the positive photosensitive resin layer and the photomask, contamination of the photomask can be suppressed.

[0035] The thickness of the release film is preferably 5 μm or more, more preferably 10 μm or more, from the viewpoint of improving transport stability during formation of the positive photosensitive resin layer and suppressing thickness unevenness of the positive photosensitive resin layer, while the thickness of the release film is preferably 300 μm or less, more preferably 200 μm or less, from the viewpoint of handleability during peeling.

[0036] Examples of light-shielding components include dyes, organic pigments, and inorganic pigments. Two or more of these may be contained. More specifically, examples include those exemplified as colorants in WO 2018 / 168325, organic pigments such as soluble azo pigments, insoluble azo pigments, metal complex azo pigments, phthalocyanine pigments, and condensed polycyclic pigments, iron oxides such as pine soot, ultramarine, iron black, hematite, goethite, and magnetite, titanium, chromium, lead, and metal composites thereof. Two or more of these may be used. Among these, carbon black is preferred from the viewpoint of availability, and titanium nitride is preferred from the viewpoint of light transmittance of exposure light.

[0037] The content of the light-shielding component in the positive photosensitive resin layer is preferably 5 to 30% by mass.

[0038] The positive photosensitive resin composition refers to a composition having positive photosensitivity in which the irradiated portion dissolves in a developer, and preferably contains a photosensitizer (dissolution inhibitor) and an alkali-soluble resin. Furthermore, the composition may contain a plasticizer, a leveling agent, a surfactant, a rust inhibitor, a crosslinking agent, a silane coupling agent, an antifoaming agent, a stabilizer, etc., within a range that does not impair the desired properties. Furthermore, the composition preferably contains a solvent, which allows the viscosity of the positive photosensitive resin composition to be adjusted to a desired range.

[0039] Examples of the photosensitizer (dissolution inhibitor) include those exemplified as photosensitizers (dissolution inhibitors) contained in the positive photosensitive composition in WO 2018 / 168325.

[0040] The content of the photosensitizer (dissolution inhibitor) in the positive photosensitive resin layer is preferably 5 to 25% by mass.

[0041] Examples of alkali-soluble resins include resins having hydroxyl groups and / or carboxyl groups, with (b) resins having phenolic hydroxyl groups being preferred. When a quinone diazide compound is used as the photosensitizer (dissolution inhibitor), the inclusion of a (b) resin having a phenolic hydroxyl group allows the phenolic hydroxyl group and the quinone diazide compound to form hydrogen bonds, thereby further suppressing the occurrence of film loss and peeling during development in the unexposed areas of the positive-type photosensitive resin layer, making the opaque wiring electrode pattern less visible. Examples of (b) resins having a phenolic hydroxyl group include novolac resins such as phenol novolac resins and cresol novolac resins, polymers of monomers having phenolic hydroxyl groups, and copolymers with styrene, acrylonitrile, acrylic monomers, etc. Two or more of these may be included.

[0042] Examples of the monomer having a phenolic hydroxyl group include 4-hydroxystyrene and hydroxyphenyl (meth)acrylate.

[0043] Among these, (b-1) an acrylic resin having a phenolic hydroxyl group and a carboxyl group (hereinafter, may be referred to as "(b-1) resin") and (b-2) a phenol novolac resin (hereinafter, may be referred to as "(b-2) resin") are preferred.

[0044] Examples of the developer used in the development step in the light-shielding pattern formation step described below include those exemplified below. In recent years, development using an aqueous sodium carbonate solution has been required in some cases because the change in alkali concentration over time during development is smaller than that with strong alkaline developers such as an aqueous tetramethylammonium hydroxide solution or an aqueous potassium hydroxide solution, and also from the standpoint of safety. Aqueous sodium carbonate solutions tend to have lower developability than other developers such as aqueous tetramethylammonium hydroxide solutions, but the inclusion of resin (b-1) can improve the developability relative to aqueous sodium carbonate solutions, which have smaller change in concentration over time.

[0045] The weight average molecular weight of the (b-1) resin is preferably 9,000 to 13,000.The acid value of the (b-1) resin is preferably 30 to 250 mgKOH / g from the viewpoint of solubility in a developer.

[0046] It is preferable to contain a (b-2) resin together with the (b-1) resin. By further containing the (b-2) resin, the positive photosensitive resin layer becomes more easily softened by heating, enabling transfer at low temperatures, thereby suppressing distortion of the transparent substrate due to heat. Furthermore, when an aqueous sodium carbonate solution is used as a developer, the developability of the (b-2) resin is lower than that of the (b-1) resin, making it possible to adjust the solubility in the developer.

[0047] The weight-average molecular weight of the (b-2) resin is preferably 100 to 1,500 from the viewpoint of transferring at a lower temperature. On the other hand, the weight-average molecular weight of the (b-2) resin is preferably 3,000 to 15,000 from the viewpoint of appropriately reducing the solubility in the developer. Two or more types of (b-2) resins having different weight-average molecular weights may be contained.

[0048] The mass ratio ((b-1) / (b-2)) of the content of the (b-1) resin to the content of the (b-2) resin is preferably 1.0 or more from the viewpoint of improving developability in an aqueous sodium carbonate solution. On the other hand, the mass ratio ((b-1) / (b-2)) is preferably 3.0 or less from the viewpoint of transferring at a lower temperature.

[0049] The content of the alkali-soluble resin in the positive photosensitive resin layer is preferably 45 to 65% by mass.

[0050] The positive photosensitive resin composition preferably further contains a benzotriazole-based compound. By containing a benzotriazole-based compound, the transferability of the positive photosensitive resin layer to the opaque wiring electrode pattern is further improved. In addition, corrosion of metal contained in the opaque wiring electrode pattern and ion migration can be suppressed. Among the benzotriazole-based compounds, carboxybenzotriazole is preferred from the viewpoint of improving transferability and because it volatilizes less during the heating step.

[0051] Examples of the solvent include those exemplified as solvents contained in the positive photosensitive composition in WO 2018 / 168325.

[0052] Examples of methods for applying the positive photosensitive resin composition onto the release film include spin coating using a spinner, spray coating, roll coating, screen printing, or coating using a slit coater, blade coater, die coater, calendar coater, meniscus coater, or bar coater. The coating thickness of the positive photosensitive resin composition is preferably set so that the thickness T1 of the positive photosensitive resin layer after drying falls within the preferred range described below.

[0053] When the positive photosensitive resin composition 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. Examples of the heating and drying device are preferably an oven, a hot plate, etc.

[0054] The thickness T1 [μm] of the positive photosensitive resin layer is preferably 0.3 or more, more preferably 0.5 or more, from the viewpoint of making the opaque wiring electrode pattern less visible. On the other hand, T1 [μm] is preferably 2.0 or less, from the viewpoint of reducing the development time and further improving processability. The thickness T1 [μm] of the positive photosensitive resin layer can be determined by measuring the thickness at five randomly selected locations using a stylus profilometer and calculating the average value.

[0055] Furthermore, it is preferable that the sum of the thickness T1 [μm] of the positive photosensitive resin layer and the thickness T2 [μm] of the opaque wiring electrode pattern is 1.5 to 10.0, and that T1 and T2 satisfy the following formula (1): 0.1 < T1 / (T1 + T2) < 0.5 (1) By making the sum of T1 [μm] and T2 [μm] 1.5 or more and satisfying the above formula (1), the conductivity can be further improved and the opaque wiring electrode pattern can be made less visible. The sum of T1 [μm] and T2 [μm] is more preferably 2.0 or more. On the other hand, by making the sum of T1 [μm] and T2 [μm] 10.0 or less and satisfying the above formula (1), when the wiring electrode-equipped substrate has an overcoat layer, unevenness on the transparent substrate can be reduced and the generation of bubbles due to the unevenness when the overcoat layer is laminated can be suppressed. The sum of T1 [μm] and T2 [μm] is more preferably 5.0 or less, and even more preferably 3.5 or less.

[0056] A light-shielding layer is formed by transferring a positive-type photosensitive resin layer containing a light-shielding component onto the surface of a transparent substrate on which an opaque wiring electrode pattern is formed. Examples of transfer methods include thermocompression bonding of a dry film obtained by the above-described method so that the positive-type photosensitive resin layer is in contact with the transparent substrate. The thermocompression bonding temperature is preferably 70°C or higher, more preferably 100°C or higher, from the viewpoint of improving transferability. On the other hand, the thermocompression bonding temperature is preferably 150°C or lower, from the viewpoint of suppressing thermal deactivation of the photosensitizer (dissolution inhibitor). For example, the light-shielding layer does not need to be transferred to areas where the opaque wiring electrode pattern is desired to be exposed, such as pad portions and terminal portions, to ensure electrical connection with external elements. Furthermore, the light-shielding layer does not need to be transferred to openings in the opaque wiring electrode pattern. By not transferring the transfer layer to openings in the opaque wiring electrode pattern, the time required for developing the light-shielding layer can be further shortened and processability can be further improved.

[0057] Next, the release film is peeled off as needed. When exposure is performed through the release film in the light-shielding pattern forming step described below, the release film may be peeled off after exposure.

[0058] Next, in the light-shielding pattern forming step, the light-shielding layer is exposed using the opaque wiring electrode pattern as a mask and developed to form light-shielding patterns in areas corresponding to the opaque wiring electrode pattern. By exposing using the opaque wiring electrode pattern as a mask, light-shielding patterns corresponding to areas corresponding to the opaque wiring electrode pattern can be formed without the need for a separate exposure mask. When the opaque wiring electrode pattern forming step includes a step of forming a first opaque wiring electrode pattern on one side of a transparent substrate, a step of forming an insulating layer on the first opaque wiring electrode pattern, and a step of forming a second opaque wiring electrode pattern on the insulating layer, it is preferable to form light-shielding patterns in areas corresponding to the first opaque wiring electrode pattern and the second opaque wiring electrode pattern.

[0059] The exposure is preferably performed from the side opposite to the side on which the opaque wiring electrode pattern is formed, regardless of the side on which the opaque wiring electrode pattern is formed. Furthermore, for example, when it is necessary to ensure electrical continuity with external elements, such as pad portions and terminal portions, and the light-shielding layer is removed from a portion where the opaque wiring electrode pattern is to be exposed, the exposure may be performed from the side on which the light-shielding layer is formed using an exposure mask.

[0060] The exposure light preferably emits light in the ultraviolet region, i.e., in the wavelength region of 200 nm to 450 nm, which matches the absorption wavelength of the photosensitizer (dissolution inhibitor) contained in the light-shielding layer. Examples of light sources for obtaining such exposure light include mercury lamps, halogen lamps, xenon lamps, LED lamps, semiconductor lasers, and KrF or ArF excimer lasers. Among these, the i-line (wavelength 365 nm) of a mercury lamp and LED lamps are preferred. The exposure light may be applied to the substrate while it is stationary, or may be applied to the substrate while it is being transported over the light source in a direction such that the exposure light is applied to the surface opposite the surface on which the light-shielding layer is formed.

[0061] The exposed light-shielding layer is developed to remove the exposed portions, thereby forming a light-shielding pattern in the area corresponding to the opaque wiring electrode pattern.

[0062] The developer is preferably one that does not inhibit the conductivity of the opaque wiring electrode pattern, and is preferably an alkaline developer. Examples of alkaline developers include those exemplified as developers in WO 2018 / 168325. As mentioned above, in recent years, aqueous sodium carbonate solutions have been preferably used, which are highly safe and exhibit little change in alkali concentration over time during development.

[0063] Examples of the developing method include a method of spraying a developer onto the surface of the light-shielding layer while the substrate is left standing or rotated, a method of immersing the light-shielding layer in a developer, and a method of applying ultrasonic waves to the light-shielding layer while immersing it in a developer.

[0064] The light-shielding pattern obtained by the development step may be subjected to a rinse treatment with a rinse liquid. Examples of the rinse liquid include those exemplified as rinse liquids in WO 2018 / 168325.

[0065] The obtained light-shielding pattern may be further heated at 100°C to 300°C. Heating increases the hardness of the light-shielding pattern, suppresses chipping or peeling due to contact with other members, and improves adhesion to the opaque wiring electrode pattern. Examples of heating methods include heating with an oven, an inert oven, or a hot plate, and heating with electromagnetic waves such as an infrared heater.

[0066] The method may include a step of forming an overcoat layer on the light-shielding pattern of the obtained substrate with wiring electrodes. Examples of the overcoat layer include an insulating layer and an adhesive layer having adhesiveness. Two or more of these may be laminated. Examples of methods for forming the insulating layer include the methods exemplified in International Publication No. 2018 / 168325. Examples of methods for forming the adhesive layer include a method of laminating a transparent adhesive film onto the light-shielding pattern using a rubber roller or the like.

[0067] Next, a black transfer film that is preferably used as a dry film in the step of forming a light-shielding layer by transferring a positive photosensitive resin layer in the method for producing a substrate with wiring electrodes of the present invention will be described.

[0068] The black transfer film has a positive photosensitive resin layer containing (a) a black pigment, (b) a resin having a phenolic hydroxyl group, and (c) a quinone diazide compound on a release film.

[0069] Examples of the release film include those exemplified as the release film in the light-shielding layer forming step using a dry film in the above-described method for producing a substrate with wiring electrodes of the present invention.

[0070] Examples of the positive photosensitive resin layer include those exemplified as the positive photosensitive resin layer in the above-mentioned method for producing a substrate with wiring electrodes of the present invention.

[0071] (a) The black pigment may be either an organic pigment or an inorganic pigment. Examples of organic pigments include soluble azo pigments, insoluble azo pigments, metal complex azo pigments, phthalocyanine pigments, and condensed polycyclic pigments. Examples of inorganic pigments include carbon black, graphite, pine soot, iron oxides such as iron black, hematite, goethite, and magnetite, titanium, chromium, lead, and metal composites thereof. Two or more of these may be contained. The content of the black pigment in the positive photosensitive resin layer is preferably 5 to 30% by mass.

[0072] As the (b) resin having a phenolic hydroxyl group, the above-mentioned (b-1) resin and (b-2) resin are preferred, and the preferred range of the mass ratio of their contents is also as described above.

[0073] The thickness T1 [μm] of the positive photosensitive resin layer is preferably 0.3 or more, more preferably 0.5 or more, from the viewpoint of making the opaque wiring electrode pattern less visible in the method for producing a substrate with wiring electrodes. On the other hand, T1 [μm] is preferably 2.0 or less, from the viewpoint of reducing the development time and further improving processability in the method for producing a substrate with wiring electrodes.

[0074] The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.

[0075] The materials used in each example are as follows: The transmittance of the transparent substrate at a wavelength of 365 nm was measured using an ultraviolet-visible spectrophotometer (U-3310, manufactured by Hitachi High-Technologies Corporation).

[0076] (Production Example 1: Acrylic Resin Having Carboxy Groups) 150 g of diethylene glycol monoethyl ether acetate (hereinafter "DMEA") was charged into a reaction vessel under a nitrogen atmosphere and heated to 80°C using an oil bath. To this was added dropwise 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 over 1 hour. After completion of the dropwise addition, the mixture was stirred for an additional 6 hours to allow the polymerization reaction to proceed. Thereafter, 1 g of hydroquinone monomethyl ether was added to terminate 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 completed, the mixture was stirred for an additional 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 carboxy groups with a copolymerization ratio (by mass): EA / 2-EHMA / St / GMA / AA=20 / 40 / 20 / 5 / 15. The acid value of the resulting acrylic resin having carboxy groups was measured in accordance with JIS K 0070 (1992) and found to be 103 mgKOH / g. The weight-average molecular weight of the resulting acrylic resin having carboxy groups was 17,000.

[0077] (Production Example 2: Acrylic Resin Having Phenolic Hydroxyl Groups and Carboxy Groups) 150 g of 2-methoxy-1-methylethyl acetate (hereinafter "PMA") was charged into a reaction vessel under a nitrogen atmosphere and heated to 80°C using an oil bath. To this was added dropwise a mixture consisting of 20 g of EA, 20 g of 2-EHMA, 20 g of 4-hydroxystyrene (hereinafter "HS"), 15 g of N-methylolacrylamide (hereinafter "MAA"), 25 g of AA, 0.8 g of 2,2'-azobisisobutyronitrile, and 10 g of PMA over 1 hour. After completion of the dropwise addition, the mixture was heated and stirred at 80°C for an additional 6 hours to carry out a polymerization reaction. Thereafter, 1 g of hydroquinone monomethyl ether was added to terminate 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 groups and carboxy 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 1 and was found to be 153 mgKOH / g. The weight-average molecular weight of the resulting acrylic resin having phenolic hydroxyl groups and carboxy groups was 10,000.

[0078] (Production Example 3: Photosensitive conductive paste (D-1)) Into a 100 mL clean bottle were placed 17.5 g of the acrylic resin having a carboxy group obtained in Production Example 1, 0.5 g of a photopolymerization initiator N-1919 (manufactured by ADEKA Corporation), 1.5 g of an epoxy resin "ADEKA RESIN (registered trademark)" EP-4530 (epoxy equivalent 190, manufactured by ADEKA Corporation), 3.5 g of a diacrylate "Light Acrylate (registered trademark)" BP-4EA (manufactured by Kyoeisha Chemical Co., Ltd.), and 19.0 g of DMEA, and these were mixed using "Awatori MIXER (registered trademark)" ARE-310 (manufactured by THINKY Corporation) to obtain 42.0 g of a resin solution. The resulting 42.0 g of resin solution was mixed with 62.3 g of Ag particles having an average particle size of 0.3 μm and kneaded using a three-roller EXAKT M50 (manufactured by EXAKT), and then 7 g of DMEA was added and mixed to obtain 111.3 g of photosensitive conductive paste (D-1). The viscosity of the resulting photosensitive conductive paste (D-1) was measured using a Brookfield viscometer at a temperature of 25°C and a rotation speed of 3 rpm, and was found to be 10,000 mPa s.

[0079] (Production Example 4: Photosensitive conductive paste (D-2)) Into a 100 mL clean bottle were placed 3.0 g of the acrylic resin having a carboxy group obtained in Production Example 1, 0.3 g of a photopolymerization initiator N-1919 (manufactured by ADEK Corporation), 1.2 g of diacrylate "Light Acrylate (registered trademark)" BP-4EA, 0.5 g of a dispersant "BYK (registered trademark)"-LP21116 (manufactured by BYK-Chemie), 79.0 g of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA"), and 16.0 g of silver fine particles (manufactured by Nisshin Engineering Inc.) having an average surface carbon coating layer thickness of 1 nm and a particle size of 40 nm, and mixed using "Awatori Rentaro (registered trademark)" ARE-310 (manufactured by Thinky Corporation) to obtain 100.0 g of photosensitive conductive paste (D-2). The viscosity of the obtained photosensitive conductive paste (D-2) was measured using an E-type viscometer at a temperature of 25° C. and a rotation speed of 100 rpm, and was found to be 3 mPa·s.

[0080] (Production Example 5: Quinone diazide compound) Under a dry nitrogen stream, 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 diazide sulfonyl acid chloride were dissolved in 450 g of 1,4-dioxane and the solution was brought to room temperature. To this was added dropwise 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane so that the temperature in the system did not exceed 35°C. After the dropwise addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried in a vacuum dryer to obtain a quinone diazide compound.

[0081] (Production Example 6: Positive-type photosensitive resin composition (E-1)) Into a 100 mL clean bottle were placed 3.42 g of phenol novolak resin WR-104 (manufactured by DIC Corporation, weight-average molecular weight: 6900), 0.88 g of the quinone diazide compound obtained in Production Example 5, 0.17 g of crosslinking agent "Nicalac (registered trademark)" MW-390 (manufactured by Sanwa Chemical Co., Ltd.), 0.22 g of carboxybenzotriazole "VERZONE (registered trademark)" C-BTA (manufactured by Daiwa Chemical Industry Co., Ltd.), 0.01 g of leveling agent "BYK (registered trademark)"-331 (manufactured by BYK-Chemie), and 44.20 g of PGMEA, and these were mixed using a rotation-revolution vacuum mixer "Awatori Rentaro (registered trademark)" ARE-310 (manufactured by Thinky Corporation) to obtain 48.90 g of a resin solution. The obtained 48.90 g of resin solution, 0.66 g of carbon black MA100 (manufactured by Mitsubishi Chemical Corporation), and 0.44 g of dispersant "BYK"-LP21116 (manufactured by BYK-Chemie) were mixed together, and the mixture was kneaded using an Ultra Apex Mill (manufactured by Kotobuki Industries Co., Ltd.) equipped with a centrifugal separator filled with 70% by volume of 0.05 mmφ zirconia beads (manufactured by Toray Industries, Inc.), to obtain 50.0 g of a positive photosensitive resin composition (E-1).

[0082] (Production Example 7: Positive-type photosensitive resin composition (E-2)) A positive-type photosensitive resin composition (E-2) was obtained in the same manner as in Production Example 6, except that 3.42 g of phenol novolak resin WR-104 (manufactured by DIC Corporation) was changed to 2.54 g of phenol novolak resin WR-104 (manufactured by DIC Corporation) and 0.88 g of the acrylic resin having a phenolic hydroxyl group and a carboxyl group obtained in Production Example 2.

[0083] (Production Example 8: Positive-type photosensitive resin composition (E-3)) A positive-type photosensitive resin composition (E-3) was obtained in the same manner as in Production Example 6, except that 3.42 g of phenol novolac resin WR-104 (manufactured by DIC Corporation) was changed to 2.10 g of phenol novolac resin WR-104 (manufactured by DIC Corporation) and 1.31 g of the acrylic resin having a phenolic hydroxyl group and a carboxy group obtained in Production Example 2.

[0084] (Production Example 9: Positive-type photosensitive resin composition (E-4)) A positive-type photosensitive resin composition (E-4) was obtained in the same manner as in Production Example 6, except that 3.42 g of phenol novolac resin WR-104 (manufactured by DIC Corporation) was changed to 2.84 g of phenol novolac resin WR-104 (manufactured by DIC Corporation) and 0.58 g of the acrylic resin having a phenolic hydroxyl group and a carboxyl group obtained in Production Example 2.

[0085] (Production Example 10: Positive-type photosensitive resin composition (E-5)) A positive-type photosensitive resin composition (E-5) was obtained in the same manner as in Production Example 6, except that 3.42 g of phenol novolac resin WR-104 (manufactured by DIC Corporation) was changed to 1.55 g of phenol novolac resin WR-104 (manufactured by DIC Corporation) and 1.86 g of the acrylic resin having a phenolic hydroxyl group and a carboxy group obtained in Production Example 2.

[0086] (Production Example 11: Positive-type photosensitive resin composition (E-6)) A positive-type photosensitive resin composition (E-6) was obtained in the same manner as in Production Example 6, except that 3.42 g of phenol novolak resin WR-104 (manufactured by DIC Corporation) was changed to 3.42 g of the acrylic resin having a phenolic hydroxyl group and a carboxyl group obtained in Production Example 2.

[0087] The evaluations in each of the examples and comparative examples were carried out by the following methods.

[0088] (1) Thickness of Positive Photosensitive Resin Layer The thickness of the positive photosensitive resin layer of the black transfer film obtained in Reference Examples 1 to 11 was measured at five randomly selected locations using a stylus-type step gauge "Surfcom" (registered trademark) 1400 (manufactured by Tokyo Seimitsu Co., Ltd.), and the average value was calculated. For Comparative Examples 1 and 3, the cross section of the light-shielding layer formed on the opaque wiring electrode pattern in the <Light-shielding layer formation step> was observed by SEM, and the thickness was measured at five randomly selected locations, and the average value was calculated.

[0089] (2) Thickness, Line Width, and Light Transmittance of Opaque Wiring Electrode Patterns For the opaque wiring electrode patterns formed in the <Opaque wiring electrode pattern forming process> in Examples 1 to 16 and Comparative Examples 1 to 4, the thickness was measured at five randomly selected locations using a stylus-type step profiler "Surfcom" (registered trademark) 1400 (manufactured by Tokyo Seimitsu Co., Ltd.), and the average value was calculated. Furthermore, the line width of five randomly selected fine line pattern portions was measured using an optical microscope, and the average value was calculated. However, in Examples 2 and 9, the measurements were performed on the patterns after rinsing. Furthermore, the light transmittance at wavelengths of 365 nm and 550 nm was measured using a microsurface spectrophotometer (VSS 400: manufactured by Nippon Denshoku Industries Co., Ltd.) for the portion corresponding to the pad portion 6 of the visibility and conductivity evaluation pattern shown in FIG. 4 .

[0090] (3) Developability For the positive-type photosensitive resin layers exposed in the <Light-shielding pattern forming step> in Examples 1 to 16 and Comparative Examples 1 and 3, the time required for the transparent substrate in the exposed area to be completely exposed by development using a 2.38 mass % aqueous solution of tetramethylammonium hydroxide (TMAH) as a developer was measured.

[0091] (4) Exposure Sensitivity In the <Light-shielding pattern forming step> in Examples 1 to 16 and Comparative Examples 1 to 4, the development time with a 2.38 mass % TMAH aqueous solution was set to 50 seconds, and the exposure sensitivity was evaluated as the minimum exposure amount that could dissolve the photosensitive resin layer in the exposed area.

[0092] (5) Sodium Carbonate Developability In the evaluation of developability in (3) above, a 5.0 mass % sodium carbonate aqueous solution was used as the developer instead of the 2.38 mass % TMAH aqueous solution, and the time required for the transparent substrate in the exposed area to be completely exposed was measured. However, if the transparent substrate was not completely exposed within 180 seconds, it was evaluated as "NG".

[0093] (6) Difficulty in Visibility For the substrates with wiring electrodes obtained in Examples 1 to 16 and Comparative Examples 1 to 4, a black film was placed on the side opposite to the surface on which the opaque wiring electrode pattern was formed, and then light was projected onto the substrates with wiring electrodes using a projector. Ten people each visually inspected the substrate from a distance of 30 cm to evaluate whether the mesh-like electrode portion was visible. The difficulty in visibility was evaluated based on the number of people who were able to see the mesh-like electrode portion.

[0094] (7) Conductivity A resistance tester was used to measure the resistance between terminals of the substrates with wiring electrodes obtained in Examples 1 to 16 and Comparative Examples 1 to 4. The distance between the terminals was 17 mm, the width was 15 mm, and the pad portion 6 was 2 mm long and 15 mm wide.

[0095] (8) Overcoat processability Three types of transparent adhesive films, "LUCIACS (registered trademark)" CS9861UAS (tape thickness 25 μm), "LUCIACS (registered trademark)" CS9862UAS (tape thickness 50 μm), and "LUCIACS (registered trademark)" CS9863UAS (tape thickness 75 μm) (all manufactured by Nitto Denko Corporation), were prepared, and after peeling off the carrier film on one side, they were attached using a rubber roller to the opaque wiring electrode pattern-forming surface of the wiring electrode-attached substrates obtained in Examples 1 to 16 and Comparative Examples 1 to 4. The presence or absence of bubbles was observed using an optical microscope (Keyence Corporation, VHX-6000). The case where no bubbles were observed in all three types was evaluated as "A", the case where bubbles were observed in one type was evaluated as "B", and the case where bubbles were observed or generated in two or more types was evaluated as "C".

[0096] (9) Transferability In Examples 1 to 16, the transfer temperatures in the <Light-shielding layer forming step> were set to 90°C, 100°C, and 110°C, and the transferability was evaluated from the minimum transfer temperature at which the film could be transferred onto the opaque wiring electrode pattern without any gaps.

[0097] Reference Example 1 A non-silicone release agent AL-5 (manufactured by Lintec Corporation) was applied to one side of a PET film "Lumirror (registered trademark)" FB40 (manufactured by Toray Industries, Inc.) (thickness: 16 μm), followed by heat treatment and drying to form a release layer having a thickness of 100 nm on the surface of the substrate, thereby obtaining a release film. For the obtained release film, an acrylic adhesive tape "31B" manufactured by Nitto Denko Corporation was attached to the surface on which the release layer was formed using a 2 kg roller. After leaving it to stand for 30 minutes, the peel force was measured when peeled at a peel angle of 180° and a peel speed of 0.3 m / min, and was found to be 1,480 mN / 20 mm.

[0098] The positive photosensitive resin composition (E-1) obtained in Production Example 6 was applied to the release layer surface of the obtained release film using a coater so that the thickness after drying would be 0.7 μm, and the coating was dried at 80° C. for 4 minutes to form a positive photosensitive resin layer, thereby obtaining a black transfer film (F-1).

[0099] (Reference Examples 2 to 11) Black transfer films (F-2) to (F-11) were obtained in the same manner as in Example 1, except that the type of the positive photosensitive resin composition forming the positive photosensitive resin layer and the thickness of the positive photosensitive resin layer were changed as shown in Table 1.

[0100]

[0101] Example 1 <Process for Forming an Opaque Wiring Electrode Pattern> The photosensitive conductive paste (D-1) obtained in Production Example 3 was printed by screen printing on one side of a PET film "Lumirror (registered trademark)" T60 (manufactured by Toray Industries, Inc., thickness: 75 μm, transmittance at a wavelength of 365 nm: 77%, transmittance at a wavelength of 550 nm: 89%) so that the thickness after drying would be 1.6 μm, and the paste was dried at 100° C. for 10 minutes. An exposure device (PEM-6M; manufactured by Union Optical Co., Ltd.) was used to expose the paste to an exposure dose of 500 mJ / cm through an exposure mask having a pad portion 6 and a mesh-shaped fine line pattern portion 7 shown in FIG. 4 .２ The pattern was exposed to a wavelength of 365 nm (equivalent to a wavelength of 365 nm). The mesh-shaped pattern shown in FIG. 5 had a mesh pitch P of 150 μm and a mesh angle θ of 90°, and was a negative pattern having openings 9 with a width of 4 μm and light-shielding portions 8. The pattern was then immersed in a 0.2% by mass aqueous sodium carbonate solution for 30 seconds as a developer, rinsed with ultrapure water, and cured in an IR heater furnace at 140° C. for 30 minutes to form an opaque wiring electrode pattern. The line width and thickness of the opaque wiring electrode pattern were measured using the above-mentioned method, resulting in a line width of 6 μm and a thickness of 1.6 μm. The light transmittance at wavelengths of 365 nm and 550 nm was also measured using the above-mentioned method, and both were 1%.

[0102] <Light-shielding layer forming step> The black transfer film (F-1) obtained in Reference Example 1 was thermocompressed onto the obtained opaque wiring electrode pattern at 110°C and a speed of 0.2 m / min so that the positive photosensitive resin layer of the black transfer film (F-1) was in contact with the obtained opaque wiring electrode pattern, and the release film was peeled off.

[0103] <Light-shielding pattern forming step> Using the opaque wiring electrode pattern as a mask, an exposure device (PEM-6M) was used to expose the opaque wiring electrode pattern from the side opposite the surface on which the pattern was formed to an exposure dose of 100 J / cm (equivalent to a wavelength of 365 nm). ２ , 300 J / cm ２ , 500 J / cm ２ , 1,000J / cm ２ , 2,000J / cm ２ , 4,000mJ / cm ２ Thereafter, the positive photosensitive dry film was exposed to light from the transfer surface side using an exposure device (PEM-6M) through an exposure mask that shielded the areas other than those corresponding to the pad portions of the opaque wiring electrode pattern. ２ The substrate was exposed to light at a wavelength of 365 nm. Development was then performed using a 2.38% by mass aqueous solution of TMAH as a developer until the exposed transparent substrate was exposed, forming a light-shielding pattern on top of the opaque wiring electrode pattern. The substrate was then heated in a box oven at 140° C. for 60 minutes to obtain a substrate with wiring electrodes.

[0104] Example 2 <Opaque Wiring Electrode Pattern Formation Process> A copper film was formed on one surface of a PET film "Lumirror (registered trademark)" T60 (manufactured by Toray Industries, Inc.) by vapor deposition to a thickness of 2.5 μm. Next, resist LC-140 (manufactured by Rohm and Haas Electronic Materials Co., Ltd.) was applied onto the copper film by spin coating and dried at 100° C. for 5 minutes. Next, an exposure device (PEM-6M; manufactured by Union Optical Co., Ltd.) was used to apply an exposure mask having a pad portion 6 and a mesh-shaped fine line pattern portion 7 shown in FIG. 4 at an exposure dose of 45 mJ / cm. ２ The pattern was exposed to light at a wavelength of 365 nm (equivalent to a wavelength of 365 nm). Here, the mesh-shaped pattern shown in FIG. 6 had a mesh pitch P of 150 μm and a mesh angle θ of 90°, and was a positive pattern having openings 9 and light-shielding portions 8 with a light-shielding width of 16 μm. Thereafter, immersion development was performed for 30 seconds using a 2.38 mass% TMAH aqueous solution as the developer, followed by rinsing with ultrapure water for 30 seconds. Next, etching was performed using a ferric chloride aqueous solution to reduce the line width to 6 μm, and then rinsing with ultrapure water for 30 seconds. Next, immersion development was performed for 4 minutes using resist stripper JELK-101 (manufactured by Kanto Chemical Co., Ltd.), followed by rinsing with ultrapure water for 30 seconds to form an opaque wiring electrode pattern. The line width and thickness of the opaque wiring electrode pattern were measured using the above-mentioned method, and the line width was 4 μm and the thickness was 2.5 μm. Furthermore, when the light transmittance at wavelengths of 365 nm and 550 nm was measured using the above-mentioned method, both were 0%.

[0105] The <light-shielding layer forming step> and <light-shielding pattern forming step> were carried out in the same manner as in Example 1 to obtain a substrate with wiring electrodes.

[0106] Example 3 A substrate with wiring electrodes was obtained in the same manner as in Example 1, except that the opening width of the exposure mask used in the <opaque wiring electrode pattern forming step> was changed to 10 μm.

[0107] (Example 4) <Process for forming an opaque wiring electrode pattern> The photosensitive conductive paste (D-2) obtained in Production Example 4 was applied by spin coating to one surface of alkali-free glass "AN Wizus" (registered trademark) (manufactured by AGC Corporation, transmittance at a wavelength of 365 nm: 91%, transmittance at a wavelength of 550 nm: 92%) so as to have a thickness of 1 μm after drying, and dried at 90° C. for 8 minutes. Using an exposure device (PEM-6M; manufactured by Union Optical Co., Ltd.) and an exposure mask having a pad portion 6 and a mesh-shaped fine line pattern portion 7 shown in FIG. 4, an exposure dose of 150 mJ / cm was applied. ２ The pattern was exposed to light at a wavelength of 365 nm (equivalent to a wavelength of 365 nm). The mesh-shaped pattern shown in FIG. 5 had a mesh pitch P of 150 μm and a mesh angle θ of 90°, and was a negative pattern having openings 9 with a width of 6 μm and light-shielding portions 8. The pattern was then developed using a 0.1% by mass aqueous TMAH solution as a developer for twice the time it took for the exposed portions to dissolve. The pattern was then rinsed with ultrapure water for 30 seconds and cured in a box oven at 240°C for 60 minutes to form an opaque wiring electrode pattern. The line width and thickness of the opaque wiring electrode pattern were measured using the above-mentioned method, resulting in a line width of 6 μm and a thickness of 0.5 μm. Furthermore, the light transmittance at wavelengths of 365 nm and 550 nm was measured using the above-mentioned method, and both were 0%.

[0108] <Light-shielding layer forming process> A light-shielding layer was formed on the formed wiring electrode pattern in the same manner as in Example 1, except that the black transfer film (F-2) obtained in Reference Example 2 was used instead of the black transfer film (F-1) obtained in Reference Example 1.

[0109] The <Light-shielding pattern forming step> was carried out in the same manner as in Example 1 to obtain a substrate with wiring electrodes.

[0110] Examples 5, 7-8, 10-11 Substrates with wiring electrodes were obtained in the same manner as in Example 1, except that the black transfer film used in the <light-shielding layer forming step> was changed as shown in Tables 2 and 3.

[0111] Example 6 A substrate with wiring electrodes was obtained in the same manner as in Example 4, except that the black transfer film used in the <Light-shielding layer forming step> was changed as shown in Table 2.

[0112] Example 9 A substrate with wiring electrodes was obtained in the same manner as in Example 2, except that the black transfer film used in the <Light-shielding layer forming step> was changed as shown in Table 3.

[0113] (Examples 12 to 16) Substrates with wiring electrodes were obtained in the same manner as in Example 1, except that the black transfer film used in the <Light-shielding layer forming step> was changed as shown in Tables 3 and 4, and a 5.0 mass % aqueous sodium carbonate solution was used as the developer instead of the 2.38 mass % aqueous TMAH solution in the <Light-shielding pattern forming step>.

[0114] Comparative Example 1 A substrate with wiring electrodes was obtained in the same manner as in Example 1, except that in the <light-shielding layer forming step>, the positive photosensitive resin composition (E-1) obtained in Production Example 6 was applied by spin coating onto the opaque wiring electrode pattern so that the thickness after drying in the areas where the opaque wiring electrode pattern was not formed was 2.6 μm, and then dried at 100° C. for 10 minutes to form a light-shielding layer. The thickness of the light-shielding layer was measured by the method described above and was found to be 1.0 μm.

[0115] Comparative Example 2 A substrate with wiring electrodes was obtained in the same manner as in Example 1, except that the <light-shielding layer forming step> and the <light-shielding pattern forming step> were not performed.

[0116] (Comparative Example 3) A substrate with wiring electrodes was obtained in the same manner as in Example 2, except that in the <light-shielding layer forming step>, the positive photosensitive resin composition (E-1) obtained in Production Example 6 was applied by spin coating onto the opaque wiring electrode pattern so that the thickness after drying in the areas where the opaque wiring electrode pattern was not formed would be 2.6 μm, and then dried at 100° C. for 10 minutes to form a light-shielding layer. The thickness of the light-shielding layer was measured by the method described above and was found to be 0.3 μm.

[0117] Comparative Example 4 A substrate with wiring electrodes was obtained in the same manner as in Example 2, except that the <light-shielding layer forming step> and the <light-shielding pattern forming step> were not performed.

[0118] The evaluation results of each of the Examples and Comparative Examples are shown in Tables 2 to 4.

[0119]

[0120]

[0121]

[0122] 1: Transparent substrate 2: Opaque wiring electrode pattern 3: Light-shielding pattern 4: Insulating layer 5: Light-shielding layer 6: Pad portion 7: Fine line pattern portion P: Mesh pitch θ: Mesh angle L: Line length 8: Light-shielding portion 9: Opening

Claims

1. A process of forming an opaque wiring electrode pattern on at least one side of a transparent substrate, A step of forming a light-shielding layer on the opaque wiring electrode pattern forming surface of the transparent substrate by transferring a positive-type photosensitive resin layer containing a light-shielding component, and A step of forming a light-shielding pattern in the area corresponding to the opaque wiring electrode pattern by exposing the light-shielding layer to the opaque wiring electrode pattern and developing it, using the opaque wiring electrode pattern as a mask. A method for manufacturing a substrate with wiring electrodes having the same properties.

2. The method for manufacturing a substrate with wiring electrodes according to claim 1, wherein the thickness T1 [μm] of the positive-type photosensitive resin layer is 0.3 to 2.

0.

3. A method for manufacturing a substrate with wiring electrodes according to claim 1 or 2, wherein the sum of the thickness T1 [μm] of the positive-type photosensitive resin layer and the thickness T2 [μm] of the opaque wiring electrode pattern is 1.5 to 10.0, and T1 and T2 satisfy the following formula (1). 0.1<T1 / (T1+T2)<0.5 (1)

4. The method for manufacturing a substrate with wiring electrodes according to claim 1 or 2, wherein the sum of the thickness T1 [μm] of the positive photosensitive resin layer and the thickness T2 [μm] of the opaque wiring electrode pattern is 1.5 to 3.5, and T1 and T2 satisfy the following formula (1). 0.1<T1 / (T1+T2)<0.5 (1)

5. A method for manufacturing a substrate with wiring electrodes according to claim 1 or 2, wherein the thickness T2 [μm] of the opaque wiring electrode pattern is 1.0 to 5.

0.

6. The method for manufacturing a substrate with wiring electrodes according to claim 1 or 2, wherein the positive-type photosensitive resin layer contains (b-1) an acrylic resin having a phenolic hydroxyl group and a carboxyl group.

7. The method for manufacturing a substrate with wiring electrodes according to claim 6, wherein the positive-type photosensitive resin layer further contains (b-2) phenol novolac resin.

8. The method for manufacturing a substrate with wiring electrodes according to claim 7, wherein the mass ratio ((b-1) / (b-2)) of the content of the (b-2) phenol novolac resin in the positive-type photosensitive resin layer to the content of the (b-2) acrylic resin is 1.0 or more and 3.0 or less.

9. The method for manufacturing a substrate with wiring electrodes according to claim 1 or 2, wherein the line width of the opaque wiring electrode pattern is 1 to 10 μm.

10. The method for manufacturing a substrate with wiring electrodes according to claim 1 or 2, wherein the substrate with wiring electrodes has at least a fine line pattern portion, and in the fine line pattern portion, the ratio of the area on which the opaque wiring electrode pattern is formed to the entire transparent substrate is 20 area % or less.

11. The method for manufacturing a substrate with wiring electrodes according to claim 1 or 2, wherein the light transmittance of the opaque wiring electrode pattern at a wavelength of 365 nm is 15% or less.

12. A method for manufacturing a substrate with wiring electrodes according to claim 1 or 2, wherein the opaque wiring electrode pattern comprises silver and / or copper.