TWI896698B - Method of forming metal pattern and method of manufacturing metal mask for vapor deposition - Google Patents

Abstract

A method for forming a metal pattern and a method for manufacturing a metal mask for evaporation having a metal pattern obtained by using the metal pattern forming method, the metal pattern forming method comprising: preparing a laminate having a negative photosensitive resin layer on a substrate; irradiating the negative photosensitive resin layer with a directional exposure light from the side opposite to the side on which the substrate is provided; The steps include: exposing the negative photosensitive resin layer in a patterned manner through the exposure mask with light component incident obliquely in the thickness direction of the light mask; developing the negative photosensitive resin layer exposed in the patterned manner to form a resin pattern having a tapered shape; and forming a metal pattern having a tapered shape corresponding to the shape of the resin pattern.

Description

Method for forming metal pattern and method for manufacturing metal mask for evaporation

The present invention relates to a method for forming a metal pattern and a method for manufacturing a metal mask for evaporation.

In display devices with touch panels, such as electrocapacitive input devices (organic electroluminescent (EL) displays and liquid crystal displays), a conductive layer pattern, including the electrode pattern of the sensor corresponding to the visual perception area, the edge wiring portion, and the wiring for the lead-out portion, is provided within the touch panel. Typically, because forming a patterned layer requires fewer steps to achieve the desired pattern shape, a method is widely used in which a layer of a photosensitive resin composition is deposited on an arbitrary substrate using a photosensitive transfer member, exposed through a mask having the desired pattern, and then developed. A known method for forming pixels in an organic EL display device involves placing a metal mask (evaporation mask) containing through-holes in close contact with an organic EL display substrate, placing the mask in an evaporation apparatus, and then evaporating an organic material to form the pixels.

Conventional methods for manufacturing metal masks are known, such as those described in Japanese Patent Application Laid-Open No. 2006-152396 or Japanese Patent Application Laid-Open No. 2017-226918. Japanese Patent Application Publication No. 2006-152396 describes a method for manufacturing a metal mask. The method is characterized in that: in a method for manufacturing a metal mask based on a mask master for electrocasting, a first substrate coated with a resist is sequentially exposed using a plurality of photomasks having similar transfer patterns formed in predetermined shapes and then developed. A predetermined shaped protrusion having inclined sidewalls is formed on the first substrate. A first conductive film is formed over the entire surface of the first substrate on the side where the predetermined shaped protrusion is formed. Metal is deposited on the upper surface of the first conductive film by electroplating. The deposited metal is peeled off from the first conductive film to produce a metal mask having a predetermined shape. A master master having predetermined-shaped recesses is used. On the conductive upper surface of a second substrate, convex portions substantially identical to the predetermined-shaped convex portions are formed using a resin based on the predetermined-shaped recesses of the master master. The second substrate having the resin-based convex portions is peeled off from the master master to produce the electrocasting mask master. A desired metal film is deposited and formed by electroplating on the second conductive film exposed to the electrocasting mask master until a thickness is achieved in which openings having sidewalls substantially identical to the inclined sidewalls of the predetermined-shaped recesses of the mask master are formed. The electrocasting mask master is then peeled off from the electrocasting mask master.

Japanese Patent Application Publication No. 2017-226918 describes a method for manufacturing a fine metal mask using an electrocasting and electroplating method. The method comprises: (a) preparing a carrier glass and evaporating a sacrificial layer on the carrier glass; (b) evaporating an electrode metal for electrocasting and electroplating to form an electrode layer; (c) coating the electrode layer with a photoresist; (d) exposing and developing the photoresist using a photolithography method to perform patterning; and (e) applying a patterned photoresist to the patterned photoresist. (f) forming a metal pattern by removing the photoresist; (g) forming a mask pattern on the electrode layer by forming a pattern corresponding to the metal pattern; (h) performing a heat treatment to improve the toughness of the patterned electroplated layer and the electrode layer; (i) inspecting the electroplated layer and the mask pattern formed on the electrode layer; and (j) separating the electroplated layer and the electrode layer from the carrier glass.

Japanese Patent Application Laid-Open No. 2019-173181 is a known example of a conventional evaporation mask with a substrate. Japanese Patent Application Laid-Open No. 2019-173181 describes an evaporation mask with a substrate, characterized by comprising a glass substrate and a plurality of evaporation masks formed on the substrate by electroplating and comprising an electroplated layer having a porous region and a non-porous region surrounding the porous region. The plurality of evaporation masks are arranged in each of a plurality of segments and a plurality of rows.

One embodiment of the present invention aims to provide a method for forming a metal pattern with a superior tapered shape. Another embodiment of the present invention aims to provide a method for manufacturing a metal mask for evaporation with a superior tapered shape.

The present invention includes the following aspects. <1> A method for forming a metal pattern, comprising: Preparing a laminate having a negative photosensitive resin layer on a substrate; irradiating the negative photosensitive resin layer with light having a component incident obliquely in the thickness direction of an exposure mask from a side of the negative photosensitive resin layer opposite to a side on which the substrate is provided, thereby pattern-exposing the negative photosensitive resin layer through the exposure mask; Developing the pattern-exposed negative photosensitive resin layer to form a resin pattern having a tapered shape; and Forming a metal pattern having a tapered shape corresponding to the shape of the resin pattern. <2> The method for forming a metal pattern as described in <1>, wherein, during the step of exposing the pattern, a scattering layer having a diffusion transmittance of 5% or greater and an exposure light source are sequentially disposed on the side of the exposure mask opposite the negative photosensitive resin layer, and scattered light is irradiated from the exposure light source through the scattering layer. <3> The method for forming a metal pattern as described in <2>, wherein the scattering layer contains a black matrix material and particles present in the black matrix material, and the difference in refractive index between the black matrix material and the particles is 0.05 or greater. <4> The method for forming a metal pattern as described in <2> or <3>, wherein the scattering layer contains a black matrix material and particles present in the black matrix material, and the particles have an average primary particle size of 0.3 μm or greater. <5> The method for forming a metal pattern according to any one of <2> to <4>, wherein the scattering layer has a concavo-convex pattern on at least one surface. <6> The method for forming a metal pattern according to <5>, wherein the concavo-convex pattern comprises a plurality of convex portions, and the distance between the tops of adjacent convex portions is 10 μm to 50 μm. <7> The method for forming a metal pattern according to any one of <2> to <6>, wherein the scattering layer and the exposure mask are arranged at positions that do not contact each other. <8> The method for forming a metal pattern according to any one of <2> to <6>, wherein the scattering layer contacts the exposure mask and is arranged on the side of the exposure mask opposite to the negative photosensitive resin layer. <9> The method for forming a metal pattern as described in any one of <2> to <6>, wherein the exposure mask is a scattering exposure mask having the scattering layer formed on a surface opposite to the surface on which the light-shielding pattern is formed. <10> The method for forming a metal pattern as described in any one of <1> to <9>, wherein the preparing step includes using a transfer material having a dummy support and a negative photosensitive resin layer disposed on the dummy support, and transferring the negative photosensitive resin layer of the transfer material to the substrate to form the laminate. <11> The method for forming a metal pattern as described in <10>, wherein the pattern exposure in the pattern exposure step is performed by contact exposure, wherein the dummy support is brought into contact with the exposure mask. <12> The method for forming a metal pattern as described in <10>, wherein the pattern exposure in the pattern exposure step is performed by contact exposure, wherein the dummy support is removed and the exposure mask is brought into contact with the laminate having the negative photosensitive resin layer. <13> The method for forming a metal pattern as described in any one of <1> to <12>, wherein the substrate is a conductive substrate. <14> The method for forming a metal pattern as described in any one of <1> to <13>, wherein the metal pattern is formed by electroplating. <15> The method for forming a metal pattern as described in any one of <1> to <14>, further comprising the step of removing the resin pattern after forming the metal pattern. <16> The method for forming a metal pattern as described in <15>, wherein the resin pattern is removed using a chemical solution. <17> The method for forming a metal pattern as described in any one of <1> to <16>, further comprising the step of removing the substrate from the metal pattern. <18> The method for forming a metal pattern as described in any one of <1> to <17>, wherein the resin pattern comprises a pyramidal or conical resin pattern. <19> The method for forming a metal pattern as described in any one of <1> to <18>, wherein the thickness of the negative photosensitive resin layer is 10 μm or greater. <20> The method for forming a metal pattern as described in any one of <1> to <19>, wherein the obtained metal pattern is a metal pattern for a metal mask for evaporation. <21> A method for manufacturing a metal mask for evaporation, comprising the step of forming a metal pattern using the method for forming a metal pattern as described in any one of <1> to <20>. [Effects of the Invention]

According to one embodiment of the present invention, a method for forming a metal pattern with a superior tapered shape can be provided. According to another embodiment of the present invention, a method for manufacturing a metal mask for evaporation with a superior tapered shape can be provided.

The present invention is described below. The description will be provided with reference to the accompanying drawings, but reference symbols may be omitted. In this specification, numerical ranges indicated using "to" include the numerical values before and after the "to" as the lower and upper limits. In this specification, "(meth)acrylic acid" refers to either or both acrylic acid and methacrylic acid, and "(meth)acrylate" refers to either or both acrylic acid and methacrylate. Furthermore, in the present invention, when a composition contains multiple substances corresponding to each component, the amount of each component in the composition refers to the total amount of the corresponding multiple substances present in the composition, unless otherwise specified. In this specification, the term "step" includes not only independent steps but also steps that perform their intended function, even if they cannot be clearly distinguished from other steps. In the notation of groups (atomic radicals) in this specification, the terms "unsubstituted" and "unsubstituted" include both groups without substituents and groups with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, "exposure," unless otherwise specified, includes not only exposure with light but also drawing with particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and actinic radiation (active energy radiation) such as electron beams. In this specification, chemical formulas are sometimes described as simplified formulas omitting hydrogen atoms. In this invention, "mass%" and "weight%" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning. In this invention, a combination of two or more preferred embodiments constitutes a more preferred embodiment. Unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) used in the present invention are molecular weights obtained by gel permeation chromatography (GPC) using TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all products manufactured by TOSOH CORPORATION) columns, using THF (tetrahydrofuran) as the solvent and a differential refractometer for detection, and conversion using polystyrene as a standard substance.

(Method for Forming a Metal Pattern) The method for forming a metal pattern of the present invention comprises: preparing a laminate having a negative photosensitive resin layer on a substrate; irradiating the negative photosensitive resin layer with light having a component incident obliquely in the thickness direction of an exposure mask from a side of the negative photosensitive resin layer opposite to the side on which the substrate is disposed, thereby pattern-exposing the negative photosensitive resin layer through the exposure mask; developing the pattern-exposed negative photosensitive resin layer to form a resin pattern having a tapered shape; and forming a metal pattern having a tapered shape corresponding to the shape of the resin pattern.

Conventional metal patterning methods utilize etching techniques based on photolithography to create through-holes in metal plates. For example, after patterning a photoresist on a 100-200μm thick stainless steel (SUS) substrate, an etchant is used to etch the SUS substrate into the desired opening shape. However, methods using chemical etching to process metal plates pose challenges in dimensional accuracy and stability, as the metal plate is etched not only through its thickness but also along its surface, causing so-called side etching. For this reason, methods for producing fine metal masks using electroplating have been proposed as a method for producing high-precision metal masks. In one example of a method for manufacturing a metal mask using electrocasting, a metal coating (i.e., a conductive film) is first formed on one surface of a base substrate made of a non-conductive material such as glass by sputtering, for example, to impart conductivity. A high-precision opening pattern is then transferred onto the conductive film using a photoresist mask. Next, a power source is applied to the conductive film in a plating bath, depositing nickel or a nickel alloy to the desired thickness. Finally, the deposited metal coating is removed, leaving the metal mask. To create a metal mask with tapered openings, the photoresist pattern must have a tapered shape with slanted sidewalls.

Thus, the inventors discovered that conventional metal pattern formation methods present problems with tapered shapes. In the metal pattern formation method of the present invention, light having a component that is incident obliquely in the thickness direction of the exposure mask is irradiated from the side of the negative photosensitive resin layer opposite to the side on which the substrate is disposed. This pattern-wise exposure of the negative photosensitive resin layer results in a tapered shape, particularly at the side portions of the resulting resin pattern, as determined by the thickness of the negative photosensitive resin layer. Furthermore, through the above-mentioned aspect, the tapered shape of the resin pattern and the tapered shape of the resulting metal pattern can be fully controlled. Therefore, it is inferred that a metal pattern with an excellent tapered shape can be obtained.

The metal pattern produced using the metal pattern forming method of the present invention has an inverted tapered shape or a right tapered shape when inverted. For example, the metal pattern can be suitably used as a metal mask for evaporation, and more suitably as an FMM (fine metal mask) for manufacturing organic EL display devices, and particularly suitably as an FMM for manufacturing organic light-emitting diodes (OLEDs).

FIG1 shows a schematic diagram illustrating a preferred example of a method for forming a metal pattern according to the present invention. FIG1 comprises FIG1(a) through FIG1(e), which correspond to stages of the respective steps. FIG1(a) through FIG1(e) show schematic cross-sectional views of a portion of the formed metal pattern, taken perpendicular to the plane of the substrate. As shown in FIG1(a), in the step of preparing the laminate, a laminate 100 having a negative photosensitive resin layer 104a is prepared on a substrate 102. The negative photosensitive resin layer 104a in the laminate 100 is pattern-exposed with light having a component incident obliquely in the thickness direction of an exposure mask (not shown) from the side of the negative photosensitive resin layer 104a opposite to the side on which the substrate 102 is disposed. This light is then developed to form a resin pattern 104 having a tapered shape, as shown in Figure 1(b). Next, a metal pattern 106 is formed, as shown in Figure 1(c), using electroplating or other methods, in an inverted tapered shape corresponding to the shape of the resin pattern 104. The taper angle of the resin pattern is θ1, and the taper angle of the metal pattern is θ2. θ1 and θ2 are the same not only in Figure 1(c) but also in Figures 1(b), 1(d), and 1(e). Resin pattern 104 is removed from substrate 102 having resin pattern 104 and metal pattern 106 using a chemical solution, etc., to obtain substrate 102 having metal pattern 106 as shown in Figure 1(d). Substrate 102 can be further removed from substrate 102 having metal pattern 106. By removing substrate 102, only metal pattern 106 can be obtained as shown in Figure 1(e). When substrate 102 is removed as shown in Figure 1(e), it is preferable that metal pattern 106 be a pattern in which all metal portions (not shown) are connected.

<Preparation Step> The metal pattern forming method of the present invention includes preparing a laminate having a negative photosensitive resin layer on a substrate (also referred to as the "preparation step"). Preferably, the preparation step includes using a transfer material having a dummy support and a negative photosensitive resin layer disposed on the dummy support, and transferring the negative photosensitive resin layer on the transfer material to the substrate to form the laminate. The negative photosensitive resin layer and the transfer material having the negative photosensitive resin layer used in the present invention will be described later. The laminate comprises at least a substrate and a negative photosensitive resin layer. It may have other layers such as dummy supports and a release layer. Preferably, the laminate comprises a substrate, a negative photosensitive resin layer, and dummy supports, or a substrate and a negative photosensitive resin layer. More preferably, the laminate comprises a substrate, a negative photosensitive resin layer, and dummy supports. The thickness of the negative photosensitive resin layer is not particularly limited and can be appropriately set to correspond to the desired thickness of the resin pattern described below. However, from the perspective of the taper angle and dimensional stability of the resulting metal pattern, a thickness of 8 μm or greater is preferred, 10 μm or greater is more preferred, 15 μm or greater is even more preferred, 20 μm or greater is particularly preferred, and 30 μm or greater is optimal. The upper limit of the thickness of the negative photosensitive resin layer is preferably 100 μm or less.

-Substrate- Preferably, the substrate is a plate-shaped substrate, more preferably a metal substrate. Preferably, the substrate is a conductive substrate, i.e., a substrate having conductivity at least on its surface. More preferably, the substrate is composed of a conductive material, i.e., a substrate having conductivity throughout. Suitable substrates include, for example, thin plates made of metals such as stainless steel, or glass having a conductive nickel film formed on its upper surface by electrolytic plating as an insulating material. Suitable glass includes alkali-free glass or sodium glass. Conductive materials used in the substrate include, for example, nickel, chromium, tungsten, indium tin oxide (ITO), and the like. Furthermore, when imparting conductivity to a substrate, conductive films can be formed using electroless plating, or physical methods such as sputtering, vacuum evaporation, and ion plating can be used. Furthermore, examples of materials for the base substrate include glass plates, stainless steel plates, and silicon substrates. When using a substrate having a conductive layer on its surface, the thickness of the conductive layer is preferably thin, as long as it provides the conductivity required for electrolytic plating. Specifically, the thickness of the conductive layer is preferably, for example, 0.5 μm to 5 μm.

The method for producing the laminate is not particularly limited. Examples include methods of forming a negative photosensitive resin layer on a substrate using a transfer material, coating and drying a negative photosensitive resin composition on a substrate, and laminating the negative photosensitive resin layer in the transfer material to the substrate. If the transfer material includes a pseudo-support, it is preferably peeled off after lamination. Furthermore, if the transfer material includes a cover film, the cover film can be removed from the surface of the negative photosensitive resin layer before lamination.

The method for laminating the substrate and the transfer material (the negative photosensitive resin layer in the transfer material) is not particularly limited, and known transfer methods and lamination methods can be used. Preferably, the substrate is superimposed on the negative photosensitive resin layer in the transfer material, and pressure and heat are applied using a mechanism such as a roller to achieve this lamination. Furthermore, known laminating presses such as laminating presses, vacuum laminating presses, and automatic cutting laminating presses, which can further improve productivity, can be used for this lamination.

Furthermore, the lamination is preferably performed using a roll-to-roll method. The roll-to-roll method is described below. In the present invention, the roll-to-roll method refers to a method that includes using a rollable and unrollable substrate as the substrate, unwinding at least one of the substrate and the transfer material (also referred to as the "unwinding step"), and rolling up the laminate (also referred to as the "rolling step"). Furthermore, in at least one step (preferably all steps, or all steps except the heating step), the substrate and the transfer material are conveyed while laminating the substrate and the transfer material. There are no particular limitations on the unwinding method in the unwinding step and the winding method in the winding step. Any known method can be used in a roll-to-roll manufacturing method.

<Pattern Exposure Step> The metal pattern forming method of the present invention includes the step of irradiating the negative photosensitive resin layer with light having a component incident obliquely in the thickness direction of an exposure mask from the side of the negative photosensitive resin layer opposite to the side on which the substrate is provided, thereby pattern-exposing the negative photosensitive resin layer through the exposure mask (also referred to as the "pattern exposure step"). The method of irradiating the negative photosensitive resin layer with light having a component incident obliquely in the thickness direction of the exposure mask is not particularly limited, and examples include a method of irradiating the exposure mask with scattered light and a method of irradiating the exposure mask with light having a wide irradiation angle using an optical member such as a lens. The method for generating scattered light is not particularly limited, and known methods can be used. For example, a method using a scattering layer to generate scattered light can be used. The method for generating light with a wide illumination angle is not particularly limited, and known methods can be used. For example, a method in which light emitted from an LED (light-emitting diode) with a narrow illumination angle is transmitted through a wide-angle lens or a fisheye lens to achieve a wide illumination angle can be used. Preferably, the pattern exposure step comprises irradiating the negative photosensitive resin layer with scattered light from a side opposite to the side on which the substrate is disposed through an exposure mask, and pattern-exposing the negative photosensitive resin layer using the light transmitted through the exposure mask. A preferred example of the pattern exposure step is, for example, irradiating the negative photosensitive resin layer with scattered light from an exposure light source positioned on the opposite side of the exposure mask from the negative photosensitive resin layer through the exposure mask. The irradiation with scattered light is preferably performed by placing a scattering layer having a diffusion transmittance of 5% or greater and an exposure light source in this order on the opposite side of the exposure mask from the negative photosensitive resin layer, and irradiating the scattered light from the exposure light source through the scattering layer. In the present invention, pattern exposure refers to pattern-like exposure, i.e., exposure in which the negative photosensitive resin layer has exposed and unexposed areas.

In the pattern exposure step, the detailed arrangement and specific dimensions of the pattern are not particularly limited. For example, they can be appropriately selected based on the display device being manufactured (e.g., a touch panel). Furthermore, during the pattern exposure, a mask (light-shielding mask) is used as the exposure mask to achieve the desired shape. The exposure mask is not particularly limited, and masks made of known materials can be used.

-Exposure Light Source- As the exposure light source in the present invention, any known light source can be used. Any light source that emits light of a wavelength capable of exposing the negative photosensitive resin layer (e.g., 365 nm or 405 nm) can be appropriately selected and used. Specifically, examples include ultra-high-pressure mercury lamps, high-pressure mercury lamps, metal halogen lamps, and LEDs (Light Emitting Diodes). The light used for exposure is not particularly limited as long as it can expose the negative photosensitive resin layer. Light having a wavelength of 365 nm or 405 nm is preferred, light having a wavelength of 365 nm is more preferred, and light having a wavelength of 365 nm is particularly preferred. The exposure dose is not particularly limited as long as it can expose the negative photosensitive resin layer, but is preferably 5 mJ/cm ² to 1,000 mJ/cm ² , and more preferably 10 mJ/cm ² to 500 mJ/cm ² .

When using a transfer material comprising a dummy support and a negative photosensitive resin layer disposed on the dummy support, exposure can be performed after the dummy support is peeled off from the negative photosensitive resin layer during the pattern exposure step, or the dummy support can be peeled off after exposure is performed through the dummy support. The dummy support can be peeled off, for example, by conveying the laminate comprising the negative photosensitive resin layer and the dummy support at a speed of 0.5 m/min to 4.0 m/min while stretching the laminate so that the angle between the dummy support and the laminate is 10° to 180°. By removing the dummy support before exposure, foreign matter contained within or attached to the dummy support can be prevented from adversely affecting exposure. To prevent contamination of the negative photosensitive resin layer due to contact between the negative photosensitive resin layer and the exposure mask, and to prevent adverse effects on exposure caused by foreign matter attached to the exposure mask, exposure is preferably performed through the dummy support. Specifically, a dummy support is provided on the negative photosensitive resin layer in the laminate, and the exposure in the resin pattern forming step is preferably performed through the dummy support. Furthermore, the pattern exposure in the pattern exposure step is preferably performed by contact exposure, wherein the dummy support is brought into contact with the exposure mask. Furthermore, the pattern exposure in the pattern exposure step is preferably performed by contact exposure, wherein the dummy support is removed and the exposure mask is brought into contact with the laminate having the negative photosensitive resin layer. Exposure methods using an exposure mask can employ known high-definition exposure mechanisms such as mask-contact exposure, proximity exposure, or projection exposure using a photolithography machine. When using a photolithography machine for exposure, the distance between the exposure mask and the negative photosensitive resin layer (exposure proximity gap) can be arbitrarily set, preferably between 0μm and 500μm, more preferably between 10μm and 300μm, and particularly preferably between 25μm and 200μm. Also, binary masks, gray masks, halftone masks, and the like can be used as exposure masks.

-Scattering Layer- During the pattern exposure step, irradiation with light (preferably scattered light) having a component that is obliquely incident in the thickness direction of the exposure mask is preferably performed through a scattering layer (preferably a scattering layer having a diffuse transmittance of 5% or greater) disposed between the exposure light source and the exposure mask. The scattering layer can be provided separately, or a scattering material can be incorporated into another layer of the laminate, such as the exposure mask substrate or a pseudo-support in a dry film photoresist, to impart the scattering layer function. From the perspective of the resulting tapered angle between the resin pattern and the metal pattern, it is preferable to dispose the scattering layer and the exposure mask in a position where they do not contact each other. The distance between the scattering layer and the exposure mask can be, for example, 0 μm to 200 μm. In addition, from the perspective of the tapered angle between the resulting resin pattern and the metal pattern, it is preferable to place the scattering layer on the side of the exposure mask opposite to the negative photosensitive resin layer. Diffusive transmittance is measured using the index of light diffusion transmittance. Light diffusion transmittance refers to the transmittance of light irradiated onto the scattering layer, excluding the diffuse light component of the parallel component from the total transmittance of all light rays, including both parallel and diffuse components, that pass through the scattering layer. The diffuse light transmittance can be calculated according to JIS K 7136, "Plastics - Calculation Method for Haze of Transparent Materials (2000)." That is, the haze value (haze value) is expressed by the following formula. Therefore, the diffuse light transmittance of the scattering layer serving as the test object can be determined using a haze meter. Haze value (haze value) % = [Diffuse light transmittance (Td) / Total light transmittance (Tt)] × 100 The measurement device used in this invention is the NDH7000II haze meter from NIPPON DENSHOKU INDUSTRIES Co., Ltd.

The diffuse transmittance of the scattering layer is preferably 5% or greater, more preferably 50% or greater, even more preferably 70% or greater, and particularly preferably 90% or greater. The upper limit of the diffuse transmittance is not particularly limited; for example, it can be 100%.

The scattering angle of the scattering layer is preferably 15° or greater, more preferably 20° or greater, even more preferably 20° or greater and 80° or less, and particularly preferably 40° or greater and 70° or less. The scattering angle refers to the width (the sum of the positive and negative angles) of the angle between the intensity of light transmitted through the scattering layer, where the intensity is half that of the normal direction, 0°. It is sometimes expressed as the full angle at half maximum. The scattering angle can be measured using a goniometer, for example. The scattering characteristics of light are generally symmetrical between the positive and negative sides; even if the positive and negative sides are asymmetrical, the definition of the scattering angle does not change. If the scattering angle value varies depending on the orientation of the measurement surface, the largest value is set as the scattering angle of the scattering layer.

The scattering layer is not particularly limited. From the perspective of easy adjustment of the diffusion transmittance and easy availability, the scattering layer is preferably a scattering layer containing a black matrix material and particles present in the black matrix material (hereinafter sometimes referred to as a scattering layer containing a black matrix material and particles), or a scattering layer having unevenness on at least one surface.

- Scattering Layer Containing Black Matrix Material and Particles- One embodiment of the scattering layer used in the present invention includes a layer containing a black matrix material and particles (hereinafter sometimes referred to as specific particles) present in the black matrix material and used to impart light scattering properties to the scattering layer. The scattering layer containing specific particles is preferably a layer containing specific particles dispersed in a transparent black matrix material. Examples of black matrix materials include glass, quartz, and resin materials. When glass or quartz is used as the black matrix material, the specific particles can be kneaded and uniformly dispersed in the glass or quartz to form the scattering layer. When using a resin material as the black matrix material, a resin capable of forming a UV-transmissive resin layer is preferred. Examples include acrylic resins, polycarbonate resins, polyester resins, polyethylene resins, polypropylene resins, epoxy resins, urethane resins, and silicone resins. When using a resin material as the black matrix material, the scattering layer can be formed using known methods. For example, a sheet-shaped scattering layer can be obtained by melt-kneading the resin particles of the black matrix material and specific particles, followed by injection molding. Alternatively, the scattering layer can be formed by curing a resin composition containing a resin precursor monomer and specific particles. Alternatively, the scattering layer can be formed by curing a resin composition containing specific particles mixed into a mixture containing a resin material and a solvent as an optional component. The method for forming the scattering layer is not limited to the above method.

To impart sufficient light scattering properties to the scattering layer, the specific particles comprise a black matrix material and particles present within the black matrix material. The refractive index difference between the black matrix material and the particles is preferably 0.05 or greater, more preferably 0.05 to 1.0, and even more preferably 0.05 to 0.6. If the refractive index difference between the black matrix material and the specific particles is within this range, the intensity of scattered light can be significantly increased. This also suppresses the reduction in energy imparted by excessive reflection of incident light, which is a concern when the scattered light intensity is too high. Furthermore, sufficient energy can be imparted to cure the negative photosensitive resin layer.

Furthermore, to impart sufficient light scattering properties to the scattering layer, the specific particles comprise a black matrix material and particles present within the black matrix material. The average primary particle size of the specific particles is preferably 0.3 μm or greater. The average primary particle size of the specific particles is more preferably in the range of 0.3 μm to 2.0 μm, and particularly preferably in the range of 0.5 μm to 1.5 μm. When the average primary particle size falls within this range, Mie scattering of ultraviolet light occurs, increasing the intensity of forward scattered light and facilitating the provision of sufficient energy to cure the negative photosensitive resin layer. The average primary particle size of the specific particles is calculated by measuring the particle sizes of 200 random specific particles within the viewing angle using an electron microscope and taking the arithmetic average of the measured values. In addition, if the particle shape is not spherical, the longest side is used as the particle diameter.

Examples of specific particles include inorganic particles such as zirconium oxide particles ( _ZrO2 particles), niobium oxide particles ( _{Nb2O5 particles} ), titanium oxide particles ( _TiO2 particles), aluminum oxide particles ( _{Al2O3 particles} ), and silicon dioxide particles ( _SiO2 particles), and organic particles such as cross-linked polymethyl methacrylate.

The scattering layer may contain only one specific particle or two or more. The specific particle content is not particularly limited. The desired diffusion transmittance or scattering angle is preferably achieved by adjusting the type, size, content, shape, and refractive index of the specific particles in the scattering layer. The specific particle content can be set, for example, to 5% to 50% by mass relative to the total mass of the scattering layer.

-Scattering Layer with Concavities and convexities on At Least One Surface- Another embodiment of the scattering layer includes one having concavities and convexities on at least one surface. The concavities and convexities on at least one surface of the scattering layer scatter light, and the scattered light impinges on the negative photosensitive resin layer through the scattering layer. For the concavities and convexities in the scattering layer, the distance between the tops of adjacent convexities is preferably 10 μm to 50 μm. For the concavities and convexities, the bottoms of adjacent convexities are in contact with each other. From the perspective of light scattering, it is preferred that adjacent convexities be densely formed without gaps or other such spaces. By adjusting the size, shape, and density of the convex portions per unit area, a desired diffusion transmittance or scattering angle can be achieved. The shape of the convex portions is not particularly limited; they can be appropriately selected from hemispherical, conical, pyramidal, or ridged shapes, depending on the desired diffusion transmittance and scattering angle.

A commercially available scattering layer having a concave-convex surface on at least one surface can be used. Examples of commercially available products include the lens diffuser plate (registered trademark) manufactured by OPTICAL SOLUTIONS Corporation. Product names include (hereinafter referred to as the same) LSD5ACUVT10, LSD10ACUVT10, LSD20ACUVT10, LSD30ACUVT10, LSD40ACUVT10, LSD60ACUVT10, and LSD80ACUVT10 (all made of UV-transmitting acrylic resin). Lens diffuser plate (registered trademark): LSD5AC10, LSD10AC10, LSD20AC10, LSD30AC10, LSD40AC10, LSD60AC10, and LSD80AC10 (all made of acrylic resin). Lens Diffuser Plates (Registered Trademark): LSD5PC10, LSD10PC10, LSD20PC10, LSD30PC10, LSD40PC10, LSD60PC10, LSD80PC10, LSD60×10PC10, LSD60×1PC10, LSD40×1PC10, LSD30×5PC10 (all made of polycarbonate). Lens Diffuser Plates (Registered Trademark): LSD5U3PS (all made of quartz glass).

As other scattering layers, there are Fly eye lens FE10 manufactured by Nihon Tokushu Kogaku Jushi Co., Ltd., Diffuser manufactured by FIT Corporation, SDXK-1FS, SDXK-AFS, SDXK-2FS manufactured by SUNTECHOPT Corporation, light diffusion film MX manufactured by Fillplus, Inc., acrylic diffusion sheets ADF901, ADF852, ADF803, ADF754, ADF705, ADF656, ADF607, ADF558, ADF509, ADF451 manufactured by SHIBUYA OPTICAL CO., LTD., Nano buckling (registered trademark) manufactured by Oji F-Tex Co., Ltd., LINTEC Corporation's light diffusion films HDA060, HAA120, GBA110, DCB200, FCB200, IKA130, EDB200; 3M Japan Limited's Scotch Cal (registered trademark) light diffusion films 3635-30, 3635-70; KIMOTO CO., LTD.'s Light Up (registered trademark) SDW, EKW, K2S, LDS, PBU, GM7, SXE, MXE, SP6F; Opt Saver (registered trademark) L-9, L-11, L-19, L-20, L-35, L-52, L-57, STC3, STE3; and Chemical Matte (registered trademark) 75PWX, 125PW, 75PBA, 75BLB, 75PBB, Opulse (registered trademark) PBS-689G, PBS-680G, PBS-689HF, PBS-680HG, PBS-670G manufactured by KEIWA Inc., UDD-147D2, UDD-148D2, SHBS-227C1, SHBS-228C2, UDD-247D2, PBS-630L, PBS-630A, PBS-632A, BS-539, BS-530, BS-531, BS-910, BS-911, BS-912, Kuraray Co., Legend (registered trademark) PC, CL, HC, OC, TR, MC, SQ, EL, OE manufactured by Ltd.; D120P, D121UPZ, D121UP, D261SIIIJ1, D261IVJ1, D263SIII, S263SIV, D171, D171S, D174S, etc. manufactured by Tsujiden Co., Ltd.

The thickness of the scattering layer is preferably 2 mm or less, more preferably 1 mm or less, and even more preferably 100 μm or less. The thickness of the scattering layer is preferably 0.5 μm or greater, and even more preferably 1 μm or greater. The thickness of the scattering layer is the arithmetic mean of the values measured at any five locations on a cross-section of the scattering layer using a scanning electron microscope (SEM).

Irradiation with scattered light is not limited to irradiation through a separate scattering layer. For example, a scattering exposure mask having light scattering properties can be suitably used for layers other than the light-blocking portion of the exposure mask. Using a scattering exposure mask (also referred to as a "scattering exposure mask") results in scattered light passing through the exposure mask. From the perspective of the resulting tapered angles of the resin and metal patterns, a preferred embodiment is one in which the scattering layer is formed on the surface opposite to the surface on which the light-blocking pattern is formed.

During the pattern exposure step, the scattering layer's placement is not particularly limited, as long as it is between the exposure light source and the exposure mask. For example, the exposure mask, scattering layer, and exposure light source may be positioned in this order on the side of the negative photosensitive resin layer opposite the side where the substrate is located.

The following diagrams illustrate an example of the placement of the scattering layer when irradiating the film with scattered light (preferably light having a component incident obliquely in the thickness direction of the exposure mask) through the scattering layer. Figure 2 is a schematic cross-sectional view showing a first embodiment of the placement of the scattering layer during light irradiation in the pattern exposure step. The exposed laminate precursor shown in Figure 2 comprises a substrate 12, a negative photosensitive resin layer 16, a polyethylene terephthalate (PET) film serving as a pseudo-support 24, and an exposure mask 26 having a light-shielding area 26A. A scattering layer 28 is positioned on the side of the exposure light source (not shown) (the side of the negative photosensitive resin layer 16 opposite the substrate 12 side) so as not to contact the exposure mask 26. In Figures 2-4, the beam diameter of the irradiating light is schematically indicated by arrows. As shown in Figure 2, the scattered light that passes through the scattering layer 28 is scattered at an angle relative to the normal direction of the negative photosensitive resin layer 16. Therefore, the side surface of the patterned cured layer 16A formed by the cured regions in the negative photosensitive resin layer 16 has a gentle slope relative to the substrate surface. The taper angle of the side surface of the patterned cured layer 16A relative to the substrate surface is preferably 50° or less.

Figure 3 is a schematic cross-sectional view showing a second embodiment of the placement of a scattering layer during light exposure in the pattern exposure step. The exposed laminate precursor in Figure 3 has the same layer structure as the exposed laminate precursor shown in Figure 2. In the second embodiment shown in Figure 3, scattering layer 28 is positioned in contact with exposure mask 26. The scattering layer 28 can be integrally formed on the light source side of exposure mask 26 by coating, laminating, or other methods. In the second embodiment shown in Figure 3, scattered light that passes through the scattering layer 28 and is scattered enters the area without the light-shielding region 26A of the exposure mask 26 as scattered light. As shown in Figure 3, the patterned cured layer 16A formed in the cured area of the negative photosensitive resin layer 16 has a gentle slope relative to the substrate surface when viewed from the side. The patterned cured layer 16A preferably has a taper angle of 50° or less relative to the substrate surface in a cross-section parallel to the normal to the substrate.

Figure 4 is a schematic cross-sectional view showing an example of a third embodiment of a scattering exposure mask used as a scattering layer during light irradiation in the pattern exposure step. In the third embodiment shown in Figure 4, a scattering exposure mask 32 having a diffusion transmittance of 5% or greater is used as the exposure mask. The scattering exposure mask 32 has light-shielding regions 32A located in desired areas of the scattering substrate. The diffusion transmittance of the scattering exposure mask is as described above. In the third embodiment shown in Figure 4 , light irradiated from an exposure light source (not shown) located on the side of the negative photosensitive resin layer 16 opposite to the side on which the substrate 12 is disposed transmits through the scattering exposure mask 32, becoming scattered light. Since this light enters the negative photosensitive resin layer 16 at an angle relative to the substrate's normal direction, as shown in Figure 4 , the patterned cured layer 16A formed in the cured region of the negative photosensitive resin layer 16 exhibits a gentle slope relative to the substrate's surface when viewed from the side. The patterned cured layer 16A preferably has a taper angle of 50° or less relative to the substrate's surface in a cross-section parallel to the substrate's normal direction.

In any aspect, in the metal pattern formation method of the present invention, diffuse light is irradiated from an exposure light source onto an exposure mask, and the negative photosensitive resin layer is exposed to a pattern through the exposure mask. Consequently, the side surfaces of the negative photosensitive resin layer, which form a pattern in the hardened areas, have a gentle slope relative to the substrate surface, making them less prone to steep slopes. This enables the formation of a laminated structure exhibiting the various advantages described above. To improve the flatness of the pattern after exposure, a heat treatment is preferably performed before the resin pattern formation step. A step called PEB (Post Exposure Bake) can reduce the roughness of pattern edges caused by ripples in the negative photosensitive resin layer during exposure.

<Resin Pattern Formation Step> The metal pattern formation method of the present invention includes a step of developing the negative photosensitive resin layer exposed to the pattern to form a resin pattern having a tapered shape (also referred to as the "resin pattern formation step"). The thickness of the formed resin pattern can be appropriately selected based on the relationship between the hole pitch, the opening diameter, and the deposition angle. However, from the perspective of the tapered angle and dimensional stability of the resulting metal pattern, a thickness of 10 μm or greater is preferred, 15 μm or greater is more preferred, 20 μm or greater is even more preferred, and 30 μm or greater is particularly preferred. The upper limit is preferably 100 μm or less. The thickness of the resin pattern, metal pattern, and each layer in the present invention is measured by observing a cross-section of the transferred material or the laminate in a direction perpendicular to the plane using a scanning electron microscope (SEM). Unless otherwise specified, the thickness values are the average of 10 or more measurements.

In the present invention, the "tapered shape" of a resin pattern refers to a situation where the width (W1) of the top (opposite side of the substrate) and the width (W2) of the bottom (substrate side) of the resin pattern satisfy the relationship W1 < W2. The taper angle refers to the angle between the side of the pattern and the substrate, and can be approximated by the angle between a straight line connecting the top and bottom ends of the resin pattern and the substrate surface. The taper angle can be appropriately selected based on the relationship between the hole pitch, opening diameter, and evaporation angle, with 10° to 80° being preferred, 20° to 70° being more preferred, and 30° to 60° being particularly preferred. Furthermore, the resin pattern in the present invention is preferably in a right tapered shape relative to the tapered shape of the substrate.

In the present invention, the tapered shape of the resin pattern can be adjusted by, for example, selecting the angle and intensity of the component of light that obliquely enters the exposure mask. For example, when using a scattering layer, adjustments can be made to the scattering angle and diffuse transmittance of the scattering layer, as well as the intensity of the exposure light source.

The shape of the resin pattern is not particularly limited and can be appropriately selected as needed. However, from the perspective of further enhancing the effects of the present invention, the resin pattern preferably includes a pyramidal shape, and more preferably includes a pyramidal or conical shape. Furthermore, from the perspective of further exerting the effects of the present invention, the resin pattern is preferably a resin pattern in which the maximum diameter of the surface on the side opposite to the substrate side is less than 100 μm, more preferably a resin pattern in which the maximum diameter of the surface on the side opposite to the substrate side is less than 50 μm, further preferably a resin pattern in which the maximum diameter of the surface on the side opposite to the substrate side is greater than 0.1 μm and less than 20 μm, and particularly preferably a resin pattern in which the maximum diameter of the surface on the side opposite to the substrate side is greater than 0.2 μm and less than 10 μm. Furthermore, from the perspective of further exerting the effects of the present invention, the resin pattern is preferably a resin pattern in which the area of the surface opposite to the substrate side is less than 1,200 μm ² , more preferably a resin pattern in which the area of the surface opposite to the substrate side is less than 500 μm ² , further preferably a resin pattern in which the area of the surface opposite to the substrate side is greater than 0.1 μm ² and less than 250 μm ² , and particularly preferably a resin pattern in which the area of the surface opposite to the substrate side is greater than 1 μm ² and less than 100 μm ² .

In the resin pattern forming step, the negative photosensitive resin layer, which has been exposed in a patterned manner, is developed to form a resin pattern having a tapered shape. If the transfer material includes an intermediate layer, the intermediate layer in the unexposed areas is removed along with the negative photosensitive resin layer in the resin pattern forming step. Alternatively, the intermediate layer in the exposed areas can be removed by dissolving or dispersing it in a developer solution during the resin pattern forming step.

The exposed negative photosensitive resin layer in the resin pattern formation step can be developed using a developer. The developer is not particularly limited as long as it can remove the non-image areas (non-exposed areas) of the negative photosensitive resin layer. For example, known developers such as those described in Japanese Patent Application Laid-Open No. 5-72724 can be used. Preferably, the developer is an aqueous alkaline solution containing a compound with a pKa of 7 to 13 at a concentration of 0.05 to 5 mol/L (liter). The developer may contain a water-soluble organic solvent and/or a surfactant. As a developer, the developer described in paragraph 0194 of International Publication No. 2015/093271 is also preferred.

The development method is not particularly limited and can be any of flood development, spray development, spray and spin development, and dip development. Spray development involves spraying a developer onto the exposed negative photosensitive resin layer to remove the unexposed areas. After the resin pattern formation step, a cleaning solution is preferably sprayed, and development residue is preferably removed while wiping with a brush. The developer liquid temperature is not particularly limited, but is preferably between 20°C and 40°C.

<Metal Pattern Forming Step> The metal pattern forming method of the present invention includes the step of forming a metal pattern having a tapered shape corresponding to the shape of the resin pattern (also referred to as the "metal pattern forming step"). The thickness of the formed metal pattern is not particularly limited and can be appropriately selected as needed. However, from the perspective of the strength and durability of the resulting metal pattern, a thickness of 5 μm or greater is preferred, 10 μm or greater is more preferred, 12 μm or greater is even more preferred, and 15 μm or greater is particularly preferred. Furthermore, the upper limit is preferably 100 μm or less, and more preferably 50 μm or less.

In the present invention, the term "tapered shape corresponding to the shape of the resin pattern" in the metal pattern refers to the tapered shape of the metal pattern formed to correspond to the shape of the tapered resin pattern. As described above, as long as the resin pattern satisfies the relationship W1 < W2, then when measuring the width (W3) of the top of the metal pattern (the side opposite to the substrate side) and the width (W4) of the bottom of the metal pattern (the substrate side), the relationship W3 > W4 is achieved. For example, the metal pattern corresponding to the resin pattern formed into a right tapered shape described later has an inverted tapered shape. The taper angle of the metal pattern's tapered shape refers to the angle between the side of the metal pattern and the substrate. It can be approximated by the angle between a straight line connecting the top and bottom ends of the metal pattern and the substrate surface. The taper angle of the metal pattern can be appropriately selected, with 100° to 170° being preferred, 110° to 160° being more preferred, and 120° to 150° being particularly preferred.

From the perspective of further exerting the effects of the present invention, it is preferred that the metal pattern be a metal pattern having an opening portion having the above-mentioned tapered shape. From the perspective of further exerting the effects of the present invention, the above-mentioned metal pattern is preferably a resin pattern including an opening portion with a maximum diameter of less than 100 μm on at least one surface in the surface direction of the metal pattern, more preferably a resin pattern including an opening portion with a maximum diameter of less than 50 μm on at least one surface in the surface direction of the metal pattern, further preferably a resin pattern including an opening portion with a maximum diameter of greater than 0.1 μm and less than 20 μm on at least one surface in the surface direction of the metal pattern, and particularly preferably a resin pattern including an opening portion with a maximum diameter of greater than 0.2 μm and less than 10 ^μm2 on at least one surface in the surface direction of the metal pattern. Furthermore, from the perspective of further exerting the effects of the present invention, the above-mentioned metal pattern is preferably a resin pattern in which the opening area of the opening portion on at least one surface in the surface direction of the metal pattern is less than 1,200 μm ² , more preferably a resin pattern in which the opening area of the opening portion on at least one surface in the surface direction of the metal pattern is less than 500 μm ² , further preferably a resin pattern in which the opening area of the opening portion on at least one surface in the surface direction of the metal pattern is greater than 0.1 μm ² and less than 250 μm ² , and particularly preferably a resin pattern in which the opening area of the opening portion on at least one surface in the surface direction of the metal pattern is greater than 1 μm ² and less than 100 μm ² .

The method for forming the metal pattern in the metal pattern forming step is not particularly limited, as long as it can form a metal pattern having an inverted tapered shape corresponding to the shape of the resin pattern. Electroplating (electrocasting) is preferred. That is, the metal pattern is preferably formed by electroplating. For example, the following method can be used to form the metal pattern by electroplating. A conductive portion of the substrate on which the resin pattern is formed is connected to a plating power source and immersed in a plating bath for depositing the desired metal. The electroplated material is deposited as a film on the exposed portion of the upper surface of the substrate, with the electroplated metal deposited within a range less than the thickness of the resin pattern, and growing into an inverted tapered metal pattern. Examples of plating baths include nickel sulfamate and nickel-cobalt alloy baths with cobalt added. During the electroplating process, the thickness of the plating layer is controlled by the current value and the duration of the current flow or immersion. The composition of the plating bath, the plating temperature, the current value during the plating process, the plating time, and other factors are not particularly limited and can be appropriately selected as needed. Furthermore, the metal deposition is not limited to electroplating; electroless plating methods can also be used. Furthermore, the electroplating process can be performed at a temperature ranging from room temperature (e.g., 5°C to 30°C) to approximately 60°C.

The metal used in the metal pattern can include various metals, such as nickel, nickel-cobalt alloys, iron-nickel alloys, and copper. Iron-nickel alloys containing 30% to 45% nickel by mass are preferred, and indium steel, an alloy primarily composed of 36% nickel and 64% iron by mass, is even more preferred. When the metal pattern is made of indium steel, the thermal expansion coefficient of the metal pattern is, for example, approximately 1.2× ^10⁻⁶ /°C.

<Resin Pattern Removal Step> The metal pattern forming method of the present invention preferably further includes, after the metal pattern forming step, a step of removing the resin pattern (also referred to as the "resin pattern removal step"). The method for removing the resin pattern in the resin pattern removal step is not particularly limited, but is preferably performed using a chemical solution. An example of a method for removing the resin pattern includes immersing the substrate having the resin pattern and the metal pattern in a chemical solution while stirring at a temperature preferably between 30°C and 80°C, more preferably between 50°C and 80°C, for 1 to 30 minutes.

Examples of chemical solutions include those obtained by dissolving inorganic base components such as sodium hydroxide and potassium hydroxide, or organic base components such as primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds in water, dimethyl sulfoxide, N-methylpyrrolidone, or mixed solutions thereof. Alternatively, chemical solutions can be used for removal by spraying, showering, or coating methods.

<Substrate Removal Step> The metal pattern forming method of the present invention preferably further includes, after the step of forming the metal pattern, the step of removing the substrate from the metal pattern. The metal pattern, after the substrate is removed, has an opening pattern with inclined sidewalls and an inverted tapered shape that complements the photoresist pattern and can be suitably used as a thin metal mask. The method for removing the substrate from the metal pattern in the substrate removal step is not particularly limited; any method that preferably peels the substrate and the metal pattern can be employed. Furthermore, the metal pattern is preferably a pattern in which all metal portions are connected. There are no specific restrictions on the peeling method. For example, the substrate can be peeled by stretching the web in a 180° folded position. There are no specific restrictions on the peeling speed, but 1 mm/s to 50 mm/s is preferred.

<Other Steps> The metal pattern forming method of the present invention may include any steps (other steps) other than those described above. These other steps are not particularly limited and may be any known steps. In addition, as an example of the resin pattern forming step and other steps in the present invention, the method described in paragraphs 0035 to 0051 of Japanese Patent Application Laid-Open No. 2006-23696 can also be appropriately used in the present invention. Furthermore, the metal pattern forming method of the present invention may include the steps of polishing the obtained metal pattern and cleaning the obtained metal pattern.

<Applications of Metal Patterns> The applications of the metal pattern produced by the metal pattern forming method of the present invention are not particularly limited. The metal pattern can be suitably used as a metal mask, further suitably used as a metal mask for vapor deposition, and particularly suitably used as a metal mask for vapor deposition of organic light-emitting materials. Suitable examples of the organic light-emitting materials include red (R), green (G), or blue (B) organic light-emitting materials (RGB organic light-emitting materials) used in organic EL display devices, and particularly suitable examples include RGB organic light-emitting materials used in organic EL diodes. Furthermore, the metal pattern produced using the metal pattern forming method of the present invention can be particularly suited for use as a metal mask for vapor deposition used in the manufacture of organic EL light-emitting diodes (OLEDs). Furthermore, other uses for the metal pattern produced using the metal pattern forming method of the present invention are not particularly limited, and examples include use in solder paste printing, dot matrix printing for touch panels, and fluorescent printing for PDPs (Plasma Display Panels).

The following describes in detail the negative photosensitive resin layer and the transfer material having the negative photosensitive resin layer used in the present invention.

<<Negative Photosensitive Resin Layer>> The transfer material used in the present invention comprises at least a negative photosensitive resin layer. The negative photosensitive resin layer may contain a polymerizable compound, a polymerization initiator, and other components.

-Polymerizable Compound- The negative photosensitive resin layer preferably contains a polymerizable compound. A polymerizable compound is a compound having a polymerizable group. Examples of polymerizable groups include free radical polymerizable groups and cationic polymerizable groups. Free radical polymerizable groups are preferred from the perspective of achieving better curing sensitivity.

The polymerizable compound preferably includes a polymerizable compound having an ethylenically unsaturated group (hereinafter also referred to as an "ethylenically unsaturated compound"). Preferably, the ethylenically unsaturated group is a (meth)acryloyl group.

The ethylenically unsaturated compound preferably includes a difunctional or higher functional ethylenically unsaturated compound. "Difunctional or higher functional ethylenically unsaturated compound" refers to a compound having two or more ethylenically unsaturated groups in one molecule.

(Meth)acrylate compounds are preferred as ethylenically unsaturated compounds. From the perspective of film strength after curing, for example, ethylenically unsaturated compounds preferably include bifunctional ethylenically unsaturated compounds (preferably bifunctional (meth)acrylate compounds) and trifunctional or higher-functional ethylenically unsaturated compounds (preferably trifunctional or higher-functional (meth)acrylate compounds).

Examples of the bifunctional ethylenically unsaturated compound include tricyclodecane dimethanol di(meth)acrylate, tricyclodecane diethanol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate.

Examples of commercially available bifunctional ethylenically unsaturated compounds include tricyclic decanedimethanol diacrylate [product name: NK Ester A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.], tricyclic decanedimethanol dimethacrylate [product name: NK Ester DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.], 1,9-nonanediol diacrylate [product name: NK Ester A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.], 1,10-decanediol diacrylate [product name: NK Ester A-DOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.], and 1,6-hexanediol diacrylate [product name: NK Ester A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.]. Co., Ltd. Manufacturing].

Examples of trifunctional or higher-functional ethylenically unsaturated compounds include dipentatriol (tri/tetra/penta/hexa) (meth)acrylate, pentatriol (tri/tetra) (meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, ditrihydroxymethylpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and glycerol tri(meth)acrylate.

Here, "(tri/tetra/penta/hexa) (meth)acrylate" encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate. Furthermore, "(tri/tetra) (meth)acrylate" encompasses tri(meth)acrylate and tetra(meth)acrylate. For tri- or higher-functional ethylenically unsaturated compounds, the upper limit of the number of functional groups is not particularly limited; for example, it can be 20 or fewer functional groups, or even 15 or fewer functional groups.

Examples of commercially available trifunctional or higher-functional ethylenically unsaturated compounds include dipentatriol hexaacrylate (product name: KAYARAD DPHA, Shin-Nakamura Chemical Co., Ltd.).

More preferably, the ethylenically unsaturated compound includes 1,9-nonanediol di(meth)acrylate or 1,10-decanediol di(meth)acrylate and dipentatriol (tri/tetra/penta/hexa) (meth)acrylate.

Examples of ethylenically unsaturated compounds include caprolactone-modified compounds of (meth)acrylate compounds [KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.], alkylene oxide-modified compounds of (meth)acrylate compounds [KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by DAICEL-ALLNEX LTD., etc.], and ethoxylated triacrylates [NK Ester manufactured by Shin-Nakamura Chemical Co., Ltd.]. A-GLY-9E, etc.].

Examples of ethylenically unsaturated compounds include urethane (meth)acrylate compounds. Preferred urethane (meth)acrylate compounds are trifunctional or higher-functional urethane (meth)acrylate compounds. Examples of trifunctional or higher-functional urethane (meth)acrylate compounds include 8UX-015A (manufactured by TAISEI FINE CHEMICAL CO., LTD.), NK Ester UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and NK Ester UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.).

From the viewpoint of improving developing properties, the ethylenically unsaturated compound preferably includes an ethylenically unsaturated compound having an acid group.

Examples of the acid group include a phosphoric acid group, a sulfonic acid group, and a carboxyl group. Among these, a carboxyl group is preferred as the acid group.

Examples of ethylenically unsaturated compounds having acid groups include trifunctional to tetrafunctional ethylenically unsaturated compounds having acid groups [compounds obtained by introducing carboxyl groups into the backbone of pentaerythritol tri- and tetraacrylate (PETA) (acid value: 80 KOH/g to 120 mgKOH/g)] and pentafunctional to hexafunctional ethylenically unsaturated compounds having acid groups [compounds obtained by introducing carboxyl groups into the backbone of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA) (acid value: 25 KOH/g to 70 mgKOH/g)]. Trifunctional or higher ethylenically unsaturated compounds having acid groups can be used in combination with difunctional ethylenically unsaturated compounds having acid groups, if necessary.

The ethylenically unsaturated compound having an acid group is preferably at least one compound selected from the group consisting of bifunctional or higher-functional ethylenically unsaturated compounds having a carboxyl group and their carboxylic anhydrides. If the ethylenically unsaturated compound having an acid group is at least one compound selected from the group consisting of bifunctional or higher-functional ethylenically unsaturated compounds having a carboxyl group and their carboxylic anhydrides, developing properties and film strength are further improved.

Examples of bifunctional or higher-functional ethylenically unsaturated compounds having a carboxyl group include ARONIX (registered trademark) TO-2349 [manufactured by TOAGOSEI CO., LTD.], ARONIX (registered trademark) M-520 [manufactured by TOAGOSEI CO., LTD.], and ARONIX (registered trademark) M-510 [manufactured by TOAGOSEI CO., LTD.].

As the ethylenically unsaturated compound having an acid group, a polymerizable compound having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942 can be preferably used, and the contents described in the publication are incorporated herein by reference.

The molecular weight of the ethylenically unsaturated compound is preferably 200 to 3,000, more preferably 250 to 2,600, further preferably 280 to 2,200, and particularly preferably 300 to 2,200.

Among the ethylenically unsaturated compounds, the content of ethylenically unsaturated compounds having a molecular weight of 300 or less is preferably 30 mass% or less, more preferably 25 mass% or less, and even more preferably 20 mass% or less, based on the content of all ethylenically unsaturated compounds contained in the negative photosensitive resin layer.

The negative photosensitive resin layer may contain only one ethylenically unsaturated compound, or may contain two or more ethylenically unsaturated compounds.

The content of the ethylenically unsaturated compound is preferably 1% to 70% by mass, more preferably 10% to 70% by mass, even more preferably 20% to 60% by mass, and particularly preferably 20% to 50% by mass, relative to the total mass of the negative photosensitive resin layer. If the negative photosensitive resin layer contains a bifunctional or higher-functional ethylenically unsaturated compound, it may further contain a monofunctional ethylenically unsaturated compound.

When the negative photosensitive resin layer contains a difunctional or higher-functional ethylenically unsaturated compound, the difunctional or higher-functional ethylenically unsaturated compound is preferably the main component of the ethylenically unsaturated compound contained in the negative photosensitive resin layer. When the negative photosensitive resin layer contains a difunctional or higher-functional ethylenically unsaturated compound, the content of the difunctional or higher-functional ethylenically unsaturated compound relative to the total content of the ethylenically unsaturated compound contained in the negative photosensitive resin layer is preferably 60% to 100% by mass, more preferably 80% to 100% by mass, and even more preferably 90% to 100% by mass.

When the negative photosensitive resin layer contains an ethylenically unsaturated compound having an acid group (preferably a bifunctional or higher functional ethylenically unsaturated compound having a carboxyl group or a carboxylic anhydride thereof), the content of the ethylenically unsaturated compound having an acid group is preferably 1% by mass to 50% by mass, more preferably 1% by mass to 20% by mass, and even more preferably 1% by mass to 10% by mass, relative to the total mass of the negative photosensitive resin layer.

-Polymerization Initiator- The negative photosensitive resin layer preferably contains a polymerization initiator. Polymerization initiators include thermal polymerization initiators and photopolymerization initiators, with photopolymerization initiators being preferred. Examples of photopolymerization initiators include photopolymerization initiators having an oxime ester structure (hereinafter also referred to as "oxime-based photopolymerization initiators"), photopolymerization initiators having an α-aminoalkylphenone structure (hereinafter also referred to as "α-aminoalkylphenone-based photopolymerization initiators"), photopolymerization initiators having an α-hydroxyalkylphenone structure (hereinafter also referred to as "α-hydroxyalkylphenone-based polymerization initiators"), photopolymerization initiators having an acylphosphine oxide structure (hereinafter also referred to as "acylphosphine oxide-based photopolymerization initiators"), and photopolymerization initiators having an N-phenylglycine structure (hereinafter also referred to as "N-phenylglycine-based photopolymerization initiators").

The photopolymerization initiator preferably comprises at least one selected from the group consisting of oxime-based photopolymerization initiators, α-aminoalkylphenone-based photopolymerization initiators, α-hydroxyalkylbenzophenone-based photopolymerization initiators, and N-phenylglycine-based photopolymerization initiators. More preferably, the photopolymerization initiator comprises at least one selected from the group consisting of oxime-based photopolymerization initiators, α-aminoalkylphenone-based photopolymerization initiators, and N-phenylglycine-based photopolymerization initiators. For example, the photopolymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-095716 and paragraphs 0064 to 0081 of JP-A-2015-014783 can be used.

Examples of commercially available photopolymerization initiators include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(o-benzoyloxime) [Product name: IRGACURE (registered trademark) OXE-01, manufactured by BASF], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(o-acetyloxime) [Product name: IRGACURE (registered trademark) OXE-02, manufactured by BASF], [8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylphenyl)- [Product Name: IRGACURE (Registered Trademark) OXE-03, manufactured by BASF], 1-[4-[4-(2-Benzofurylcarbonyl)phenyl]thio]phenyl]-4-methyl-1-pentanone-1-(o-acetyloxime) [Product Name: IRGACURE (Registered Trademark) OXE-04, manufactured by BASF], 2-(Dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4 -(4-[(2-hydroxy-2-methylpropionyl)benzyl]phenyl]-1-butanone [Product name: IRGACURE (registered trademark) 379EG, manufactured by BASF], 2-methyl-1-(4-methylthiophenyl)-2-[(2-hydroxy-2-methylpropionyl)benzyl]phenyl]-2-methylpropan-1-one [Product name: IRGACURE (registered trademark) 127, manufactured by BASF], 2 Benzyl-2-dimethylamino-1-(4-(1,2-diphenyl)-butanone-1-one [Product Name: IRGACURE (Registered Trademark) 369, manufactured by BASF], 2-Hydroxy-2-methyl-1-phenyl-propane-1-one [Product Name: IRGACURE (Registered Trademark) 1173, manufactured by BASF], 1-Hydroxycyclohexylphenyl ketone [Product Name: IRGACURE (Registered Trademark) 184, manufactured by BASF], 2,2-Dimethoxy-1,2-diphenylethane-1-one [Product Name: IRGACURE 651, manufactured by BASF Corporation] and oxime ester compounds [Product name: Lunar (registered trademark) 6, manufactured by DKSH JAPAN K.K.], 1-(Biphenyl-4-yl)-2-methyl-2-ortho-linopropan-1-one [Product name: APi-307 (registered trademark), manufactured by Shenzhen UV-ChemTech LTD], 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(o-benzoyloxime) [Product name: TR-PBG-305, Changzhou Tronly New Electronic Materials CO., LTD.], 3-cyclohexyl-1-[9-ethyl-6-(2-furylcarbonyl)-9H-carbazol-3-yl]-1,2-propanedione-2-(o-acetyl oxime) [Product Name: TR-PBG-326, manufactured by Changzhou Tronly New Electronic Materials CO., LTD.], 3-cyclohexyl-1-(6-(2-(benzyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)propane-1,2-dione-2-(o-benzoyl oxime) [Product Name: TR-PBG-391, manufactured by Changzhou Tronly New Electronic Materials CO., LTD.].

The negative photosensitive resin layer may contain a single polymerization initiator or two or more polymerization initiators. The polymerization initiator content is preferably 0.1% by mass or greater, and more preferably 0.5% by mass or greater, relative to the total mass of the negative photosensitive resin layer. The upper limit of the polymerization initiator content is preferably 10% by mass or less, and more preferably 5% by mass or less, relative to the total mass of the negative photosensitive resin layer.

-Alkali-Soluble Acrylic Resin- The negative photosensitive resin layer may contain an alkali-soluble acrylic resin. The inclusion of an alkali-soluble acrylic resin in the negative photosensitive resin layer improves the solubility of the negative photosensitive resin layer (non-exposed area) in the developer.

In the present invention, "alkali solubility" means a dissolution rate of 0.01 μm/s or greater, as determined by the following method. A 25% by mass solution of a target compound (e.g., resin) in propylene glycol monomethyl ether acetate is applied to a glass substrate and then heated in a 100°C oven for 3 minutes to form a coating film (2.0 μm thick). The coating film is then immersed in a 1% by mass aqueous solution of sodium carbonate (liquid temperature 30°C) to determine the dissolution rate (μm/s) of the coating film. Alternatively, if the target compound is insoluble in propylene glycol monomethyl ether acetate, the target compound is dissolved in an organic solvent other than propylene glycol monomethyl ether acetate with a boiling point below 200°C (e.g., tetrahydrofuran, toluene, or ethanol).

The alkali-soluble acrylic resin is not limited as long as it has the alkali solubility described above. The term "acrylic resin" refers to a resin containing at least one of a (meth)acrylic acid-derived unit and a (meth)acrylate-derived unit.

The total proportion of the constituent units derived from (meth)acrylic acid and the constituent units derived from (meth)acrylate in the alkali-soluble acrylic resin is preferably 30 mol% or more, and more preferably 50 mol% or more.

In the present invention, when the content of a "constituent unit" is specified by molar fraction (molar ratio), unless otherwise specified, the "constituent unit" is assumed to have the same meaning as "monomer unit." Furthermore, in the present invention, when a resin or polymer contains two or more specific constituent units, the content of the specific constituent units is assumed to mean the total content of the two or more specific constituent units, unless otherwise specified.

From the perspective of developing properties, it is preferred that the alkaline-soluble acrylic resin contain carboxyl groups. One method for introducing carboxyl groups into an alkaline-soluble acrylic resin is to synthesize the alkaline-soluble acrylic resin using a monomer containing a carboxyl group. Using this method, the monomer containing a carboxyl group is introduced into the alkaline-soluble acrylic resin as a constituent unit containing a carboxyl group. Examples of monomers containing carboxyl groups include acrylic acid and methacrylic acid.

The alkali-soluble acrylic resin may have one carboxyl group or two or more carboxyl groups. The constituent unit having a carboxyl group in the alkali-soluble acrylic resin may be a single type or two or more types.

The content of the structural unit having a carboxyl group is preferably 5 mol% to 50 mol% relative to the total amount of the alkali-soluble acrylic resin, more preferably 5 mol% to 40 mol%, and even more preferably 10 mol% to 30 mol%.

From the perspective of moisture permeability and strength after curing, alkaline-soluble acrylic resins preferably have constituent units with aromatic rings. Preferred constituent units with aromatic rings are those derived from styrene compounds. Examples of monomers that form constituent units with aromatic rings include monomers that form constituent units derived from styrene compounds and benzyl (meth)acrylate.

Examples of monomers forming the constituent units derived from the styrene compound include styrene, p-methylstyrene, α-methylstyrene, α,p-dimethylstyrene, p-ethylstyrene, p-tert-butylstyrene, tert-butoxystyrene, and 1,1-diphenylethylene. Styrene or α-methylstyrene is preferred, and styrene is more preferred.

The constituent unit having an aromatic ring in the alkali-soluble acrylic resin may be a single type or may be two or more types.

When the alkali-soluble acrylic resin has a constituent unit having an aromatic ring, the content of the constituent unit having an aromatic ring is preferably 5 mol% to 90 mol%, more preferably 10 mol% to 90 mol%, and even more preferably 15 mol% to 90 mol%, relative to the total amount of the alkali-soluble acrylic resin.

From the perspective of viscosity and strength after hardening, alkaline-soluble acrylic resins preferably contain constituent units having an aliphatic cyclic skeleton.

Examples of the aliphatic ring in the aliphatic cyclic skeleton include a dicyclopentane ring, a cyclohexane ring, an isoborane ring, and a tricyclodecane ring. Among these, the tricyclodecane ring is preferred as the aliphatic ring in the aliphatic cyclic skeleton.

Examples of monomers that form a constituent unit having an aliphatic cyclic skeleton include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isoborneol (meth)acrylate.

The constituent unit having an aliphatic cyclic skeleton in the alkali-soluble acrylic resin may be of a single type or of two or more types.

When the alkali-soluble acrylic resin has a constituent unit having an aliphatic cyclic skeleton, the content of the constituent unit having an aliphatic cyclic skeleton is preferably 5 mol% to 90 mol%, more preferably 10 mol% to 80 mol%, and even more preferably 10 mol% to 70 mol%, relative to the total amount of the alkali-soluble acrylic resin.

From the perspective of viscosity and hardened strength, alkaline-soluble acrylic resins with reactive groups are preferred.

As the reactive group, a free radical polymerizable group is preferred, and an ethylenically unsaturated group is more preferred. Furthermore, when the alkaline-soluble acrylic resin has an ethylenically unsaturated group, it is preferred that the alkaline-soluble acrylic resin has a structural unit having an ethylenically unsaturated group in a side chain.

In the present invention, "main chain" refers to the longest bond in the polymer compound molecules constituting the resin, and "side chain" refers to the atomic group branching from the main chain.

As the ethylenically unsaturated group, a (meth)acrylic acid group or a (meth)acryloyloxy group is preferred, and a (meth)acryloyloxy group is more preferred.

The constituent unit having an ethylenically unsaturated group in the alkaline acrylic resin may be a single type or may be two or more types.

When the alkaline-soluble acrylic resin contains constituent units having ethylenically unsaturated groups, the content of the constituent units having ethylenically unsaturated groups relative to the total amount of the alkaline-soluble acrylic resin is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 50 mol%, and even more preferably 15 mol% to 40 mol%.

As a mechanism for introducing reactive groups into alkaline-soluble acrylic resins, there can be cited methods of reacting hydroxyl groups, carboxyl groups, primary amino groups, secondary amino groups, acetylacetyl groups, and sulfonic acid groups with epoxy compounds, blocked isocyanate compounds, isocyanate compounds, vinyl sulfone compounds, aldehyde compounds, hydroxymethyl compounds, and carboxylic anhydrides.

A preferred example of a mechanism for introducing reactive groups into an alkali-soluble acrylic resin is to synthesize an alkali-soluble acrylic resin having carboxyl groups through a polymerization reaction, then react some of the carboxyl groups of the alkali-soluble acrylic resin with glycidyl (meth)acrylate through a polymerization reaction to introduce (meth)acryloyloxy groups into the alkali-soluble acrylic resin. This mechanism can produce an alkali-soluble acrylic resin having (meth)acryloyloxy groups on its side chains.

The polymerization reaction is preferably carried out at a temperature of 70°C to 100°C, more preferably 80°C to 90°C. Azo initiators are preferred as polymerization initiators, for example, V-601 (product name) or V-65 (product name) manufactured by FUJIFILM Wako Pure Chemical Corporation. Furthermore, the polymerization reaction is preferably carried out at a temperature of 80°C to 110°C. A catalyst such as an ammonium salt is preferably used in the polymerization reaction.

The weight average molecular weight (Mw) of the alkali-soluble acrylic resin is preferably 10,000 or greater, more preferably 10,000 to 100,000, and even more preferably 15,000 to 50,000.

From the perspective of developing properties, the acid value of the alkali-soluble acrylic resin is preferably 50 mgKOH/g or greater, more preferably 60 mgKOH/g or greater, even more preferably 70 mgKOH/g or greater, and particularly preferably 80 mgKOH/g or greater. In the present invention, the acid value of the alkali-soluble acrylic resin is measured according to the method described in JIS K0070:1992. From the perspective of suppressing dissolution of the exposed negative photosensitive resin layer (exposed portion) in the developer, the upper limit of the acid value of the alkali-soluble acrylic resin is preferably 200 mgKOH/g or less, and more preferably 150 mgKOH/g or less.

Specific examples of the alkali-soluble acrylic resin are shown below. The content ratio (molar ratio) of each constituent unit in the alkali-soluble acrylic resin described below can be appropriately set within the above-described preferred Mw range depending on the intended purpose.

【Chemical formula 1】

【Chemical formula 2】

【Chemical formula 3】

The negative photosensitive resin layer may contain a single alkaline-soluble acrylic resin or may contain two or more alkaline-soluble acrylic resins.

From the perspective of developing properties, the content of the alkaline-soluble acrylic resin relative to the total mass of the negative photosensitive resin layer is preferably 10% to 90% by mass, more preferably 20% to 80% by mass, and even more preferably 25% to 70% by mass.

-Polymer Containing Constituent Units Having a Carboxylic Anhydride Structure- The negative photosensitive resin layer may further contain a polymer containing constituent units having a carboxylic anhydride structure (hereinafter also referred to as "polymer B") as a binder. The inclusion of polymer B in the negative photosensitive resin layer can improve developing properties and strength after curing.

The carboxylic anhydride structure may be either a chain carboxylic anhydride structure or a cyclic carboxylic anhydride structure, with the cyclic carboxylic anhydride structure being preferred.

The ring of the cyclic carboxylic acid anhydride structure is preferably a 5- to 7-membered ring, more preferably a 5- or 6-membered ring, and even more preferably a 5-membered ring.

The structural unit having a carboxylic anhydride structure is preferably a structural unit containing a divalent group obtained by removing two hydrogen atoms from a compound represented by the following formula P-1 in the main chain, or a structural unit containing a monovalent group obtained by removing one hydrogen atom from a compound represented by the following formula P-1, which is bonded to the main chain directly or via a divalent linking group.

【Chemical formula 4】

In formula P-1, ^RA1a represents a substituent, ^{n1a RA1a} groups may be the same or different, ^Z1a represents a divalent group forming a ring including -C(=O)-OC(=O)-, and ^n1a represents an integer greater than or equal to 0.

Examples of the substituent represented by ^RA1a include an alkyl group.

Z ^1a is preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and even more preferably an alkylene group having 2 carbon atoms.

n ^1a represents an integer greater than 0. When ^{Z 1a} represents an alkylene group having 2 to 4 carbon atoms, n ^1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0.

When n ^1a represents an integer greater than or equal to 2, the multiple R ^A1a may be the same or different. Furthermore, the multiple R ^A1a may be mutually bonded to form a ring, but it is preferred that they be mutually bonded without forming a ring.

As the constituent units having a carboxylic acid anhydride structure, constituent units derived from unsaturated carboxylic acid anhydrides are preferred, constituent units derived from unsaturated cyclic carboxylic acid anhydrides are more preferred, constituent units derived from unsaturated aliphatic cyclic carboxylic acid anhydrides are further preferred, constituent units derived from maleic anhydride or itaconic anhydride are particularly preferred, and constituent units derived from maleic anhydride are most preferred.

The constituent unit having a carboxylic acid anhydride structure in the polymer B may be a single type or two or more types.

The content of the structural units having a carboxylic anhydride structure relative to the total amount of polymer B is preferably 0 mol% to 60 mol%, more preferably 5 mol% to 40 mol%, and even more preferably 10 mol% to 35 mol%.

The negative photosensitive resin layer may contain only one type of polymer B, or may contain two or more types of polymers B.

When the negative photosensitive resin layer includes polymer B, from the viewpoint of developability and strength after curing, the content of polymer B relative to the total mass of the negative photosensitive resin layer is preferably 0.1 mass% to 30 mass%, more preferably 0.2 mass% to 20 mass%, even more preferably 0.5 mass% to 20 mass%, and particularly preferably 1 to 20 mass%.

-Surfactant- The negative photosensitive resin layer can contain a surfactant. Examples of surfactants include those described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060-0071 of Japanese Patent Application Laid-Open No. 2009-237362.

Examples of surfactants include fluorine-based surfactants, silicone-based surfactants (also called silicone-based surfactants), and nonionic surfactants. Fluorine-based surfactants and silicone-based surfactants are preferred. Commercially available fluorine-based surfactants include Megaface (registered trademark) F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, and F-5 56、F-557、F-558、F-559、F-560、F-561、F-565、F-563、F-568、F-575、F-780、EXP、MFS-330、R-41、R-41-LM、R-01、R-40、R-40-LM、RS-43、TF-1956、RS-90、R-94、RS-72-K、DS-21（The above are DIC Corporation), Fluorad (registered trademark) FC430, FC431, FC171 (all manufactured by Sumitomo 3M Limited), Surflon (registered trademark) S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC Inc.), PolyFox (registered trademark) PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA Solutions Inc.), FTERGENT (registered trademark) 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F (all manufactured by NEOS Corporation), etc.

Acrylic compounds are also preferably used as fluorine-based surfactants. These compounds have a molecular structure with functional groups containing fluorine atoms, and when heated, the fluorine-containing functional groups are partially cleaved, causing the fluorine atoms to volatilize. Examples of such fluorine-based surfactants include the Megaface (registered trademark) DS series manufactured by DIC Corporation (Chemical Industry Daily (February 22, 2016), Nikkei Industry News (February 23, 2016)), for example, Megaface (registered trademark) DS-21. Fluorine-based surfactants are also preferably polymers of fluorine-containing vinyl ether compounds having fluorinated alkyl or fluorinated alkylene ether groups and hydrophilic vinyl ether compounds. Block polymers can also be used as fluorine-based surfactants. Fluorine-based surfactants can also preferably be fluorinated polymers comprising repeating units derived from a (meth)acrylate compound containing fluorine atoms and repeating units derived from a (meth)acrylate compound containing two or more (preferably five or more) alkoxy groups (preferably ethoxy or propoxy).

Fluoropolymers with ethylenically unsaturated side chains can also be used as fluorine-based surfactants. Examples include Megaface (registered trademark) RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

Examples of silicone-based surfactants include linear polymers composed of siloxane bonds and modified silicone polymers with organic groups introduced into the side chains or terminals. Specific examples of commercially available silicone-based surfactants include DOWSIL (registered trademark) 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray). Co., Ltd.), X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (all manufactured by Shin-Etsu Chemical Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials Inc.), BYK307, BYK323, BYK330 (all manufactured by BYK Chemie GmbH), etc.

Examples of nonionic surfactants include glycerol, trihydroxymethylpropane, trihydroxymethylethane, and ethoxylates and propoxylates thereof (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan esters, Fatty acid esters, PLURONIC (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (all manufactured by BASF), TETRONIC (registered trademark) 304, 701, 704, 901, 904, 150R1 (all manufactured by BASF), SOLSPERSE (registered trademark) 20000 (all manufactured by Japan Lubrizol Corporation), NCW-101, NCW-1001, NCW-1002 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), Pionin (registered trademark) D-6112, D-6112-W, D-6315 (all manufactured by TAKEMOTO OIL & FAT Co., Ltd.), OLFIN E1010, Surfynol 104, 400, 440 (all manufactured by Nissin Chemical Industry Co., Ltd.), etc.

The negative photosensitive resin layer may contain only one surfactant or two or more surfactants.

When the negative photosensitive resin layer contains a surfactant, the content of the surfactant is preferably 0.01% to 3% by mass, more preferably 0.05% to 1% by mass, and even more preferably 0.1% to 0.8% by mass, relative to the total mass of the negative photosensitive resin layer.

-Other Components- The negative photosensitive resin layer may contain components other than those already described (hereinafter also referred to as "other components"). Examples of such other components include heterocyclic compounds, aliphatic thiol compounds, blocked isocyanate compounds, hydrogen-donating compounds, particles (e.g., metal oxide particles), and colorants. Other components also include, for example, the thermal polymerization inhibitors described in paragraph 0018 of Japanese Patent No. 4502784 and the other additives described in paragraphs 0058-0071 of Japanese Patent Application Laid-Open No. 2000-310706.

The negative photosensitive resin layer can be formed by drying a coating layer made of the negative photosensitive resin layer-forming coating liquid described above. The formation of the negative photosensitive resin layer is described in detail in the section on transfer materials.

- Impurities in the Negative Photosensitive Resin Layer- From the perspective of improving reliability and patterning properties, the impurity content in the negative photosensitive resin layer is preferably as low as possible. Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, and their ions, as well as halide ions (chloride ions, bromide ions, iodide ions, etc.). Of these, sodium ions, potassium ions, and chloride ions are easily incorporated as impurities, so the following contents are particularly preferred. On a mass basis, the impurity content in each layer is preferably 1,000 ppm or less, more preferably 200 ppm or less, and particularly preferably 40 ppm or less. The lower limit on a mass basis can be set to 0.01 ppm or greater, and can be set to 0.1 ppm or greater. Methods for reducing impurities to the above range include selecting impurity-free raw materials for each layer, preventing impurity incorporation during layer formation, and removing them through washing. These methods can bring the impurity content within the above range. For example, impurities can be quantified using known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

Furthermore, the negative photosensitive resin layer preferably contains low levels of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane. On a mass basis, the content of these compounds in each layer is preferably 1,000 ppm or less, more preferably 200 ppm or less, and particularly preferably 40 ppm or less. While there is no specific lower limit, from the perspective of practical reducibility and measurement limits, it can be set to 10 ppb or more, and preferably 100 ppb or more, on a mass basis. Compound impurities can be suppressed using the same methods as those for metal impurities described above. Furthermore, they can be quantified using known measurement methods.

Although the above description is about a negative photosensitive resin layer, it is preferable that the resin pattern formed from the negative photosensitive resin layer also have the same impurity amount.

-Negative Photosensitive Resin Layer Thickness The thickness of the negative photosensitive resin layer can be appropriately selected, with a thickness of 10 μm or greater being preferred, 15 μm or greater being more preferred, 20 μm or greater being even more preferred, and 30 μm or greater being particularly preferred. The upper limit is preferably 100 μm or less.

-Method for Forming a Negative Photosensitive Resin Layer- A negative photosensitive resin layer can be formed by preparing a negative photosensitive resin composition containing the components used to form the negative photosensitive resin layer and a solvent, applying the composition, and drying the composition. Alternatively, the composition can be prepared by preliminarily dissolving the components in a solvent to form a solution, and then mixing the resulting solutions in a predetermined ratio. The composition prepared in this manner can be filtered using, for example, a filter with a pore size of 0.2 μm to 30 μm. A negative photosensitive resin layer can be formed by coating a negative photosensitive resin composition on a dummy support or cover film and drying the composition. The coating method is not particularly limited and can be performed by known methods such as slit coating, spin coating, curtain coating, die coating, and inkjet coating. Alternatively, the negative photosensitive resin layer can be formed on top of an intermediate layer (described later) or other layers formed on the dummy support or cover film.

-Negative Photosensitive Resin Composition- A negative photosensitive resin composition preferably includes the components used to form a negative photosensitive resin layer and a solvent. By incorporating a solvent into each component, the viscosity can be adjusted, and the negative photosensitive resin layer can be properly formed by coating and drying.

The negative photosensitive resin composition preferably contains a solvent. An organic solvent is preferred as the solvent. Examples of such organic solvents include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam, n-propanol, and 2-propanol. Preferred solvents include a mixed solvent of methyl ethyl ketone and propylene glycol monomethyl ether acetate or a mixed solvent of diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate.

Solvents described in paragraphs 0054 and 0055 of U.S. Patent Application Publication No. 2005/282073 can also be used as solvents. The contents of that specification are incorporated herein by reference. Also, organic solvents with a boiling point of 180°C to 250°C (high-boiling-point solvents) can be used as solvents as needed. The negative photosensitive resin composition may contain a single solvent or two or more solvents. When the negative photosensitive resin composition contains a solvent, the total solid content of the negative photosensitive resin composition is preferably 5% to 80% by mass, more preferably 5% to 40% by mass, and even more preferably 5% to 30% by mass relative to the total mass of the negative photosensitive resin composition.

When the negative photosensitive resin composition contains a solvent, from the perspective of coatability, the viscosity of the negative photosensitive resin composition at 25°C is preferably 1 mPa·s to 50 mPa·s, more preferably 2 mPa·s to 40 mPa·s, and even more preferably 3 mPa·s to 30 mPa·s. Viscosity is measured using a viscometer. For example, a viscometer manufactured by TOKI SANGYO CO., LTD. (product name: VISCOMETER TV-22) can be preferably used. However, the viscometer is not limited to the above-mentioned viscometer.

When the negative photosensitive resin composition contains a solvent, for example, from the perspective of coatability, the surface tension of the negative photosensitive resin composition at 25°C is preferably 5 mN/m to 100 mN/m, more preferably 10 mN/m to 80 mN/m, and even more preferably 15 mN/m to 40 mN/m. Surface tension is measured using a surface tensiometer. For example, the Automatic Surface Tensiometer CBVP-Z manufactured by Kyowa Interface Science Co., Ltd. can be preferably used. However, the surface tensiometer is not limited to the one described above.

<<Transfer Material>> The transfer material used in the present invention comprises at least a negative photosensitive resin layer, and preferably comprises at least a pseudo-support and a negative photosensitive resin layer.

-Dummy Support- The transfer material used in the present invention preferably has a dummy support. The dummy support is a removable support that supports the negative photosensitive resin layer. The dummy support used in the present invention is preferably light-transmissive to enable exposure of the negative photosensitive resin layer through the dummy support during exposure. Light-transmissive means that the transmittance of the main wavelength of light used in pattern exposure is 50% or greater. To improve exposure sensitivity, the transmittance of the main wavelength of light used in pattern exposure is preferably 60% or greater, and more preferably 70% or greater. As a method for measuring transmittance, one example is the MCPD Series manufactured by Otsuka Electronics Co., Ltd. A glass substrate, resin film, or paper can be used as a pseudo-support. Resin film is particularly preferred from the perspectives of strength and flexibility. Examples of resin films include polyethylene terephthalate film, cellulose triacetate film, polystyrene film, and polycarbonate film. Biaxially oriented polyethylene terephthalate film is particularly preferred.

The thickness of the dummy support is not particularly limited, but a range of 5μm to 200μm is preferred. For ease of handling and versatility, a range of 10μm to 150μm is even more preferred. The thickness of the dummy support can be selected based on the material, taking into account factors such as support strength, flexibility required for bonding to the substrate, and light transmittance required during exposure.

Preferred aspects of the pseudo-support are described in, for example, paragraphs 0017 and 0018 of Japanese Patent Application Laid-Open No. 2014-85643, the contents of which are incorporated herein by reference.

-Coating Film- The transfer material used in the present invention preferably has a covering film on the surface opposite to the side on which the dummy support is provided. Resin films, paper, and the like can be used as the covering film. Resin films are particularly preferred from the perspectives of strength and flexibility. Examples of resin films include polyethylene films, polypropylene films, polyethylene terephthalate films, cellulose triacetate films, polystyrene films, and polycarbonate films. Among these, polyethylene films, polypropylene films, and polyethylene terephthalate films are preferred.

The average thickness of the cover film is not particularly limited, but is preferably, for example, 1 μm to 2 mm.

-Intermediate Layer- The transfer material or the laminate used in the present invention may include an intermediate layer (e.g., a water-soluble resin layer). Preferably, the intermediate layer comprises the polymer described below.

[Polymer] The interlayer can contain a polymer. Preferred polymers for the interlayer are water-soluble resins or alkali-soluble resins. In the present invention, "water-soluble" means a solubility of 0.1 g or greater in 100 g of water at pH 7.0 at 22°C, and "alkali-soluble" means a solubility of 0.1 g or greater in 100 g of a 1% by mass aqueous solution of sodium carbonate at 22°C. The terms "water-soluble and alkali-soluble" may refer to either water-soluble or alkali-soluble, or both. Preferably, the solubility of the polymer in 100 g of water at pH 7.0 at 22°C is 1 g or greater, and more preferably 5 g or greater. Examples of water-soluble resins include cellulose resins, polyvinyl alcohol resins, polyvinyl pyrrolidone resins, acrylamide resins, (meth)acrylate resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof. Cellulose resins are preferred, and at least one resin selected from the group consisting of hydroxypropyl cellulose and hydroxypropyl methyl cellulose is more preferred. Alkaline-soluble resins are preferably alkaline-soluble acrylic resins, and acrylic resins having acid groups capable of forming salts are even more preferred.

The interlayer may contain a single polymer or two or more. From the perspective of adhesion, the polymer content is preferably 20% to 100% by mass, and more preferably 50% to 100% by mass, relative to the total mass of the interlayer.

[Ultraviolet Absorber] The interlayer may contain a UV absorber to control absorption. The UV absorber is not particularly limited as long as it is a compound that absorbs UV light with a wavelength of 400 nm or less. Examples of UV absorbers include phenyl ketone compounds, benzotriazole compounds, benzoate compounds, salicylate compounds, tris(III) compounds, and cyanoacrylate compounds. Specifically, examples of benzotriazole compounds include 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(2H-benzotriazol-2-yl)-4-6-bis(1-methyl-1-phenylethyl)phenol, 2-[5-chloro(2H)-benzotriazol-2-yl]-4-methyl-6-(t-butyl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-di-t-pentylphenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, and mixtures, modified products, polymers, and derivatives thereof. For example, tristilbium compounds include 2-(4,6-diphenyl-1,3,5-tristilbium-2-yl)-5-[(hexyl)oxy]phenol, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-tristilbium, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-tristilbium, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-isooctyloxyphenyl)-s-tristilbium, and mixtures, modified products, polymers, and derivatives thereof. These can be used alone or in combination. The content of the UV-absorbing material is not particularly limited and can be appropriately set to achieve the desired optical density of the photosensitive resin layer.

[Surfactant] From the perspective of thickness uniformity, it is preferable to include a surfactant in the interlayer. Surfactants can be any of those containing fluorine atoms, those containing silicon atoms, and those containing neither fluorine atoms nor silicon atoms. From the perspective of suppressing the formation of streaks in the negative photosensitive resin layer and the interlayer and improving adhesion, surfactants containing fluorine atoms are preferred, and those containing perfluoroalkyl and polyalkylene oxide groups are even more preferred. Surfactants can be anionic, cationic, nonionic, or amphoteric. Nonionic surfactants are preferred. From the perspective of suppressing surfactant precipitation, the solubility of the surfactant in 100g of water at 25°C is preferably 1g or greater.

The interlayer may contain a single surfactant or two or more. From the perspective of suppressing the occurrence of streaks in the negative photosensitive resin layer and the interlayer and maintaining good adhesion, the content of the surfactant in the interlayer is preferably 0.05% to 2.0% by mass, more preferably 0.1% to 1.0% by mass, and particularly preferably 0.2% to 0.5% by mass, relative to the total mass of the interlayer.

[Inorganic Filler] The interlayer may contain an inorganic filler. The inorganic filler used in the present invention is not particularly limited. Examples include silica particles, alumina particles, and zirconia particles, with silica particles being particularly preferred. From the perspective of transparency, smaller particles are preferred, with an average particle size of 100 nm or less being particularly preferred. For example, commercially available products such as NOWTEX (registered trademark) are suitable.

From the perspective of adhesion between the interlayer and the negative photosensitive resin layer, the volume fraction of the particles in the interlayer (the volume ratio of the particles in the interlayer) relative to the total volume of the interlayer is preferably 5% to 90%, more preferably 10% to 80%, and even more preferably 20% to 60%.

[pH Adjuster] The interlayer may contain a pH adjuster. The inclusion of a pH adjuster can further stably maintain the coloring or decoloring state of the pigment in the interlayer and further improve the adhesion between the negative photosensitive resin layer and the interlayer. The pH adjuster used in the present invention is not particularly limited. Examples include sodium hydroxide, potassium hydroxide, lithium hydroxide, organic amines, and organic ammonium salts. From the perspective of water solubility, sodium hydroxide is preferred. From the perspective of adhesion between the negative photosensitive resin layer and the interlayer, organic ammonium salts are preferred.

[Intermediate Layer Thickness] From the perspective of adhesion between the negative photosensitive resin layer and the intermediate layer, as well as pattern formation, the thickness of the intermediate layer is preferably 0.3μm to 10μm, more preferably 0.3μm to 5μm, and particularly preferably 0.3μm to 2μm. It is also preferable that the thickness of the intermediate layer is thinner than that of the negative photosensitive resin layer.

The interlayer may have two or more layers. If the interlayer has two or more layers, the thickness of each layer is not particularly limited as long as it is within the above range. From the perspective of adhesion between the interlayer and the negative photosensitive resin layer and pattern formation, the thickness of the layer closest to the negative photosensitive resin layer among the two or more layers in the interlayer is preferably 0.3 μm to 10 μm, more preferably 0.3 μm to 5 μm, and particularly preferably 0.3 μm to 2 μm.

[Method for Forming an Intermediate Layer] The intermediate layer of the present invention can be formed by preparing an intermediate layer-forming composition containing the intermediate layer-forming components and a water-soluble solvent, applying the composition, and drying the composition. Alternatively, the composition can be prepared by dissolving the components separately in a solvent to form a solution, and then mixing the resulting solutions in predetermined proportions. The composition prepared in this manner can be filtered using a filter with a pore size of 3.0 μm, for example. The intermediate layer can be formed on the dummy support by applying the intermediate layer-forming composition to the dummy support and drying the composition. The coating method is not particularly limited, and coating can be performed by known methods such as slit coating, rotary coating, curtain coating, and inkjet coating.

The intermediate layer-forming composition preferably includes ingredients for forming the intermediate layer and a water-soluble solvent. By including a water-soluble solvent in each ingredient to adjust the viscosity and perform coating and drying, the intermediate layer can be properly formed.

As the water-soluble solvent, any known water-soluble solvent can be used. Examples thereof include water and alcohols having 1 to 6 carbon atoms, with water being preferred. Specific examples of alcohols having 1 to 6 carbon atoms include methanol, ethanol, n-propanol, isopropanol, n-butanol, n-pentanol, and n-hexanol. Among these, at least one selected from the group consisting of methanol, ethanol, n-propanol, and isopropanol is preferred.

-Other Layers- The transfer material of the present invention may have layers other than those described above (hereinafter also referred to as "other layers"). Examples of such other layers include thermoplastic resin layers. Preferred embodiments of the thermoplastic resin layer are described in paragraphs 189 to 193 of Japanese Patent Application Laid-Open No. 2014-85643, and further preferred embodiments of other layers are described in paragraphs 194 to 196 of Japanese Patent Application Laid-Open No. 2014-85643. The contents of these publications are incorporated herein.

-Transfer Material Manufacturing Method- The transfer material manufacturing method used in the present invention is not particularly limited, and known manufacturing methods, such as known methods for forming each layer, can be used. The transfer material manufacturing method preferably includes forming a negative photosensitive resin layer on a dummy support and then providing a cover film on the negative photosensitive resin layer. Furthermore, after manufacturing the transfer material, the transfer material can be rolled up to produce and store it in roll form. The roll-form transfer material can be provided in a roll-to-roll configuration, bonded to the substrate.

(Method for Manufacturing a Metal Mask for Evaporation) The method for manufacturing a metal mask for evaporation of the present invention includes forming a metal pattern on a metal mask for evaporation using the method for forming a metal pattern of the present invention. The method for manufacturing a metal mask for evaporation of the present invention preferably includes the following steps: preparing a laminate having a negative photosensitive resin layer on a substrate; irradiating the negative photosensitive resin layer with light having a component that is incident obliquely in the thickness direction of an exposure mask from a side of the negative photosensitive resin layer opposite to the side on which the substrate is disposed, thereby pattern-exposing the negative photosensitive resin layer through the exposure mask; developing the pattern-exposed negative photosensitive resin layer to form a resin pattern having a tapered shape; and forming a metal pattern having a tapered shape corresponding to the shape of the resin pattern. Furthermore, the method for manufacturing a metal mask for evaporation of the present invention may include the steps of the aforementioned method for forming a metal pattern of the present invention, and the preferred embodiments are the same. Furthermore, the metal mask for evaporation manufactured by the method for manufacturing a metal mask for evaporation of the present invention may include other components in addition to the aforementioned metal pattern. These other components are not particularly limited, and known components used in metal masks for evaporation may be used.

(Method for Manufacturing an Organic Light-Emitting Diode and Method for Manufacturing an Organic EL Display) The method for manufacturing an organic light-emitting diode or the method for manufacturing an organic EL display of the present invention utilizes a metal pattern obtained by the method for forming a metal pattern of the present invention. Preferably, the method for manufacturing an organic light-emitting diode or the method for manufacturing an organic EL display of the present invention includes a step of using the metal pattern obtained by the method for forming a metal pattern of the present invention as a metal mask for evaporation. More preferably, the metal pattern obtained by the method for forming a metal pattern of the present invention serves as a metal mask for evaporation of an organic light-emitting material, and the organic light-emitting material is evaporated onto a substrate or the like. Examples of the organic light-emitting material include red (R), green (G), or blue (B) organic light-emitting materials. Furthermore, the method for manufacturing an organic light-emitting diode or an organic EL display device of the present invention may include the steps of the aforementioned method for forming a metal pattern of the present invention, and the preferred embodiments are the same. Furthermore, the method for manufacturing an organic light-emitting diode or an organic EL display device of the present invention may include known steps other than those described above. [Examples]

The following examples further illustrate the embodiments of the present invention. The materials, amounts, ratios, processing details, and processing sequence shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Furthermore, unless otherwise specified, "parts" and "%" are by mass.

<Measurement of the Scattering Angle of the Scattering Layer> Using a Goniometer GP-200 manufactured by Murakami Color Research Laboratory Co., Ltd., we projected light perpendicularly onto the scattering layer and measured the intensity of the transmitted light over an angle range from +90° to -90°. The scattering angle was defined as the angle at which the full angular width, corresponding to the intensity at 0°, was halved.

<Preparation of Negative Photosensitive Resin Compositions 1 and 2> After mixing the compositions shown in Table 1 below, methyl ethyl ketone was added to prepare negative photosensitive resin compositions 1 and 2, respectively (indicated in Table 1 as Compositions 1 and 2. Solids concentration: 25% by mass).

【Table 1】 Ingredients (value of each ingredient: mass parts) Component 1 Component 2 Alkaline soluble acrylic resin Copolymer of styrene/methacrylic acid/methyl methacrylate = 32/28/40 (mass %), Mw = 40,000 - 55.00 Copolymer of styrene/methacrylic acid/methyl methacrylate = 52/29/19 (mass %), Mw = 60,000 50.00 - Copolymer of benzyl methacrylate/methacrylic acid = 81/19 (mass %), Mw = 40,000 - - polymerizable compounds BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd.) 36.20 20.20 BPE-200 (manufactured by Shin-Nakamura Chemical Co., Ltd.) - 9.80 Polyethylene glycol dimethacrylate obtained by adding an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide to the two ends of bisphenol A - - M-270 (manufactured by TOAGOSEI CO., LTD.) 5.00 - A-TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) - 10.00 SR-454 (manufactured by Arkema SA) - - SR-502 (manufactured by Arkema SA) - - A-9300-CL1 (manufactured by Shin-Nakamura Chemical Co., Ltd.) - - Polymerization initiator B-CIM (manufactured by KUROGANE KASEI Co., Ltd.) 7.00 3.00 sensitizers SB-PI 701 (manufactured by SANYO KASEI CO., LTD.) 0.50 0.50 chain transfer agents Colorless crystal violet (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.40 0.90 N-phenylglycine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.20 - Colorant Malachite green (manufactured by Tokyo Chemical Industry Co., Ltd.) - 0.05 rust repellent CBT-1 (manufactured by JOHOKU CHEMICAL CO., LTD.) 0.10 - A 1:1 (mass ratio) mixture of 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole - 0.14 polymerization inhibitors TDP-G (manufactured by Kawaguchi Chemical Industry Co., Ltd.) 0.30 0.10 Irganox 245 (manufactured by BASF) - - N-Nitrosophenylhydroxylamine aluminum salt (manufactured by FUJIFILM Wako Pure Chemical Corporation) - - antioxidants Phenidone (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.01 0.01 surfactants F-552 (manufactured by DIC Corporation) 0.29 0.30

In addition, the details of the compounds listed in Table 1 are shown below. BPE-500: 2,2-bis(4-(methacryloyloxypentaethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd. BPE-200: 2,2-bis(4-(methacryloyloxydiethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd. M-270: Polypropylene glycol diacrylate, manufactured by TOAGOSEI CO., LTD. A-TMPT: Trihydroxymethylpropane triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. SR-454: Ethoxylated (3) trihydroxymethylpropane triacrylate, manufactured by SARTOMER SR-502: Ethoxylated (9) trihydroxymethylpropane triacrylate, manufactured by SARTOMER A-9300-CL1: ε-Caprolactone-modified tris-(2-acryloyloxyethyl) isocyanurate, manufactured by Shin-Nakamura Chemical Co., Ltd. B-CIM: Photoradical generator (photopolymerization initiator), manufactured by Hampford, 2-(2-chlorophenyl)-4,5-diphenylimidazole dimer SB-PI 701: Sensitizer, 4,4'-bis(diethylamino)benzophenone, manufactured by Sanyo Trading Co., Ltd. CBT-1: Rust preventer, carboxybenzotriazole, manufactured by JOHOKU CHEMICAL CO., LTD. TDP-G: Polymerization inhibitor, phenothiophene, manufactured by Kawaguchi Chemical Industry Co., Ltd. Irganox 245: Hindered phenol-based polymerization inhibitor, manufactured by BASF F-552: Fluorine-based surfactant, Megaface F552, manufactured by DIC Corporation

<Preparation of Transfer Material A> On a dummy support of 16μm-thick polyethylene terephthalate film (16KS40, product name, TORAY INDUSTRIES, INC.), a bar coater was used to adjust the amount of negative photosensitive resin composition 1 applied so that the thickness of the dried negative photosensitive resin layer would be 10μm. After applying negative photosensitive resin composition 1, the film was dried in an 80°C oven to form a negative photosensitive resin layer. Next, a 16μm-thick polyethylene terephthalate (16KS40: product name, TORAY INDUSTRIES, INC.) was pressed onto the surface of the negative photosensitive resin layer as a cover film to create transfer material A.

<Preparation of Transfer Material B> The following water-soluble resin composition was applied to a 16μm-thick polyethylene terephthalate film (16KS40, TORAY INDUSTRIES, INC.), serving as a pseudo-support, using a bar coater to a dry thickness of 1μm. This was then dried in a 90°C oven to form a water-soluble resin layer as an intermediate layer. Next, using a bar coater, negative photosensitive resin composition 2 was applied onto the water-soluble resin layer, adjusting the amount of negative photosensitive resin composition 2 applied so that the thickness of the dried negative photosensitive resin layer would be 10 μm. The negative photosensitive resin layer was then dried in an 80°C oven to form a negative photosensitive resin layer. Subsequently, a 16 μm thick polyethylene terephthalate (16KS40, product name, TORAY INDUSTRIES, INC.) cover film was press-bonded to the surface of the negative photosensitive resin layer to produce transfer material B.

- Composition of the Water-Soluble Resin Composition- · Ion-exchanged water: 38.12 parts · Methanol (manufactured by Mitsubishi Gas Chemical Company, Inc.): 57.17 parts · Kuraray POVALPVA-205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.): 3.22 parts · Polyvinylpyrrolidone K-30 (manufactured by Nippon Shokubai Co., Ltd.): 1.49 parts · Megaface F-444 (fluorinated nonionic surfactant, manufactured by DIC Corporation): 0.0015 parts

<Preparation of Transfer Material C> Transfer Material C was prepared in the same manner as Transfer Material A, except that the thickness of the negative photosensitive resin layer after drying was changed to 8 μm.

<Preparation of Transfer Material D> Transfer Material D was prepared in the same manner as Transfer Material A, except that the thickness of the negative photosensitive resin layer after drying was changed to 20 μm.

(Example 1) <Laminate Formation> The cover film of the transfer material A prepared above was peeled off, and the exposed surface of the negative photosensitive resin layer on glass was plated with Ni (100 nm thick). The negative photosensitive resin layer and dummy support were then laminated under the following conditions to obtain a laminate (preparatory step). -Laminar Conditions- Substrate Temperature: 80°C Rubber Roller Temperature: 110°C Linear Pressure: 3 N/cm Conveyor Speed: 2 m/min

<Resin Pattern Formation> Next, an exposure mask (line/space = 20μm/20μm, line length 100μm) was brought into close contact with the surface of the pseudo-support of the resulting laminate. A lens diffuser sheet (registered trademark) LSD60ACUVT30 (scattering angle: 60°, diffusion transmittance: 95%, material: UV-transmitting acrylic resin) manufactured by OPTICAL SOLUTIONS Corporation was placed on the exposure mask as a scattering layer. The exposure mask and scattering layer were placed so as not to contact each other. In Table 2, the scattering layer used in Example 1 is listed as "resin layer having unevenness." Using a high-pressure mercury lamp exposure system (MAP-1200L, manufactured by Japan Science Engineering Co., Ltd., main wavelength: 365 nm), light was transmitted through a dummy support and pattern-exposed at 150 mJ/ ^cm² on the negative photosensitive resin layer (pattern exposure step). After peeling the dummy support, spray development was performed for 50 seconds using a sodium carbonate aqueous solution at a liquid temperature of 25°C, forming a tapered resin pattern (resin pattern formation step).

<Observation of Resin Pattern Cross-Sectional Shape (Taper Shape Evaluation)> The cross-sectional shape of the resin pattern was observed at 10 random locations within the substrate surface using a scanning electron microscope (SEM). As shown in Figure 5, the width of the pattern top (W1), the width at half the pattern thickness (W2), the width at the pattern bottom (W3), and the thickness (W4) were measured. The average value of these values was used to calculate the value of tan(W4/((W3-W1)/2)). The evaluation criteria are shown below. A: W3>W2>W1 is satisfied, and the above value is less than 5.67. B: W3>W2>W1 is satisfied, and the above value is 5.67 or greater. C: W3>W2>W1 is not satisfied.

<Metal Pattern Formation> Electrolytic plating was performed as follows, using a conductive substrate as an electrode. An electrodeposit (metal pattern) with a thickness of approximately 7μm was deposited on the conductive substrate in areas where the resin pattern had not been formed. In a plating bath heated to 50°C, the plating solution was added, the conductive substrate (prepared as a cathode) and nickel plates (prepared as anodes) were placed, and a power source was connected. The power source was then operated, passing a current between the conductive substrate and the nickel plates for approximately 60 minutes. A nickel electroplated layer (metal pattern) was formed on the surface of the conductive substrate in areas where the resin pattern had not been formed (metal pattern formation step).

<Removal of Resin Pattern> Next, the resin pattern was removed by immersion in a 5% by mass triethylamine aqueous solution (boiling point 89°C) adjusted to 40°C for 60 seconds, forming a tapered metal pattern on the substrate.

<Substrate Peeling> The conductive substrate with the metal pattern formed above was stretched and peeled at 50 mm/s while folding 180 degrees, resulting in a metal mask with the metal pattern.

<Cross-sectional Shape Observation (Taper Shape Evaluation)> The cross-sectional shape of the obtained metal pattern was observed at 10 random locations within the substrate surface using an electron microscope (SEM). As shown in Figure 6, the width of the pattern top (W5), the width at half the pattern thickness (W6), the width of the pattern bottom (W7), and the thickness (W8) were measured. Using the average of these values, the value of tan(W8/((W5-W7)/2)) was calculated. The evaluation criteria are shown below. A: W5>W6>W7 is satisfied, and the above value is less than 5.67. B: W5>W6>W7 is satisfied, and the above value is 5.67 or greater. C: W5>W6>W7 is not satisfied.

<Exposure Margin> The cross-sectional shape of the resin pattern obtained using the same method as the resin pattern formation was observed in the same manner as above, except that the exposure was varied by ±5%. As shown in Figure 5, the width of the pattern top (W1), the width of half the pattern film thickness (W2), the width of the pattern bottom (W3), and the film thickness (W4) were measured. Using the average of these values, the value of tan(W4/((W3-W1)/2)) was calculated. Under these conditions, evaluation was performed in the same manner as for observing the cross-sectional shape of the resin pattern (taper shape evaluation). A: The resin pattern produced by exposure with a ±5% variation in exposure satisfies W3>W2>W1, and the above value is less than 5.67. B: The resin pattern produced by exposing with a ±5% change in exposure satisfies W3>W2>W1, and the above value is 5.67 or higher. C: The resin pattern produced by exposing with a ±5% change in exposure does not satisfy W3>W2>W1.

(Examples 2-9 and Comparative Examples 1 and 2) As shown in Table 2, resin patterns and metal patterns were formed in the same manner as in Example 1, except for changes in the exposure method and transfer material. Evaluations were also conducted in the same manner as in Example 1. The evaluation results are shown in Table 2. More details are as follows.

In Example 2, the resin and metal patterns were formed in the same manner as in Example 1, except that the scattering layer used in Example 1 was replaced with a layer containing a specific resin. The specific resin layer in Example 2 was a 30 μm thick layer containing 15% by mass, based on the solid content of the specific resin layer, of silica particles with an average primary particle size of 1.5 μm (Seahoster KE-P150, manufactured by NIPPON SHOKUBAI CO., LTD., refractive index 1.43) in the black matrix material, polymethyl methacrylate (refractive index 1.50). In the scattering layer of Example 2, the refractive index difference between the black matrix material and the specific particles is 0.07, and the refractive index difference is greater than 0.05. Furthermore, the scattering angle of the scattering layer of Example 2 is 30°, and the diffuse transmittance is 90%. In Example 2, the scattering layer is formed by spin coating a layer containing a specific resin on the side of the exposure mask opposite to the side where the chromium pattern (light-blocking pattern) is formed.

In Example 3, a resin pattern and a metal pattern were formed in the same manner as in Example 1, except that the dummy support was peeled off and an exposure mask was brought into contact with the negative photosensitive resin layer for pattern exposure.

In Example 4, a resin pattern and a metal pattern were formed in the same manner as in Example 3 except that transfer material B was used.

In Example 5, a resin pattern and a metal pattern were formed in the same manner as in Example 1 except that transfer material C was used.

In Example 6, a resin pattern and a metal pattern were formed in the same manner as in Example 1 except that the transfer material D was used.

In Example 7, a resin pattern and a metal pattern were formed in the same manner as in Example 1, except that Light Up LDS (manufactured by KIMOTO CO., LTD., scattering angle: 30°, light-diffusing polymer film, resin layer with concavo-convex texture, thickness 115 μm) was used as the scattering layer.

In Example 8, a resin pattern and a metal pattern were formed in the same manner as in Example 1, except that an exposure mask (line/space = 5 μm/20 μm, line length of 100 μm) was used.

In Example 9, as an exposure mask, a resin pattern and a metal pattern are formed in the same manner as in Example 1, except that a 3μm×3μm square space portion (opening portion) SP as shown in Figure 7 is arranged two-dimensionally at intervals of 25μm in the vertical and horizontal directions (in addition, in Figure 7, only a 3×3 space portion is shown schematically), and a mask in which the portion other than the above-mentioned space portion is a light-shielding portion is used.

In Comparative Example 1, a resin pattern and a metal pattern were formed in the same manner as in Example 1, except that no scattering layer was provided.

In Comparative Example 2, a resin pattern and a metal pattern were formed in the same manner as in Example 1, except that transfer material B was used and no scattering layer was provided.

【Table 2】 Exposure method Scattering layer Types of transfer materials Negative photosensitive resin layer thickness (μm) Evaluation of the conical shape of resin patterns Evaluation of the pyramidal shape of metal patterns Exposure margin Example 1 Exposure through pseudo-support Resin layer with bumps A 10 A A A Example 2 Exposure through pseudo-support Layer containing specific particles A 10 B B A Example 3 After removing the pseudo-support, exposure Resin layer with bumps A 10 A A A Example 4 After removing the pseudo-support, exposure Resin layer with bumps B 10 A A A Example 5 After removing the pseudo-support, exposure Resin layer with bumps C 8 B B A Example 6 After removing the pseudo-support, exposure Resin layer with bumps D 20 A A A Example 7 After removing the pseudo-support, exposure Concave and convex resin layer*2 A 10 A A A Example 8 After removing the pseudo-support, exposure Resin layer with bumps A 10 A A A Example 9 After removing the pseudo-support, exposure Resin layer with bumps A 10 A A A Comparative example 1 Exposure through pseudo-support without A 10 C C C Comparative example 2 Exposure through pseudo-support without B 10 C C C

As shown in Table 2, the metal pattern forming methods of Examples 1 to 9 produced metal patterns with superior tapered shapes compared to the metal pattern forming methods of Comparative Examples 1 or 2.

(Description of Symbols) 12: Substrate, 16: Negative photosensitive resin layer, 16A: Patterned hardened layer (resin pattern), 24: Pseudo-support, 26: Exposure mask, 26A: Light-shielding area of the exposure mask, 28: Scattering layer, 32: Scattering exposure mask, 32A: Light-shielding area of the scattering exposure mask, 100: Laminated body, 102: Substrate, 104: Resin pattern, 104a: Negative photosensitive resin layer, 106: Gold Metal pattern, θ1: taper angle of resin pattern, θ2: taper angle of metal pattern, W1: width of resin pattern top, W2: width of half the thickness of resin pattern, W3: width of resin pattern bottom, W4: thickness of resin pattern, W5: width of metal pattern top, W6: width of half the thickness of metal pattern, W7: width of metal pattern bottom, W8: thickness of metal pattern, SP: space.

The disclosure of Japanese Patent Application No. 2020-130530 filed on July 31, 2020, is hereby incorporated by reference in its entirety into this specification. All documents, patent applications, and technical standards described in this specification are hereby incorporated by reference into this specification to the same extent as if specifically stated in each individual document, patent application, and technical standard.

Figure 1 is a schematic diagram illustrating a preferred example of a metal pattern forming method according to the present invention. Figure 2 is a schematic cross-sectional view illustrating a first embodiment of the arrangement of a scattering layer during light irradiation in the pattern exposure step. Figure 3 is a schematic cross-sectional view illustrating a second embodiment of the arrangement of a scattering layer during light irradiation in the pattern exposure step. Figure 4 is a schematic cross-sectional view illustrating an example of a light-scattering exposure mask using a third embodiment of the arrangement of a scattering layer during light irradiation in the pattern exposure step. Figure 5 is a schematic cross-sectional view illustrating the length and position of various components in an example of a resin pattern. Figure 6 is a schematic cross-sectional view illustrating the length and position of various components in an example of a metal pattern. Figure 7 is a schematic view illustrating an example of a pattern shape of an exposure mask.

100: Laminated body 102: Substrate 104: Resin pattern 104a: Negative photosensitive resin layer 106: Metal pattern θ1: Taper angle of resin pattern θ2: Taper angle of metal pattern

Claims (18)

A method for forming a metal pattern comprises: preparing a laminate having a negative photosensitive resin layer on a substrate; irradiating the negative photosensitive resin layer with light having a component incident obliquely in the thickness direction of an exposure mask from a side of the negative photosensitive resin layer opposite to a side on which the substrate is provided, thereby pattern-exposing the negative photosensitive resin layer through the exposure mask; and developing the pattern-exposed negative photosensitive resin layer to form a resin pattern having a tapered shape. and forming a metal pattern having a pyramidal shape corresponding to the shape of the resin pattern. The preparation step includes using a transfer material having a dummy support and a negative photosensitive resin layer disposed on the dummy support, transferring the negative photosensitive resin layer possessed by the transfer material to the substrate to form the laminate. In the pattern exposure step, the pattern is exposed by contact exposure in which the dummy support is brought into contact with the exposure mask. A method for forming a metal pattern as described in claim 1, wherein in the step of exposing the aforementioned pattern, a scattering layer with a diffusion transmittance of 5% or more and an exposure light source are sequentially arranged on the opposite side of the aforementioned exposure mask to the aforementioned negative photosensitive resin layer, and scattered light is irradiated from the aforementioned exposure light source through the aforementioned scattering layer. The method for forming a metal pattern as described in claim 2, wherein the scattering layer contains a black matrix material and particles present in the black matrix material, and the difference in refractive index between the black matrix material and the particles is greater than 0.05. The method for forming a metal pattern as described in claim 2 or claim 3, wherein the scattering layer contains a black matrix material and particles present in the black matrix material, and the average primary particle size of the particles is greater than 0.3 μm. The method for forming a metal pattern as described in claim 2, wherein the scattering layer has concavities and convexities on at least one surface. The method for forming a metal pattern as described in claim 5, wherein the aforementioned concavo-convex has a plurality of convex portions, and the distance between the tops of adjacent convex portions is 10μm to 50μm. The method for forming a metal pattern as described in claim 2, wherein the scattering layer and the exposure mask are arranged at positions that do not contact each other. The method for forming a metal pattern as described in claim 2, wherein the scattering layer is in contact with the exposure mask and is arranged on the opposite side of the negative photosensitive resin layer in the exposure mask. The method for forming a metal pattern as described in claim 2, wherein the exposure mask is a scattering exposure mask having the scattering layer formed on the surface opposite to the surface on which the light-shielding pattern is formed. The method for forming a metal pattern as described in claim 1 or claim 2, wherein the substrate is a conductive substrate. The method for forming a metal pattern as described in claim 1 or claim 2, wherein the metal pattern is formed by electroplating. The method for forming a metal pattern as described in claim 1 or claim 2, further comprising the step of removing the resin pattern after the step of forming the metal pattern. The method for forming a metal pattern as described in claim 12, wherein the resin pattern is removed by using a chemical solution. The method for forming a metal pattern as described in claim 1 or claim 2 further includes the step of removing the aforementioned substrate from the aforementioned metal pattern. The method for forming a metal pattern as described in claim 1 or claim 2, wherein the resin pattern comprises a pyramidal or conical resin pattern. The method for forming a metal pattern as described in claim 1 or claim 2, wherein the thickness of the negative photosensitive resin layer is greater than 10 μm. The method for forming a metal pattern as described in claim 1 or claim 2, wherein the obtained metal pattern is a metal pattern for metal masking for evaporation. A method for manufacturing a metal mask for evaporation, comprising the step of forming a metal pattern using the method for forming a metal pattern described in any one of claims 1 to 17.