Photosensitive transfer material and method for producing resin pattern

Abstract

A light-sensitive transfer material, and an application therefor, said material including: a temporary support body having a first surface and a second surface on the opposite side from the first surface; and a light-sensitive resin layer on the second surface of the temporary support body, the value L* of the second surface of the temporary support body measured using an SCE method being 1.5 or less.

Description

Technical Field

[0001] The present disclosure relates to a photosensitive transfer material and a method for manufacturing a resin pattern.

Background Art

[0002] In a display device (for example, an organic electroluminescence (EL) display device and a liquid crystal display device) provided with a touch panel such as a capacitive input device, the touch panel includes a conductive pattern. The conductive pattern is used, for example, as a sensor of a visual recognition unit, peripheral wiring, or extraction wiring. As a method for manufacturing a pattern such as a conductive pattern and a resin pattern, for example, a method using a photosensitive transfer material can be mentioned. As a method for manufacturing a resin pattern using a photosensitive transfer material, a method including a step of providing a photosensitive resin layer and a temporary support on a substrate using the photosensitive transfer material, a step of pattern-exposing the photosensitive resin layer through the temporary support, and a step of developing the exposed photosensitive resin layer is widely adopted (for example, Japanese Patent Application Laid-Open No. 2017-156735).

Summary of the Invention

Problems to be Solved by the Invention

[0003] In a method for manufacturing a resin pattern using a photosensitive transfer material, improvement in the linearity of the resin pattern is required. Further, the linearity of the resin pattern also affects, for example, the linearity of circuit wiring formed using the resin pattern.

[0004] An object of one embodiment of the present disclosure is to provide a photosensitive transfer material that forms a resin pattern having high linearity. Another object of the present disclosure is to provide a method for manufacturing a resin pattern having high linearity.

Means for Solving the Problems

[0005] The present disclosure includes the following aspects. <1> A temporary support having a first surface and a second surface on the opposite side of the first surface, and a photosensitive resin layer on the second surface of the temporary support. The L value of the second surface of the temporary support measured by the SCE method * is 1.5 or less. A photosensitive transfer material. <2> The photosensitive transfer material according to <1>, wherein the thickness of the temporary support is 16 μm or less. <3> The L value of the first surface of the temporary support measured by the SCE method * is 0.6 or more. The photosensitive transfer material according to <1> or <2>. <4> The L value of the first surface of the temporary support measured by the SCE method * is 2.0 or less. The photosensitive transfer material according to any one of <1> to <3>. <5> The photosensitive transfer material according to any one of <1> to <4>, wherein the thickness of the photosensitive resin layer is 1 μm to 10 μm. <6> The photosensitive transfer material according to any one of <1> to <5>, wherein the temporary support includes a particle-containing layer disposed as the outermost layer of the temporary support and a base material in this order in the lamination direction from the temporary support toward the photosensitive resin layer.

[0006] <7> A temporary support having a first surface and a second surface on the opposite side of the first surface, and a photosensitive resin layer on the second surface of the temporary support. The temporary support is a polyester film composed of two or more layers, and at least one surface layer does not contain particles. A photosensitive transfer material. <8> The photosensitive transfer material according to <7>, wherein the surface layer on the second surface side of the temporary support does not contain particles. <9> The photosensitive transfer material according to <7> or <8>, wherein the surface layer on the first surface side of the temporary support does not contain particles. <10> The L value of the second surface of the temporary support measured by the SCE method *The photosensitive transfer material according to any one of <7> to <9>, wherein the value is 1.5 or less. <11> L of the first surface of the temporary support measured by the SCE method * The photosensitive transfer material according to any one of <7> to <10>, wherein the value is 2.0 or less. <12> The photosensitive transfer material according to any one of <7> to <11>, wherein the arithmetic mean roughness Ra of the first surface of the temporary support is 1 nm to 50 nm. <13> The photosensitive transfer material according to any one of <7> to <12>, wherein the surface layer has a phase separation structure. <14> The photosensitive transfer material according to any one of <7> to <13>, wherein the surface layer contains a polyester resin having an alicyclic structure. <15> The photosensitive transfer material according to <14>, wherein the alicyclic structure is a cyclohexane ring. <16> The photosensitive transfer material according to <14> or <15>, wherein the surface layer contains a copolymerized polyethylene terephthalate having isophthalic acid as a copolymer component.

[0007] <17> A method for producing a resin pattern using the photosensitive transfer material according to any one of <1> to <16>, comprising: preparing a substrate; contacting the photosensitive transfer material with the substrate and arranging the photosensitive resin layer and the temporary support on the substrate in this order; pattern-exposing the photosensitive resin layer; developing the exposed photosensitive resin layer to form a resin pattern; A method for producing a resin pattern including the above steps.

Advantages of the Invention

[0008] According to one embodiment of the present disclosure, a photosensitive transfer material for forming a resin pattern having high linearity is provided. According to another embodiment of the present disclosure, a method for producing a resin pattern having high linearity is provided.

Brief Description of the Drawings

[0009]

Figure 1

Figure 2

Figure 3

Mode for Carrying Out the Invention

[0010] Hereinafter, embodiments of the present disclosure will be described in detail. The present disclosure is not limited to the following embodiments in any way. The following embodiments may be appropriately changed within the scope of the object of the present disclosure.

[0011] When describing the embodiments of the present disclosure with reference to the drawings, the description of overlapping components and reference numerals in the drawings may be omitted. Components denoted by the same reference numerals in the drawings mean the same components. The ratio of dimensions in the drawings does not necessarily represent the ratio of actual dimensions.

[0012] In the present disclosure, a numerical range indicated by "~" indicates a range including the numerical values described before and after "~" as the lower limit value and the upper limit value, respectively. In the numerical ranges described stepwise in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in other stepwise descriptions. Further, in the numerical ranges described in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.

[0013] In the present disclosure, the term "step" includes not only an independent step but also this term when the intended purpose of the step is achieved even if it cannot be clearly distinguished from other steps.

[0014] In the present disclosure, "mass%" and "mass%" are synonymous, and "parts by mass" and "parts by mass" are synonymous.

[0015] In the present disclosure, when a plurality of substances corresponding to a certain component are present in a composition, the amount of the above component in the composition means the total amount of the plurality of the above substances present in the composition, unless otherwise specified.

[0016] In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.

[0017] In the present disclosure, ordinal numbers (for example, "first" and "second") are terms used to distinguish a plurality of components, and do not limit the number of components and the superiority or inferiority of the components.

[0018] In the present disclosure, a group (atomic group) not marked with substitution and non-substitution includes a group with a substituent and a group without a substituent. For example, the notation "alkyl group" includes an alkyl group with a substituent (substituted alkyl group) and an alkyl group without a substituent (unsubstituted alkyl group).

[0019] In the present disclosure, a chemical structural formula may be represented by a simplified structural formula in which hydrogen atoms are omitted.

[0020] In the present disclosure, "(meth)acrylic acid" means acrylic acid or methacrylic acid.

[0021] In the present disclosure, "(meth)acrylate" means acrylate or methacrylate.

[0022] In the present disclosure, the "(meth)acryloyl group" means an acryloyl group or a methacryloyl group.

[0023] In the present disclosure, unless otherwise specified, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. Examples of the light used for exposure include actinic rays (active energy rays) such as the emission line spectrum of a mercury lamp, far ultraviolet rays and extreme ultraviolet rays (EUV (Extreme ultraviolet lithography) light) typified by an excimer laser, and X-rays.

[0024] In the present disclosure, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are molecular weights converted using polystyrene as a standard substance by detecting a compound in tetrahydrofuran (THF) with a differential refractometer using a gel permeation chromatography (GPC) analyzer using columns of TSKgel GMHxL (Tosoh Corporation), TSKgel G4000HxL (Tosoh Corporation), and TSKgel G2000HxL (Tosoh Corporation).

[0025] In the present disclosure, unless otherwise specified, the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm.

[0026] In the present disclosure, "solid content" means the components obtained by removing the solvent from all the components of the object.

[0027] <Photosensitive transfer material> The photosensitive transfer material according to the first embodiment of the present disclosure includes a temporary support having a first surface and a second surface on the opposite side of the first surface, and a photosensitive resin layer on the second surface of the temporary support, and the L value of the second surface of the temporary support measured by the SCE (Specular Component Exclude: excluding specularly reflected light. The same applies hereinafter) method is 1.5 or less. According to the above-described first embodiment, a photosensitive transfer material for forming a resin pattern having high linearity is provided. * The value is 1.5 or less. According to the above-described first embodiment, a photosensitive transfer material for forming a resin pattern having high linearity is provided.

[0028] The presumed reasons for the above-described effects will be explained below. In the method for manufacturing a resin pattern using a photosensitive transfer material, one of the factors that affects the linearity of the resin pattern is, for example, the smoothness of the surface of the temporary support. A temporary support having low surface smoothness increases the amount of light diffused on the surface of the temporary support. In the exposure of the photosensitive resin layer through the temporary support, the increase in the light diffused on the surface of the temporary support causes a decrease in the linearity of the resin pattern. On the other hand, in the photosensitive transfer material according to the first embodiment of the present disclosure, the L * value of the second surface of the temporary support measured by the SCE method is 1.5 or less. In the photosensitive transfer material, the second surface of the temporary support faces the photosensitive resin layer. The L * value measured by the SCE method is based on the diffused reflected light after removing the specularly reflected light. * a * b * in the L * of the color space system. "The L * value of the second surface of the temporary support measured by the SCE method is 1.5 or less" means that the amount of diffused light generated on the second surface of the temporary support is small, in other words, the smoothness of the second surface of the temporary support is high. A temporary support having the above characteristics reduces the diffusion of light passing through the temporary support in the exposure of the photosensitive resin layer through the temporary support. Therefore, according to the first embodiment of the present disclosure, a photosensitive transfer material capable of forming a resin pattern having high linearity is provided.

[0029] The photosensitive transfer material according to the second embodiment of the present disclosure includes a temporary support having a first surface and a second surface on the opposite side of the first surface, and a photosensitive resin layer on the second surface of the temporary support. The temporary support is a polyester film composed of two or more layers, and at least one of the surface layers (that is, at least one of the outermost layer disposed on the first surface side and the outermost layer disposed on the second surface side) does not contain particles. Even in the above-described second embodiment, a photosensitive transfer material capable of forming a resin pattern having high linearity is provided.

[0030] In the present disclosure, when the term "photosensitive transfer material according to the present disclosure" or "photosensitive transfer material" is used without any particular specification, it refers to both the first embodiment and the second embodiment.

[0031] <<Temporary support>> The photosensitive transfer material according to the present disclosure includes a temporary support having a first surface and a second surface opposite to the first surface. In the photosensitive transfer material, the temporary support supports at least a photosensitive resin layer. In the photosensitive transfer material, the temporary support is a member that can be peeled off from an adjacent layer (e.g., a photosensitive resin layer). In the photosensitive transfer material, the second surface of the temporary support faces the photosensitive resin layer.

[0032] <Temporary Support in the Photosensitive Transfer Material According to the First Embodiment of the Present Disclosure> The temporary support (hereinafter also referred to as temporary support (1)) in the photosensitive transfer material according to the first embodiment of the present disclosure will be described below. In the photosensitive transfer material according to the first embodiment of the present disclosure, the L of the second surface of the temporary support measured by the SCE method * value (hereinafter referred to as "L * The L of the second surface is sometimes called the "value". * When the value is 1.5 or less, the diffusion of light during exposure of the photosensitive resin layer through the temporary support (1) is reduced. As a result, a resin pattern with high linearity is formed. From the viewpoint of the linearity of the resin pattern, the L * The value is preferably 1.2 or less, more preferably 1.0 or less, and particularly preferably 0.7 or less. * The value may be 0.5 or less or 0.2 or less. * The lower limit of the value is not limited. * The value may be 0.1 or greater.

[0033] In the present disclosure, the L of the second surface *The value is measured by the following method. Peel the temporary support from the photosensitive transfer material. Using a spectrophotometer (e.g., CM-700d, Konica Minolta Inc.), measure the L values at a total of 10 locations at 3 cm intervals along the width direction of the second surface of the temporary support. * Use a D65 light source as the light source of the spectrophotometer. Arithmetically average the 10 measured L values obtained by the SCE method, and adopt the obtained value as the L value of the target surface by the SCE method. * *

[0034] In the photosensitive transfer material according to the first embodiment of the present disclosure, the L value of the first surface of the temporary support measured by the SCE method (hereinafter, may be referred to as "L value of the first surface") is not limited. As described above, the L value measured by the SCE method represents smoothness. The larger the L value of the first surface, the lower the smoothness of the first surface of the temporary support (1), and the better the transportability of the temporary support (1) and the photosensitive transfer material. On the other hand, the smaller the L value of the first surface, the higher the smoothness of the first surface of the temporary support (1), and the better the linearity of the resin pattern. From the viewpoint of transportability, the L value of the first surface of the temporary support (1) is preferably 0.1 or more, more preferably 0.6 or more. From the viewpoint of the linearity of the resin pattern, the L value of the first surface of the temporary support (1) is preferably 2.5 or less, more preferably 2.0 or less, still more preferably 1.5 or less, and particularly preferably 1.0 or less. The L value of the first surface of the temporary support (1) may be 0.8 or less. The L value of the first surface is measured by a method conforming to the measurement method of the L value of the second surface. * * * * * * * * * *

[0035] From the viewpoints of the linearity and transportability of the resin pattern, the ratio of the L value of the second surface to the L value of the first surface ([L value of the second surface / L value of the first surface]) in the temporary support (1) * * *Value] / [L of the first surface * The value) is preferably 2 or less, more preferably 1.5 or less, still more preferably 1 or less, and particularly preferably 0.8 or less. L of the first surface * L of the second surface with respect to the value of the first surface * The ratio of the value may be 0.7, 0.5 or less, or 0.3 or less. L of the first surface * L of the second surface with respect to the value of the first surface * The lower limit of the ratio of the value is not limited. L of the first surface * L of the second surface with respect to the value of the first surface * The ratio of the value may be 0.1 or more, 0.2 or more, or 0.3 or more. From the viewpoints of the linearity and transportability of the resin pattern, L of the first surface * L of the second surface with respect to the value of the first surface * The ratio of the value is preferably 0.1 to 2, more preferably 0.2 to 1.1, and particularly preferably 0.2 to 0.9.

[0036] L of the second surface * The value and L of the first surface * The value is adjusted, for example, by the surface shape of the temporary support (1). L * Examples of the method for reducing the value include a method of reducing the amount of particles contained in the temporary support (1), a method of reducing the particle size, a method of increasing the coating thickness of the particle-containing layer with respect to the particle size, and a method of improving the uniformity of the thickness unevenness of the temporary support (1). L * Examples of the method for increasing the value include a method of increasing the amount of particles contained in the temporary support (1), a method of increasing the particle size, and a method of reducing the coating thickness of the particle-containing layer with respect to the particle size. To improve the uniformity of the thickness unevenness of the temporary support, it is useful to increase the stretching temperature during longitudinal stretching.

[0037] The temporary support (1) preferably has light transmissivity. In the present disclosure, "having light transmissivity" means that the transmittance at the wavelength used for pattern exposure is 50% or more. From the viewpoint of improving the exposure sensitivity of the photosensitive resin layer, the transmittance of the temporary support (1) at the wavelength used for pattern exposure (more preferably a wavelength of 365 nm) is preferably 60% or more, and more preferably 70% or more. The transmittance is the ratio of the intensity of the light that has passed through the object (transmitted light) to the intensity of the light that is incident perpendicularly to the main surface of the object (incident light). The transmittance is measured using a known spectroscope (for example, "MCPD Series", Otsuka Electronics Co., Ltd.).

[0038] The thickness of the temporary support (1) is not limited. From the viewpoints of the strength as a support, the flexibility required for bonding to the substrate, and the light transmissivity required in exposure, the thickness of the temporary support (1) may be determined according to the material. From the viewpoints of ease of handling and versatility, the thickness of the temporary support (1) is preferably 100 μm or less, more preferably 50 μm or less, still more preferably 20 μm or less, and particularly preferably 16 μm or less. From the viewpoints of ease of handling and versatility, the thickness of the temporary support (1) is preferably 5 μm or more, and more preferably 10 μm or more. The thickness of the temporary support is measured by the following method. Using a scanning electron microscope, a cross-section along the thickness direction of the temporary support (the direction perpendicular to the main surface of the temporary support) is observed. Based on the observed image, the thickness of the temporary support is measured at 10 locations, and the measured values are averaged arithmetically. The obtained value is adopted as the thickness of the temporary support.

[0039] The layer structure of the temporary support (1) is not limited. The temporary support (1) may be a temporary support having a single-layer structure or a temporary support having a multi-layer structure. Hereinafter, the layer structure of the temporary support (1) will be described. However, the layer structure of the temporary support (1) is not limited to the layer structure shown below.

[0040] Examples of the temporary support (1) having a single-layer structure include a glass substrate, a resin film, and paper. From the viewpoints of strength, flexibility, and light transmittance, a resin film is preferable. Examples of the resin film include a polyethylene terephthalate (PET) film, a triacetate cellulose film, a polystyrene film, and a polycarbonate film. Among these, a PET film is preferable, and a biaxially stretched PET film is more preferable. Examples of the method for producing the resin film include an extrusion molding method.

[0041] Examples of the temporary support (1) having a multilayer structure include a temporary support including a base material and a particle-containing layer. The temporary support (1) having a multilayer structure may include a layer other than the above-described particle-containing layer (for example, an adhesive layer).

[0042] From the viewpoint of transportability, it is preferable that the temporary support (1) includes, in this order, a particle-containing layer (hereinafter sometimes referred to as the "first particle-containing layer") disposed as the outermost layer of the temporary support and a base material in the lamination direction from the temporary support toward the photosensitive resin layer. In other words, it is preferable that the temporary support (1) includes, in this order, a base material and a particle-containing layer (first particle-containing layer) disposed as the outermost layer on the first surface side of the temporary support (1). The surface of the first particle-containing layer includes the first surface of the temporary support (1).

[0043] The temporary support (1) may include, in this order, a base material and a particle-containing layer (hereinafter sometimes referred to as the "second particle-containing layer") disposed as the outermost layer of the temporary support in the lamination direction from the temporary support toward the photosensitive resin layer. In other words, the temporary support (1) may include, in this order, a base material and a particle-containing layer (second particle-containing layer) disposed as the outermost layer on the second surface side of the temporary support (1). The surface of the second particle-containing layer includes the second surface of the temporary support (1).

[0044] The temporary support (1) may include a plurality of particle-containing layers. For example, the temporary support (1) may include, in this order, a first particle-containing layer, a base material, and a second particle-containing layer in the lamination direction from the temporary support toward the photosensitive resin layer.

[0045] Examples of the base material include a glass substrate, a resin film, and paper. The base material is preferably a resin film, more preferably a polyethylene terephthalate (PET) film, and particularly preferably a biaxially stretched PET film. Examples of the resin film include the resin films described above. Examples of the method for producing the resin film include an extrusion molding method.

[0046] Examples of the particles in the particle-containing layer include inorganic particles and organic particles. Examples of the inorganic particles include particles containing an inorganic oxide. Examples of the inorganic oxide include silicon oxide (silica), titanium oxide (titania), zirconium oxide (zirconia), magnesium oxide (magnesia), and aluminum oxide (alumina). Examples of the organic particles include particles containing a polymer. Examples of the polymer include an acrylic resin, polyester, polyurethane, polycarbonate, polyolefin, and polystyrene. From the viewpoint of the abrasion resistance of the particles, the particles are preferably inorganic particles, more preferably particles containing an inorganic oxide, still more preferably particles containing at least one selected from the group consisting of silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, and aluminum oxide, and particularly preferably particles containing silicon oxide.

[0047] The particle size of the particles in the particle-containing layer is not limited. From the perspective of the linearity of the resin pattern, the average particle size of the particles is preferably 1 μm or less, more preferably 300 nm or less, still more preferably 100 nm or less, and particularly preferably 80 nm or less. From the perspective of transportability, the average particle size of the particles is preferably 5 nm or more, more preferably 20 nm or more, and particularly preferably 40 nm or more. From the perspectives of the linearity and transportability of the resin pattern, the average particle size of the particles is preferably 5 nm to 1 μm, more preferably 20 nm to 300 nm, and particularly preferably 40 nm to 100 nm. In the present disclosure, the average particle size of the particles is measured by the following method. Using a transmission electron microscope (TEM), the particle sizes of 15 particles are measured. Here, the "particle size" is the maximum value of the straight line connecting two points on the contour line of the particle in plan view. The arithmetic mean of the measured values is adopted as the average particle size of the particles.

[0048] The shape of the particles in the particle-containing layer is not limited. Examples of the shape of the particles in plan view include circular, elliptical, polygonal, and irregular shapes.

[0049] The particle-containing layer may contain a binder. Examples of the binder include polymers. Examples of the polymers include acrylic resins, polyurethanes, polyolefins, styrene-butadiene polymers, polyesters, polyvinyl chlorides, and polyvinylidene chlorides.

[0050] The thickness of the particle-containing layer is not limited. From the perspective of transportability, the thickness of the particle-containing layer (excluding the particles exposed on the surface of the particle-containing layer. The same applies hereinafter in this paragraph) is preferably 3 μm or less, more preferably 2 μm or less. Also, from the perspective of uniformly presenting the particles, the thickness of the particle-containing layer is preferably 5 nm or more, preferably 20 nm or more. The thickness of the particle-containing layer is measured by a method according to the method for measuring the thickness of the temporary support.

[0051] The method for manufacturing the particle-containing layer is not limited. The particle-containing layer is formed, for example, by applying a composition for forming a particle-containing layer onto a substrate and drying the applied composition for forming a particle-containing layer. In the above method, the composition for forming a particle-containing layer may be applied onto an unstretched film, a uniaxially stretched film, or a biaxially stretched film. The unstretched film or the uniaxially stretched film onto which the composition for forming a particle-containing layer is applied may be further stretched. The particle-containing layer may be formed together with a substrate by, for example, a coextrusion method.

[0052] The film used as the temporary support (1) preferably has no deformation (e.g., wrinkles), scratches, and defects.

[0053] From the viewpoints of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, the number of fine particles, foreign substances, defects, and precipitates contained in the temporary support (1) is preferably small. The number of fine particles, foreign substances, and defects having a diameter of 2 μm or more is 2 preferably 50 pieces / 10 mm or less, 2 more preferably 10 pieces / 10 mm or less, 2 even more preferably 3 pieces / 10 mm or less, 2 and particularly preferably 0 pieces / 10 mm.

[0054] Preferred embodiments of the temporary support (1) are described, for example, in paragraphs 0017 to 0018 of JP-A-2014-85643, paragraphs 0019 to 0026 of JP-A-2016-27363, paragraphs 0041 to 0057 of WO 2012 / 081680, paragraphs 0029 to 0040 of WO 2018 / 179370, and paragraphs 0012 to 0032 of JP-A-2019-101405. The contents of these publications are incorporated herein by reference.

[0055] Examples of the temporary support (1) include a biaxially stretched polyethylene terephthalate film having a thickness of 16 μm, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, and a biaxially stretched polyethylene terephthalate film having a thickness of 9 μm.

[0056] <Temporary support in the photosensitive transfer material according to the second embodiment of the present disclosure> Hereinafter, the temporary support (hereinafter also referred to as the temporary support (2)) in the photosensitive transfer material according to the second embodiment of the present disclosure will be described. In the photosensitive transfer material according to the second embodiment of the present disclosure, the temporary support is a polyester film composed of two or more layers, and at least one of the surface layers does not contain particles. Here, "the surface layer does not contain particles" means that when the surface layer is observed with a scanning electron microscope (SEM) and a transmission electron microscope (TEM) and 10 fields are confirmed at a magnification of 5,000 times, the average number of particles present is 0.5 particles / mm 2 The following is what it means. That is, when confirmed by the above method, if the average number of particles present is 0.5 particles / mm 2 If it is the following, it is regarded that "the surface layer does not contain particles".

[0057] The above observation method will be described more specifically. The polyester resin is removed from the polyester film that is the surface layer of the temporary support by the plasma low-temperature ashing treatment method to expose the particles. The treatment conditions are selected such that the polyester resin is ashed but the particles are not damaged as much as possible. The sample after treatment is observed at a magnification of 5,000 times using a scanning electron microscope (SEM, for example, S-4000 type manufactured by Hitachi, Ltd.), the particle image is captured by an image analyzer (LUZEX_AP manufactured by Nireco Corporation), and the presence or absence of particles and the number of particles are confirmed. In addition, when the particles are significantly damaged by the plasma low-temperature ashing treatment method, the cross-section of the temporary support is observed at 5,000 times using a transmission electron microscope (TEM, for example, H-600 type manufactured by Hitachi, Ltd.), and the presence or absence of particles and the number of particles are confirmed. When observed with SEM and TEM, if the average number of particles present is 0.5 particles / mm when 10 fields are confirmed at a magnification of 5,000 times 2 If it is the following, it is determined that the surface layer of the observation target does not contain particles.

[0058] If the temporary support (2) is a polyester film composed of two layers, then among the two layers, one layer is the surface layer on the first surface side (i.e., the layer arranged as the outermost layer on the first surface side), and the other layer is the surface layer on the second surface side (i.e., the layer arranged as the outermost layer on the second surface side). If the temporary support (2) is a polyester film composed of three or more layers, it is composed of the surface layer on the first surface side (i.e., the layer arranged as the outermost layer on the first surface side), the surface layer on the second surface side (i.e., the layer arranged as the outermost layer on the second surface side), and one layer or two or more intermediate layers sandwiched between these two surface layers. Among the two surface layers of the temporary support (2), at least one of the surface layers does not contain particles.

[0059] Also, from the viewpoint of reducing the light diffusion during the exposure of the photosensitive resin layer through the temporary support and forming a resin pattern with high linearity, it is preferable that the surface layer on the second surface side of the temporary support (2) does not contain particles. By the surface layer on the second surface side of the temporary support (2) not containing particles, light scattering by the particles can be suppressed.

[0060] Also, from the viewpoints of pattern formability during pattern exposure through the temporary support and the transparency of the temporary support, it is preferable that the surface layer on the first surface side of the temporary support (2) does not contain particles.

[0061] From the viewpoint of the linearity of the resin pattern, the L value of the second surface of the temporary support (2) measured by the SCE method * is preferably 1.5 or less, more preferably 1.2 or less, still more preferably 1.0 or less, and particularly preferably 0.7 or less. The lower limit of the L value of the second surface of the temporary support (2) * is not limited and may be, for example, 0.1 or more.

[0062] On the other hand, the L value of the first surface of the temporary support (2) measured by the SCE method *The value is preferably 2.0 or less, more preferably 1.5 or less, still more preferably 1.0 or less, and particularly preferably 0.8 or less. L on the first surface of the temporary support (2) * The lower limit of the value is not limited and may be, for example, 0.1 or more, preferably 0.6 or more.

[0063] From the viewpoint of transportability, the arithmetic mean roughness Ra of the first surface of the temporary support (2) is preferably 1 nm to 50 nm, more preferably 1 nm to 40 nm. The arithmetic mean roughness Ra of the first surface in the temporary support (2) is measured by a method conforming to JIS B 0601:1994. Specifically, it can be measured in the same manner as the arithmetic mean roughness Ra of the surface of the protective film described later.

[0064] The polyester film composed of two or more layers constituting the temporary support (2) may be any as long as the resin constituting the film mainly contains a polyester resin. Note that "the resin constituting the film mainly contains a polyester resin" means that at least 70 mol% or more of the resin constituting the film is a polyester resin.

[0065] The polyester resin constituting the polyester film is obtained by polymerization from monomers composed of dicarboxylic acids, diols, and these ester-forming derivatives. Specifically, examples of the polyester resin constituting the film include polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, polyhexamethylene terephthalate, polyhexamethylene naphthalate, and copolymers thereof, and polyethylene terephthalate is particularly preferred.

[0066] As the dicarboxylic acid component (including dicarboxylic acids and their ester-forming derivatives), which is a monomer for obtaining the polyester resin, it is preferable to use aromatic dicarboxylic acids. Examples of the aromatic dicarboxylic acid include terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid, etc., and terephthalic acid is particularly preferred. Only one type of dicarboxylic acid component may be used, or two or more types may be used in combination. For example, two or more types of aromatic dicarboxylic acids may be used in combination, or an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid may be used in combination.

[0067] Examples of the diol component (including a diol and its ester-forming derivative) which is a monomer for obtaining the polyester include ethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, etc., and ethylene glycol is particularly preferred. Only one type of diol component may be used, or two or more types may be used in combination.

[0068] The polyester resin constituting the polyester film can be produced by a conventionally known method. For example, a method of directly subjecting a dicarboxylic acid component to an esterification reaction with a diol component, and then heating the product of this reaction under reduced pressure to remove the excess diol component while performing polycondensation, a method of using a dialkyl ester of a dicarboxylic acid as the dicarboxylic acid component, subjecting this to a transesterification reaction with a diol component, and then performing polycondensation in the same manner as above, etc. may be mentioned. In this case, if necessary, conventionally known alkali metals, alkaline earth metals, manganese, cobalt, zinc, antimony, germanium, titanium compounds, etc. can also be used as a reaction catalyst.

[0069] The intrinsic viscosity of the polyester resin constituting the polyester film is preferably 0.5 dl / g to 0.8 dl / g, more preferably 0.55 dl / g to 0.70 dl / g.

[0070] The temporary support (2) preferably has a phase separation structure in the surface layer that does not contain particles. That is, the surface layer preferably does not contain particles and has a phase separation structure (specifically, it may be a sea-island structure). Although the surface layer does not contain particles, by having a phase separation structure (for example, a sea-island structure), surface irregularities derived from the phase separation structure are formed. Specifically, a film having a surface layer with a phase separation structure, for example, by biaxially stretching, regions that are easy to stretch and regions that are difficult to stretch are generated due to the phase separation structure, and minute surface irregularities can be formed by this stretching unevenness. In order to form a phase separation structure in the surface layer as described above, the surface layer preferably contains a polyester resin having an alicyclic structure. That is, when the surface layer contains a main polyester resin (for example, a polyester resin having an aromatic ring structure) and a polyester resin having an alicyclic structure with different compatibility from the main polyester resin, a phase separation structure (for example, a sea-island structure) is formed.

[0071] Examples of the alicyclic structure in the polyester resin having an alicyclic structure include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, or a cyclohexane ring, and a cyclohexane ring is particularly preferred. The polyester resin having an alicyclic structure can be obtained, for example, by using dimethyl terephthalate as a dicarboxylic acid component and 1,3-cyclopropanediol, 1,3-cyclobutanediol, 1,3-cyclopentanediol, 1,4-cyclohexanedimethanol, etc. as a diol component and performing a polycondensation reaction in the presence of 200 ppm of butyltin tris(2-ethylhexanoate).

[0072] From the viewpoints of the formability of surface irregularities and the occurrence of coating defects in the composition for forming a photosensitive resin layer, the content of the polyester resin having an alicyclic structure is preferably 3% by mass to 10% by mass based on the total mass of the surface layer.

[0073] The temporary support (2) preferably contains a copolyethylene terephthalate having isophthalic acid as a copolymerization component in the surface layer together with the polyester resin having an alicyclic structure. Here, the copolyethylene terephthalate having isophthalic acid as a copolymerization component refers to a polyester in which the most abundant diol component in the polyester resin is ethylene glycol and the most abundant dicarboxylic acid component is terephthalic acid, and which contains isophthalic acid as a dicarboxylic acid component. The copolymerization ratio of isophthalic acid is preferably in the range of 0.1 mol% to 49 mol%, more preferably 0.5 mol% to 40 mol%, based on the total dicarboxylic acid component. When the copolyethylene terephthalate having isophthalic acid as a copolymerization component is contained in the surface layer, it is preferable in terms of film-forming properties, and is preferable in terms of easily forming surface irregularities due to the difference in stretchability from the polyester resin having an alicyclic structure.

[0074] The content of the copolyethylene terephthalate having isophthalic acid as a copolymerization component is not particularly limited, but is preferably 10% by mass to 20% by mass based on the total mass constituting the surface layer.

[0075] From the viewpoints of the linearity of the resin pattern and transportability, the thickness of the surface layer is preferably 0.5 μm to 2.5 μm, more preferably 0.6 μm to 2.0 μm.

[0076] The thickness of the temporary support (2) is preferably 50 μm or less, more preferably 40 μm or less. The lower limit value of the thickness of the temporary support is, for example, 5 μm or more.

[0077] (Layer structure) In the temporary support (2), examples of the layer structure of the two-layer polyester film include an A layer (surface layer) / B layer (surface layer), and examples of the layer structure of the three-layer polyester film include A layer / B layer (intermediate layer) / A layer, A layer / B layer (intermediate layer) / C layer (surface layer). Examples of the polyester film having four or more layers include those in which the intermediate layer has a laminated structure. In addition, when the above A layer is a surface layer that does not contain particles, the B layer (surface layer), B layer (intermediate layer), and C layer (surface layer) may each be a polyester film, and may contain particles as long as the object of the present disclosure is not impaired. However, it can also be a layer (polyester film) that does not contain particles like the A layer. When the above B layer (surface layer), B layer (intermediate layer), or C layer (surface layer) is a layer containing particles, the contained particles may be organic particles or inorganic particles. Examples of the organic particles include particles such as polyimide resins, olefins or modified olefin resins, crosslinked polystyrene resins, and silicone resins. Examples of the inorganic particles include particles such as silicon oxide, calcium carbonate, aggregated alumina, aluminum silicate, mica, clay, talc, and barium sulfate.

[0078] As the above particles, those obtained by surface-modifying the particle surface with a surfactant or the like to improve the affinity with the polyester resin are preferable. Further, particles having a shape close to a spherical shape and a small difference in refractive index from the polyester resin are preferable. Examples include colloidal silica and organic particles, and silicone resin particles and crosslinked polystyrene resin particles are particularly preferable. Among them, crosslinked polystyrene resin particles composed of a styrene-divinylbenzene copolymer prepared by emulsion polymerization are preferable because their particle shape is close to a perfect sphere, the particle size distribution is uniform, and uniform protrusion formation can be achieved.

[0079] A preferred embodiment of the temporary support (2) is a polyester film composed of three or more layers, in which both surface layers do not contain particles, contain a polyester resin having an alicyclic structure, have a thickness of 0.5 μm to 2.5 μm, and the arithmetic mean roughness Ra on the first surface side is 1 nm to 50 nm or less.

[0080] Hereinafter, a method for manufacturing the temporary support (2) will be described. The polyester film composed of two or more layers, which is a temporary support (2), may be manufactured by using melt film formation by coextrusion. When obtaining a layer containing particles (polyester film), for example, particles are dispersed in ethylene glycol, which is a diol component, to form a slurry. For example, after performing high-precision filtration of coarse particles, there is a method of adding this ethylene glycol slurry at an arbitrary stage before the completion of polyester polymerization. Here, when adding particles, for example, a water sol or alcohol sol obtained during the synthesis of the particles may be added as it is without drying. Also, after mixing a water slurry of the particles with polyester pellets, a method of feeding them into a vent-type twin-screw kneading extruder to include the particles in the polyester film may be used.

[0081] Using pellets containing particles and pellets not containing particles prepared for each layer, and if necessary, after mixing the pellets containing particles and the pellets not containing particles, they are supplied to a known melt lamination extruder. As the extruder, a single-screw or twin-screw extruder can be used. Also, in order to omit the pellet drying process, a vent-type extruder equipped with a vacuum line can be used. Also, for the formation of the B layer where the extrusion amount is the largest, a so-called tandem extruder that distributes the function of melting the pellets and the function of keeping the melted pellets at a constant temperature to each extruder may be used.

[0082] The melt extruded by the extruder is filtered by a filter. As the filter, for example, a high-precision one that can collect 95% or more of foreign substances with a diameter of 5 μm or more can be used. Subsequently, it is extruded in a sheet shape from a slit-shaped die and cooled and solidified on a casting roll to produce an unstretched film. That is, a plurality of extruders, a multi-layer manifold or a merging block (for example, a merging block having a rectangular merging part) are used for lamination, the sheet is extruded from the die, and cooled by a casting roll to produce an unstretched film. In this case, it is preferable to install a static mixer and a gear pump in the flow path of the melt.

[0083] The temporary support (2) is preferably a biaxially stretched film. The stretching method may be simultaneous biaxial stretching or sequential biaxial stretching. In the case of sequential stretching, the stretching temperature in the first longitudinal stretching is preferably 90°C to 130°C, more preferably 100°C to 125°C, from the viewpoints of suppressing film breakage and suppressing thermal damage. Also, from the viewpoints of preventing stretching unevenness and scratches, it is preferable to perform stretching in two or more stages.

[0084] From the viewpoints of suppressing stretching unevenness and suppressing film breakage, the stretching ratio is preferably 3 to 4.5 times (more preferably 3.5 to 4.3 times) in the longitudinal direction and 3.2 to 5 times (more preferably 4.0 to 4.6 times) in the width direction. After stretching, it is desirable to perform heat setting at 200°C to 230°C (preferably 210°C to 230°C) for 0.5 seconds to 20 seconds (preferably 1 second to 15 seconds) from the viewpoint of obtaining specific properties such as a desired heat shrinkage rate. Further, after heat setting, it is preferable to perform a relaxation treatment of 0.1% to 7.0% in the longitudinal and / or width directions.

[0085] Hereinafter, unless otherwise specified, when simply referring to the "temporary support", it shall refer to both the above-mentioned temporary support (1) and temporary support (2).

[0086] <<Photosensitive resin layer>> The photosensitive transfer material according to the present disclosure includes a photosensitive resin layer on the second surface of the temporary support. The photosensitive resin layer is preferably a negative-type photosensitive resin layer in which the solubility of the exposed portion in the developer decreases upon exposure and the unexposed portion is removed by development. However, the photosensitive resin layer is not limited to a negative-type photosensitive resin layer. The photosensitive resin layer may be a positive-type photosensitive resin layer in which the solubility of the exposed portion in the developer improves upon exposure and the exposed portion is removed by development.

[0087] The photosensitive resin layer preferably contains a polymer A, a polymerizable compound B, and a photopolymerization initiator. The photosensitive resin layer preferably contains 10% to 90% by mass of the polymer A, 5% to 70% by mass of the polymerizable compound B, and 0.01% to 20% by mass of the photopolymerization initiator, based on the total solid mass of the photosensitive resin layer. Hereinafter, the components of the photosensitive resin layer will be described.

[0088] (Polymer A) Examples of the polymer A include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamides, polyesters, polyamide resins, epoxy resins, polyacetals, polyhydroxystyrene, polyimide resins, polybenzoxazoles, polysiloxanes, polyethyleneimines, polyallylamines, and polyalkylene glycols. The polymer A is preferably an alkali-soluble polymer. The alkali-soluble polymer compound includes a polymer compound that is easily soluble in an alkali substance. In the present disclosure, "alkali-soluble" means a property that the solubility in an aqueous solution (100 g) containing 1% by mass of sodium carbonate at 22°C is 0.1 g or more.

[0089] From the viewpoint of more excellent resolution by suppressing the swelling of the photosensitive resin layer by the developer, the acid value of the polymer A is preferably 220 mgKOH / g or less, more preferably less than 200 mgKOH / g, and particularly preferably less than 190 mgKOH / g. The lower limit of the acid value of the polymer A is not limited. From the viewpoint of more excellent developability, the acid value of the polymer A is preferably 60 mgKOH / g or more, more preferably 120 mgKOH / g or more, still more preferably 150 mgKOH / g or more, and particularly preferably 170 mgKOH / g or more. The acid value of the polymer A may be adjusted by the types of the constituent units constituting the polymer A and the content of the constituent units containing acid groups.

[0090] In the present disclosure, the "acid value" refers to the mass (mg) of potassium hydroxide required to neutralize 1 g of a sample. The unit of the acid value is expressed as mgKOH / g. The acid value can be calculated, for example, from the average content of acid groups in a compound.

[0091] The weight average molecular weight of polymer A is preferably from 5,000 to 500,000. Setting the weight average molecular weight to 500,000 or less is preferable from the viewpoint of improving resolution and developability. The weight average molecular weight of polymer A is more preferably 100,000 or less, still more preferably 80,000 or less, and particularly preferably 70,000 or less. On the other hand, setting the weight average molecular weight to 5,000 or more is preferable from the viewpoint of controlling the properties of the developed aggregates and the properties of the unexposed film (for example, edge fusion property and cut chip property). The weight average molecular weight of polymer A is more preferably 10,000 or more, still more preferably 20,000 or more, and particularly preferably 30,000 or more. The edge fusion property refers to the degree of ease of the photosensitive resin layer protruding from the end face of a roll in a photosensitive transfer material wound in a roll shape. The cut chip property refers to the degree of ease of chips flying when the unexposed film is cut with a cutter. For example, if the generated chips are transferred to the mask used for exposure, it will cause defective products. The dispersity of polymer A is preferably from 1.0 to 6.0, more preferably from 1.0 to 5.0, still more preferably from 1.0 to 4.0, and particularly preferably from 1.0 to 3.0. In the present disclosure, the dispersity is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight). In the present disclosure, the weight average molecular weight and the number average molecular weight are values measured using gel permeation chromatography.

[0092] The glass transition temperature (Tg) of polymer A is preferably 30°C or higher and 135°C or lower. When the Tg of polymer A is 135°C or lower, it is possible to suppress line width thickening or resolution deterioration when the focus position during exposure is shifted. The Tg of polymer A is more preferably 130°C or lower, still more preferably 120°C or lower, and particularly preferably 110°C or lower. When the Tg of polymer A is 30°C or higher, the edge fuse resistance can be improved. The Tg of polymer A is more preferably 40°C or higher, still more preferably 50°C or higher, particularly preferably 60°C or higher, and most preferably 70°C or higher.

[0093] From the viewpoint of suppressing line width thickening or resolution deterioration when the focus position during exposure is shifted, polymer A preferably contains a structural unit having an aromatic hydrocarbon group. Polymer A may contain one or more structural units having an aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group. The content of the structural unit having an aromatic hydrocarbon group in polymer A is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, particularly preferably 45% by mass or more, and most preferably 50% by mass or more with respect to the total mass of polymer A. The upper limit of the content of the structural unit having an aromatic hydrocarbon group in polymer A is not limited. The content of the structural unit having an aromatic hydrocarbon group in polymer A is preferably 95% by mass or less, and more preferably 85% by mass or less. When the photosensitive resin layer contains a plurality of types of polymer A, the content of the structural unit having an aromatic hydrocarbon group is determined as a weight average value. When the photosensitive resin layer contains a plurality of types of polymer A, the content of the structural unit having an aromatic hydrocarbon group is determined as a weight average value.

[0094] The structural unit having an aromatic hydrocarbon group is introduced using a monomer having an aromatic hydrocarbon group. Examples of the monomer having an aromatic hydrocarbon group include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer). Among these, a monomer having an aralkyl group or styrene is preferable. When the structural unit having an aromatic hydrocarbon group in polymer A is a structural unit derived from styrene, the content of the structural unit derived from styrene is preferably 20% by mass to 80% by mass, more preferably 25% by mass to 70% by mass, and particularly preferably 30% by mass to 60% by mass with respect to the total mass of polymer A.

[0095] Examples of the aralkyl group include substituted or unsubstituted phenylalkyl groups (excluding the benzyl group) and substituted or unsubstituted benzyl groups, and substituted or unsubstituted benzyl groups are preferable.

[0096] Examples of the monomer having a phenylalkyl group include phenylethyl (meth)acrylate.

[0097] Examples of the monomer having a benzyl group include (meth)acrylates having a benzyl group (for example, benzyl (meth)acrylate and chlorobenzyl (meth)acrylate) and vinyl monomers having a benzyl group (for example, vinylbenzyl chloride and vinylbenzyl alcohol). Among these, benzyl (meth)acrylate is preferable. When the structural unit having an aromatic hydrocarbon group in polymer A is a structural unit derived from benzyl (meth)acrylate, the content of the structural unit derived from benzyl (meth)acrylate is preferably 50% by mass to 95% by mass, more preferably 60% by mass to 90% by mass, still more preferably 70% by mass to 90% by mass, and particularly preferably 75% by mass to 90% by mass with respect to the total mass of polymer A.

[0098] Polymer A containing a structural unit having an aromatic hydrocarbon group preferably contains a structural unit having an aromatic hydrocarbon group and at least one selected from the group consisting of a structural unit derived from a first monomer and a structural unit derived from a second monomer.

[0099] Polymer A that does not contain a structural unit having an aromatic hydrocarbon group preferably contains a structural unit derived from a first monomer, and more preferably contains a structural unit derived from a first monomer and a structural unit derived from a second monomer.

[0100] The first monomer is a monomer having a carboxyl group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid semi-ester. Among these, (meth)acrylic acid is preferred. Polymer A may contain a structural unit derived from one kind or two or more kinds of the first monomers. The content of the first monomer in Polymer A is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 45% by mass, and particularly preferably 15% by mass to 35% by mass based on the total mass of Polymer A.

[0101] The second monomer is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include (meth)acrylates (e.g., methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate), esters of vinyl alcohol (e.g., vinyl acetate), and (meth)acrylonitrile. Among these, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate are preferred, and methyl (meth)acrylate is particularly preferred. The content of the second monomer in polymer A is preferably 5% by mass to 60% by mass, more preferably 15% by mass to 50% by mass, and particularly preferably 20% by mass to 45% by mass based on the total mass of polymer A.

[0102] From the viewpoint of suppressing line width thickening or resolution deterioration when the focal position during exposure is deviated, polymer A preferably contains at least one selected from the group consisting of structural units derived from monomers having an aralkyl group and structural units derived from styrene. Preferred specific examples of polymer A as described above include a copolymer of methacrylic acid, benzyl methacrylate, and styrene, and a copolymer of methacrylic acid, methyl methacrylate, benzyl methacrylate, and styrene.

[0103] In one embodiment, the polymer A preferably is a polymer containing 25% to 40% by mass of a structural unit having an aromatic hydrocarbon group, 20% to 35% by mass of a structural unit derived from a first monomer, and 30% to 45% by mass of a structural unit derived from a second monomer. Further, in another embodiment, the polymer A preferably is a polymer containing 70% to 90% by mass of a structural unit derived from a monomer having an aromatic hydrocarbon group and 10% to 25% by mass of a structural unit derived from a first monomer.

[0104] The polymer A may have a branched structure or an alicyclic structure in the side chain. For example, by using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain, a branched structure or an alicyclic structure can be introduced into the side chain of the polymer (A). The alicyclic structure in the side chain of the polymer A may be a monocyclic ring or a polycyclic ring. Also, the polymer A may have a linear structure in the side chain.

[0105] Examples of the monomer containing a group having a branched structure in the side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, tert-amyl (meth)acrylate, sec-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and tert-octyl (meth)acrylate. Among these, isopropyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl methacrylate are preferable, and isopropyl methacrylate or tert-butyl methacrylate is more preferable.

[0106] Specific examples of the monomer containing a group having an alicyclic structure in the side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. Further, specific examples of the monomer containing a group having an alicyclic structure in the side chain include (meth)acrylates having an alicyclic hydrocarbon group with 5 to 20 carbon atoms. Examples of the monomer containing a group having an alicyclic structure in the side chain include, for example, (meth)acrylic acid (bicyclo[2.2.1]heptyl-2), (meth)acrylic acid-1-adamantyl, (meth)acrylic acid-2-adamantyl, (meth)acrylic acid-3-methyl-1-adamantyl, (meth)acrylic acid-3,5-dimethyl-1-adamantyl, (meth)acrylic acid-3-ethyladamantyl, (meth)acrylic acid-3-methyl-5-ethyl-1-adamantyl, (meth)acrylic acid-3,5,8-triethyl-1-adamantyl, (meth)acrylic acid-3,5-dimethyl-8-ethyl-1-adamantyl, (meth)acrylic acid 2-methyl-2-adamantyl, (meth)acrylic acid 2-ethyl-2-adamantyl, (meth)acrylic acid 3-hydroxy-1-adamantyl, (meth)acrylic acid octahydro-4,7-methanoiden-5-yl, (meth)acrylic acid octahydro-4,7-methanoiden-1-ylmethyl, (meth)acrylic acid-1-menthyl, (meth)acrylic acid tricyclodecane, (meth)acrylic acid-3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl, (meth)acrylic acid-3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl, (meth)acrylic acid (nor)bornyl, (meth)acrylic acid isobornyl, (meth)acrylic acid fenchyl, (meth)acrylic acid-2,2,5-trimethylcyclohexyl and (meth)acrylic acid cyclohexyl.Among these, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fenthyl (meth)acrylate, 1-menthyl (meth)acrylate, and tricyclodecanyl (meth)acrylate are preferred, and cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, and tricyclodecanyl (meth)acrylate are more preferred.

[0107] The photosensitive resin layer may contain one or more polymers A. When using two or more polymers A, it is preferable to use two types of polymer A containing a structural unit having an aromatic hydrocarbon group, or to mix and use a polymer A containing a structural unit having an aromatic hydrocarbon group and a polymer A not containing a structural unit having an aromatic hydrocarbon group. In the latter case, the usage ratio of the polymer A containing a structural unit having an aromatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more with respect to the total mass of the polymer A.

[0108] The content of polymer A in the photosensitive resin layer is preferably 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, and particularly preferably 40% by mass to 60% by mass with respect to the total mass of the photosensitive resin layer. Setting the content of polymer A to 90% by mass or less is preferable from the viewpoint of controlling the development time. Setting the content of polymer A to 10% by mass or more is preferable from the viewpoint of improving the edge fuse resistance.

[0109] The synthesis of the polymer A is preferably carried out by adding an appropriate amount of a radical polymerization initiator (e.g., benzoyl peroxide and azoisobutyronitrile) to a solution obtained by diluting a monomer with a solvent (e.g., acetone, methyl ethyl ketone, and isopropanol), and heating and stirring the mixture. In some cases, synthesis may be carried out while dropping a part of the mixture into the reaction solution. After completion of the reaction, the solvent may be further added to adjust to a desired concentration. As the synthesis means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

[0110] (Polymerizable compound B) The polymerizable compound B is a compound having a polymerizable group. In the present disclosure, the "polymerizable compound" means a compound that polymerizes under the action of a polymerization initiator and is different from the above-described polymer A.

[0111] The polymerizable group is not limited as long as it is a group involved in the polymerization reaction, and examples thereof include ethylenically unsaturated groups (e.g., vinyl group, acryloyl group, methacryloyl group, styryl group, and maleimide group) and cationic polymerizable groups (e.g., epoxy group and oxetane group). The polymerizable group is preferably an ethylenically unsaturated group, and more preferably an acryloyl group or a methacryloyl group.

[0112] In terms of more excellent photosensitivity of the photosensitive resin layer, the polymerizable compound B is preferably a compound having at least one ethylenically unsaturated group (i.e., an ethylenically unsaturated compound), and more preferably a compound having two or more ethylenically unsaturated groups in one molecule (i.e., a polyfunctional ethylenically unsaturated compound). Further, in terms of more excellent resolution and peelability, the number of ethylenically unsaturated groups contained in one molecule of the ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and particularly preferably 2 or less. The ethylenically unsaturated compound is preferably a (meth)acrylate compound having a (meth)acryloyl group.

[0113] In terms of better balance among the photosensitivity, resolution, and peelability of the photosensitive resin layer, the photosensitive resin layer preferably contains a compound having two or three ethylenically unsaturated groups in one molecule (i.e., a bifunctional or trifunctional ethylenically unsaturated compound), and more preferably contains a compound having two ethylenically unsaturated groups in one molecule (i.e., a bifunctional ethylenically unsaturated compound). From the viewpoint of excellent peelability, the content of the bifunctional ethylenically unsaturated compound in the photosensitive resin layer is preferably 60% by mass or more, more preferably more than 70% by mass, and particularly preferably 90% by mass or more based on the total mass of the polymerizable compound B. The upper limit of the content of the bifunctional ethylenically unsaturated compound is not limited. The content of the bifunctional ethylenically unsaturated compound in the photosensitive resin layer may be 100% by mass based on the total mass of the polymerizable compound B. That is, all of the polymerizable compound B contained in the photosensitive resin layer may be a bifunctional ethylenically unsaturated compound.

[0114] The photosensitive resin layer preferably contains a polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups. The polymerizable compound B1 is a compound included in the above-described polymerizable compound B, which is a compound having two ethylenically unsaturated groups in one molecule (i.e., a bifunctional ethylenically unsaturated compound).

[0115] Examples of the aromatic ring include aromatic hydrocarbon rings (e.g., benzene ring, naphthalene ring, and anthracene ring), aromatic heterocyclic rings (e.g., thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring, and pyridine ring), and condensed rings thereof. The aromatic ring is preferably an aromatic hydrocarbon ring, and more preferably a benzene ring. The aromatic ring may have a substituent. The polymerizable compound B1 may have two or more aromatic rings.

[0116] From the viewpoint of improving the resolution by suppressing the swelling of the photosensitive resin layer with the developer, the polymerizable compound B1 preferably has a bisphenol structure. Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), a bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and a bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane). The bisphenol structure is preferably a bisphenol A structure. Examples of the polymerizable compound B1 having a bisphenol structure include a compound having a bisphenol structure and two ethylenically unsaturated groups (preferably (meth)acryloyl groups) respectively bonded to both ends of the bisphenol structure. Each ethylenically unsaturated group may be directly bonded to the end of the bisphenol structure or may be bonded via one or more alkyleneoxy groups. The alkyleneoxy group is preferably an ethyleneoxy group or a propyleneoxy group, and more preferably an ethyleneoxy group. The number of alkyleneoxy groups added to the bisphenol structure is not limited. The number of alkyleneoxy groups added to the bisphenol structure is preferably 4 to 16 per molecule, and more preferably 6 to 14. The polymerizable compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP-A-2016-224162. The content of the above publication is incorporated herein by reference.

[0117] The polymerizable compound B1 is preferably a bifunctional ethylenically unsaturated compound having a bisphenol A structure, and more preferably 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane. Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydodecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane (BPE-1300, Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, Shin-Nakamura Chemical Co., Ltd.), and ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, Shin-Nakamura Chemical Co., Ltd.).

[0118] Examples of the polymerizable compound B1 also include a compound represented by the following formula (I).

[0119] [Chemical formula]

[0120] In formula (I), R1 and R2 each independently represent a hydrogen atom or a methyl group, A represents C2H4, B represents C3H6, n1 and n3 each independently represent an integer from 1 to 39, n1 + n3 is an integer from 2 to 40, n2 and n4 each independently represent an integer from 0 to 29, n2 + n4 is an integer from 0 to 30, and the arrangement of the repeating units of -(A-O)- and -(B-O)- may be random or block. In the case of a block, -(A-O)- may be on the bisphenol group side, or -(B-O)- may be on the bisphenol group side. It is preferable that n1 + n2 + n3 + n4 is an integer from 2 to 20, more preferably an integer from 2 to 16, and particularly preferably an integer from 4 to 12. It is preferable that n2 + n4 is an integer from 0 to 10, more preferably an integer from 0 to 4, still more preferably an integer from 0 to 2, and particularly preferably 0.

[0121] The photosensitive resin layer may contain one or more polymerizable compounds B1.

[0122] From the viewpoint of better resolution, the content of the polymerizable compound B1 in the photosensitive resin layer is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the photosensitive resin layer. The upper limit is not particularly limited, but from the viewpoints of transferability and edge fuse resistance, it is preferably 70% by mass or less, more preferably 60% by mass or less.

[0123] From the viewpoint of better resolution, the ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound B in the photosensitive resin layer is preferably 40% or more, more preferably 50% by mass or more, still more preferably 55% by mass or more, and particularly preferably 60% by mass or more, based on mass. The upper limit of the ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound B in the photosensitive resin layer is not limited. From the viewpoint of peelability, the ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound B in the photosensitive resin layer is preferably 99% by mass or less, more preferably 95% by mass or less, still more preferably 90% by mass or less, and particularly preferably 85% by mass or less, based on mass.

[0124] The photosensitive resin layer may contain a polymerizable compound B other than the above-described polymerizable compound B1. Examples of the polymerizable compound B other than the polymerizable compound B1 include monofunctional ethylenically unsaturated compounds (i.e., compounds having one ethylenically unsaturated group in one molecule), bifunctional ethylenically unsaturated compounds having no aromatic ring (i.e., compounds having no aromatic ring and having two ethylenically unsaturated groups in one molecule), and ethylenically unsaturated compounds having three or more functional groups (i.e., compounds having three or more ethylenically unsaturated groups in one molecule).

[0125] Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate.

[0126] Examples of the bifunctional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate.

[0127] Examples of the alkylene glycol di(meth)acrylate include tricyclodecane dimethanol diacrylate (A-DCP, Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate.

[0128] Examples of the polyalkylene glycol di(meth)acrylate include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate.

[0129] Examples of the urethane di(meth)acrylate include propylene oxide-modified urethane di(meth)acrylate and ethylene oxide and propylene oxide-modified urethane di(meth)acrylate. Examples of the commercially available urethane di(meth)acrylate include 8UX-015A (Daiso Fine Chemical Co., Ltd.), UA-32P (Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (Shin-Nakamura Chemical Co., Ltd.).

[0130] Examples of the ethylenically unsaturated compound having three or more functional groups include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth) Examples include acrylates, tri(meth)acrylates of isocyanuric acid, tri(meth)acrylates of glycerin, and alkylene oxide-modified products thereof. Here, “(tri / tetra / penta / hexa)(meth)acrylate” is a concept encompassing tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and “(tri / tetra)(meth)acrylate” is a concept encompassing tri(meth)acrylate and tetra(meth)acrylate.

[0131] Examples of alkylene oxide-modified products of ethylenically unsaturated compounds having three or more functional groups include, for example, caprolactone-modified (meth)acrylate compounds (e.g., KAYARAD DPCA-20 (Nippon Kayaku Co., Ltd.) and A-9300-1CL (Shin-Nakamura Chemical Co., Ltd.)), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040 (Nippon Kayaku Co., Ltd.), ATM-35E (Shin-Nakamura Chemical Co., Ltd.), A-9300 (Shin-Nakamura Chemical Co., Ltd.), and EBECRYL 135 (Daicel Allnex)), ethoxylated glycerin triacrylate (e.g., A-GLY-9E (Shin-Nakamura Chemical Co., Ltd.)), Aronix TO-2349 (Toagosei Co., Ltd.), Aronix M-520 (Toagosei Co., Ltd.), and Aronix M-510 (Toagosei Co., Ltd.)).

[0132] From the viewpoint of resistance to processing liquids such as development, the photosensitive resin layer preferably contains a polymerizable compound B1 and an ethylenically unsaturated compound having three or more functional groups, and more preferably contains a polymerizable compound B1 and two or more ethylenically unsaturated compounds having three or more functional groups. The mass ratio of the polymerizable compound B1 to the ethylenically unsaturated compound having three or more functional groups (total mass of the polymerizable compound B1: total mass of the ethylenically unsaturated compound having three or more functional groups) is preferably from 1:1 to 5:1, more preferably from 1.2:1 to 4:1, and particularly preferably from 1.5:1 to 3:1.

[0133] As the polymerizable compound B other than the polymerizable compound B1, a polymerizable compound having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942 may be used.

[0134] The photosensitive resin layer may contain one or more kinds of polymerizable compounds B.

[0135] The content of the polymerizable compound B in the photosensitive resin layer is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and particularly preferably 20% by mass to 50% by mass with respect to the total mass of the photosensitive resin layer.

[0136] The molecular weight of the polymerizable compound B is preferably 200 to 3,000, more preferably 280 to 2,200, and particularly preferably 300 to 2,200. The molecular weight of the polymerizable compound B having a molecular weight distribution is represented by the weight average molecular weight (Mw).

[0137] From the viewpoints of resolution and linearity, the value of the ratio Mm / Mb of the content Mm of the ethylenically unsaturated compound to the content Mb of the polymer A in the photosensitive resin layer is preferably 1.0 or less, more preferably 0.9 or less, and particularly preferably 0.5 or more and 0.9 or less. The ethylenically unsaturated compound in the photosensitive resin layer preferably contains a (meth)acrylic compound, more preferably a (meth)acrylate compound, from the viewpoints of curability and resolution. The ethylenically unsaturated compound in the photosensitive resin layer contains a (meth)acrylic compound and, from the viewpoints of curability, resolution and linearity, the content ratio of the acrylic compound to the total mass of the (meth)acrylic compounds contained in the photosensitive resin layer is more preferably 60% by mass or less.

[0138] (Photoinitiator) A photoinitiator is a compound that receives actinic rays (for example, ultraviolet rays, visible light, and X-rays) and initiates the polymerization of a polymerizable compound.

[0139] The type of the photopolymerization initiator is not limited. The photopolymerization initiator according to the present disclosure includes known photopolymerization initiators. Examples of the photopolymerization initiator include, for example, a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferable.

[0140] Examples of the photoradical polymerization initiator include, for example, a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α-aminoalkylphenone structure, a photopolymerization initiator having an α-hydroxyalkylphenone structure, a photopolymerization initiator having an acylphosphine oxide structure, and a photopolymerization initiator having an N-phenylglycine structure.

[0141] From the viewpoints of photosensitivity, visibility of the exposed portion, visibility of the unexposed portion, and resolution, the photosensitive resin layer preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof as the photoradical polymerization initiator. The two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different. Examples of the derivative of the 2,4,5-triarylimidazole dimer include, for example, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0142] As the photoradical polymerization initiator, for example, the polymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-95716 and paragraphs 0064 to 0081 of JP-A-2015-14783 may be used.

[0143] Examples of the photo radical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, and anisyl (p,p'-dimethoxybenzyl).

[0144] Examples of commercially available photo radical polymerization initiators include TAZ-110 (trade name: Midori Chemical Co., Ltd.), benzophenone, TAZ-111 (trade name: Midori Chemical Co., Ltd.), 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime) (trade name: IRGACURE OXE01, BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acet yloxime) (trade name: IRGACURE OXE02, BASF), IRGACURE OXE03 (BASF), IRGACURE OXE04 (BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907, IGM Resins B.V.), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (trade name: Omnirad 127, IGM Resins B.V.), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (trade name: Omnirad 369, IGM Resins B.V.), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, IGM Resins B.V.), 1-hydroxycyclohexyl phenyl ketone (trade name: Omnirad 184, IGM Resins B.V.), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651, IGM Resins B.V.), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, IGM Resins B.V.), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, IGM Resins B.V.Company), oxime ester-based photoinitiator (trade name: Lunar 6, DKSH Japan Co., Ltd.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (alias: 2-(2-chlorophenyl)-4,5-diphenylimidazole dimer, trade name: B-CIM, Hampford), 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-305, Changzhou Qiangli Electronic New Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazole-3-yl]-, 2-(O-acetoxime) (trade name: TR-PBG-326, Changzhou Qiangli Electronic New Materials Co., Ltd.) and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazole-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, Changzhou Qiangli Electronic New Materials Co., Ltd.).

[0145] A photo cationic polymerization initiator (photoacid generator) is a compound that generates an acid upon receiving actinic rays. As the photo cationic polymerization initiator, a compound that is sensitive to actinic rays having a wavelength of 300 nm or more (preferably a wavelength of 300 nm to 450 nm) and generates an acid is preferred. Further, a photo cationic polymerization initiator that is not directly sensitive to actinic rays having a wavelength of 300 nm or more can be preferably used in combination with a sensitizer as long as it is a compound that is sensitive to actinic rays having a wavelength of 300 nm or more and generates an acid when combined with the sensitizer.

[0146] The photo cationic polymerization initiator is preferably a photo cationic polymerization initiator that generates an acid having a pKa of 4 or less, more preferably a photo cationic polymerization initiator that generates an acid having a pKa of 3 or less, and particularly preferably a photo cationic polymerization initiator that generates an acid having a pKa of 2 or less. The lower limit of the pKa is not limited. The pKa of the acid generated by the photo cationic polymerization initiator is preferably -10.0 or more.

[0147] Examples of the photo cationic polymerization initiator include ionic photo cationic polymerization initiators and non-ionic photo cationic polymerization initiators. Examples of the ionic photo cationic polymerization initiator include onium salt compounds (e.g., diaryliodonium salts and triarylsulfonium salts) and quaternary ammonium salts. As the ionic photo cationic polymerization initiator, the ionic photo cationic polymerization initiator described in paragraphs 0114 to 0133 of JP-A No. 2014-85643 may also be used. Examples of the non-ionic photo cationic polymerization initiator include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. As the trichloromethyl-s-triazines, diazomethane compounds, and imide sulfonate compounds, for example, the compounds described in paragraphs 0083 to 0088 of JP-A No. 2011-221494 may also be used. Further, as the oxime sulfonate compound, the compounds described in paragraphs 0084 to 0088 of WO 2018 / 179640 may also be used.

[0148] The photosensitive resin layer preferably contains a photo radical polymerization initiator, and more preferably contains at least one selected from the group consisting of 2,4,5-triaryl imidazole dimers and derivatives thereof.

[0149] The photosensitive resin layer may contain one or more photo polymerization initiators.

[0150] The content of the photo polymerization initiator in the photosensitive resin layer is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and particularly preferably 1.0% by mass or more with respect to the total mass of the photosensitive resin layer. The upper limit of the content of the photo polymerization initiator is not limited. The content of the photo polymerization initiator in the photosensitive resin layer is preferably 10% by mass or less, more preferably 5% by mass or less with respect to the total mass of the photosensitive resin layer.

[0151] (Dye) From the viewpoints of the visibility of the exposed portion, the visibility of the unexposed portion, the pattern visibility after development, and the resolution, the photosensitive resin layer preferably has a maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development of 450 nm or more and contains a dye (hereinafter sometimes referred to as "dye N") whose maximum absorption wavelength changes due to an acid, a base, or a radical. By including dye N in the photosensitive resin layer, the adhesion to a layer adjacent to the photosensitive resin layer (for example, a temporary support) is improved, and the resolution is improved.

[0152] In the present disclosure, the term "the maximum absorption wavelength changes due to an acid, a base, or a radical" used for the dye includes (1) a mode in which a dye in a colored state is decolorized by an acid, a base, or a radical, (2) a mode in which a dye in a decolorized state is colored by an acid, a base, or a radical, and (3) a mode in which a dye in a colored state changes to a colored state of another hue. For example, dye N may be a compound that changes from a decolorized state to a colored state by exposure or a compound that changes from a colored state to a decolorized state by exposure. Dye N may be a dye whose coloring or decoloring state changes when an acid, a base, or a radical generated in the photosensitive resin layer by exposure acts on it. Dye N may be a dye whose coloring or decoloring state changes when the state (for example, pH) in the photosensitive resin layer changes due to an acid, a base, or a radical. Further, dye N may be a dye whose coloring or decoloring state changes directly by receiving the action of an acid, a base, or a radical without passing through exposure.

[0153] From the viewpoints of the visibility of the exposed portion and the visibility of the unexposed portion, dye N is preferably a dye that is colored by an acid, a base, or a radical.

[0154] From the viewpoints of the visibility of the exposed portion, the visibility of the unexposed portion, and the resolution, dye N is preferably a dye whose maximum absorption wavelength changes due to an acid or a radical, and more preferably a dye whose maximum absorption wavelength changes due to a radical. From the viewpoints of the visibility of the exposed portion, the visibility of the unexposed portion, and the resolution, the photosensitive resin layer preferably contains a dye whose maximum absorption wavelength changes due to a radical as dye N and a photo radical polymerization initiator.

[0155] From the viewpoints of the visibility of the exposed portion, the visibility of the unexposed portion, the pattern visibility after development, and the resolution, the dye N is preferably a dye whose maximum absorption wavelength changes due to radicals, and more preferably a dye that develops color due to radicals.

[0156] Examples of the color development mechanism of the dye N in the present disclosure include modes in which a radical-reactive dye, an acid-reactive dye, or a base-reactive dye (for example, a leuco dye) develops color due to a radical, an acid, or a base generated from a photo radical polymerization initiator, a photo cationic polymerization initiator (photo acid generator), or a photo base generator contained in the photosensitive resin layer.

[0157] From the viewpoints of the visibility of the exposed portion and the visibility of the unexposed portion, the maximum absorption wavelength of the dye N in the wavelength range of 400 nm to 780 nm, which is the wavelength range at the time of color development, is preferably 550 nm or more, more preferably 550 to 700 nm, and still more preferably 550 to 650 nm. The number of maximum absorption wavelengths in the wavelength range of 400 to 780 nm, which is the wavelength range at the time of color development, may be one or two or more. When the number of maximum absorption wavelengths in the wavelength range of 400 to 780 nm, which is the wavelength range at the time of color development, is two or more, it is sufficient that the maximum absorption wavelength having the highest absorbance among the two or more maximum absorption wavelengths is 450 nm or more.

[0158] The maximum absorption wavelength of the dye N is measured by the following method. In an air atmosphere, using a spectrophotometer (for example, UV3100, Shimadzu Corporation), the transmission spectrum of a solution containing the dye N (liquid temperature: 25°C) is measured in the wavelength range of 400 nm to 780 nm, and the wavelength at which the light intensity becomes minimum is detected. The wavelength at which the light intensity becomes minimum is adopted as the maximum absorption wavelength.

[0159] Examples of the dye that develops or fades color by exposure include leuco dyes.

[0160] Examples of the dye that fades by exposure include leuco dyes, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes.

[0161] From the viewpoints of visibility of the exposed area and visibility of the unexposed area, the dye N is preferably a leuco dye.

[0162] Examples of the leuco dye include leuco dyes having a triarylmethane skeleton (triarylmethane dyes), leuco dyes having a spiropyran skeleton (spiropyran dyes), leuco dyes having a fluoran skeleton (fluoran dyes), leuco dyes having a diarylmethane skeleton (diarylmethane dyes), leuco dyes having a rhodamine lactam skeleton (rhodamine lactam dyes), leuco dyes having an indolyl phthalide skeleton (indolyl phthalide dyes), and leuco dyes having a leuco auramine skeleton (leuco auramine dyes). Among these, triarylmethane dyes or fluoran dyes are preferable, and leuco dyes having a triphenylmethane skeleton (triphenylmethane dyes) or fluoran dyes are more preferable.

[0163] From the viewpoints of visibility of the exposed area and visibility of the unexposed area, the leuco dye preferably has a lactone ring, a sultine ring, or a sultone ring. By reacting the lactone ring, sultine ring, or sultone ring in the leuco dye with a radical generated from a photo radical polymerization initiator or an acid generated from a photo cationic polymerization initiator, the leuco dye can be changed to a closed-ring state to fade, or the leuco dye can be changed to an open-ring state to develop color. The leuco dye preferably has a lactone ring, a sultine ring, or a sultone ring and is a compound in which the lactone ring, sultine ring, or sultone ring is opened by a radical or an acid to develop color, and more preferably has a lactone ring and is a compound in which the lactone ring is opened by a radical or an acid to develop color.

[0164] Specific examples of the leuco dye include p,p’,p”-hexamethyltriaminotriphenylmethane (leuco crystal violet), Pergascript Blue SRB (Ciba Geigy), crystal violet lactone, malachite green lactone, benzoyl leucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl) amino fluoran, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino) fluoran, 3,6-dimethoxy fluoran, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino) fluoran, 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilino fluoran, 3-(N,N-diethylamino)-6-methyl-7-anilino fluoran, 3-(N,N-diethylamino)-6-methyl-7-xylylidino fluoran, 3-(N,N-diethylamino)-6-methyl-7-chloro fluoran, 3-(N,N-diethylamino)-6-methoxy-7-amino fluoran, 3-(N,N-diethylamino)-7-(4-chloroanilino) fluoran, 3-(N,N-diethylamino)-7-chloro fluoran, 3-(N,N-diethylamino)-7-benzylamino fluoran, 3-(N,N-diethylamino)-7,8-benzofluorane, 3-(N,N-dibutylamino)-6-methyl-7-anilino fluoran, 3-(N,N-dibutylamino)-6-methyl-7-xylylidino fluoran, 3-piperidino-6-methyl-7-anilino fluoran, 3-pyrrolidino-6-methyl-7-anilino fluoran, 3,3-bis(1-ethyl-2-methylindol-3-yl) phthalide, 3,3-bis(1-n-butyl-2-methylindol-3-yl) phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylamino phthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-xanthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl) phthalide, and 3’,6’-bis(diphenylamino) spiroisobenzofuran-1(3H),9’-[9H]xanthen-3-one.

[0165] Examples of the coloring agent N include dyes. Examples of the dyes include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsine, methyl violet 2B, quinoline red, rose bengal, metanil yellow, thymol sulfophthalein, xylenol blue, methyl orange, para - methyl red, congo red, benzopurpurin 4B, α - naphthyl red, nile blue 2B, nile blue A, methyl violet, malachite green, para - fuchsine, victoria pure blue - naphthalene sulfonate, victoria pure blue BOH (Hodogaya Chemical Co., Ltd.), oil blue #603 (Orient Chemical Industries, Ltd.), oil pink #312 (Orient Chemical Industries, Ltd.), oil red 5B (Orient Chemical Industries, Ltd.), oil scarlet #308 (Orient Chemical Industries, Ltd.), oil red OG (Orient Chemical Industries, Ltd.), oil red RR (Orient Chemical Industries, Ltd.), oil green #502 (Orient Chemical Industries, Ltd.), spiron red BEH special (Hodogaya Chemical Co., Ltd.), m - cresol purple, cresol red, rhodamine B, rhodamine 6G, sulfonated rhodamine B, auramine, 4 - p - diethylaminophenyliminonaphthoquinone, 2 - carboxyanilino - 4 - p - diethylaminophenyliminonaphthoquinone, 2 - carboxystearylamino - 4 - p - N,N - bis(hydroxyethyl)amino - phenyliminonaphthoquinone, 1 - phenyl - 3 - methyl - 4 - p - diethylaminophenylimino - 5 - pyrazolone, and 1 - β - naphthyl - 4 - p - diethylaminophenylimino - 5 - pyrazolone.

[0166] The coloring agent N is preferably leucocrystal violet, crystal violet lactone, brilliant green, or victoria pure blue - naphthalene sulfonate.

[0167] The photosensitive resin layer may contain one or more types of the coloring agent N.

[0168] From the viewpoints of the visibility of the exposed portion, the visibility of the unexposed portion, the pattern visibility after development, and the resolution, the content of Dye N is preferably 0.1% by mass or more, more preferably 0.1% by mass to 10% by mass, still more preferably 0.1% by mass to 5% by mass, and particularly preferably 0.1% by mass to 1% by mass, based on the total mass of the photosensitive resin layer. The content of Dye N means the content of Dye N when all of the Dye N contained in the photosensitive resin layer is in the colored state. Hereinafter, a method for quantifying a dye will be described by taking a dye that develops color by radicals as an example. Prepare a solution obtained by dissolving a dye (0.001 g) in methyl ethyl ketone (100 mL) and a solution obtained by dissolving 0.01 g in methyl ethyl ketone (100 mL). Add a photo radical polymerization initiator (Irgacure OXE01, manufactured by BASF) to each solution, and then irradiate with light of 365 nm to generate radicals and bring all the dyes into the colored state. In an air atmosphere, using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), measure the absorbance of each solution at a liquid temperature of 25°C and create a calibration curve. Next, measure the absorbance of the solution in which all the dyes are colored by the same method as described above except that the photosensitive resin layer (3 g) is dissolved in methyl ethyl ketone instead of the dye. Calculate the amount of the dye contained in the photosensitive resin layer from the absorbance of the solution containing the photosensitive resin layer based on the calibration curve.

[0169] (Surfactant) From the viewpoint of thickness uniformity, the photosensitive resin layer preferably contains a surfactant. Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. The surfactant is preferably a nonionic surfactant. The surfactant is preferably a fluorine-based surfactant or a silicone-based surfactant.

[0170] Examples of commercially available fluorosurfactants include Megafac (e.g., F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-444, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, MFS-578, MFS-578-2, MFS-579, MFS-586, MFS-587, MFS-628, MFS-631, MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, and DS-21, DIC Corporation), Fluorad (e.g., FC430, FC431, and FC171, Sumitomo 3M Limited), Surflon (e.g., S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40, AGC Inc.), PolyFox (e.g., PF636, PF656, PF6320, PF6520, and PF7002, OMNOVA Solutions), and Ftergent (e.g., 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, and 683, Neos Co., Ltd.), U-120E (Unichem Co., Ltd.).

[0171] As the fluorosurfactant, an acrylic compound having a molecular structure containing a functional group containing a fluorine atom and in which the portion of the functional group containing the fluorine atom is cleaved and the fluorine atom volatilizes when heat is applied may be used. Examples of the fluorosurfactant as described above include the Megafac DS series of DIC Corporation (Chemical Industry Daily (February 22, 2016), Nikkei Industrial Newspaper (February 23, 2016), e.g., Megafac DS-21).

[0172] As the fluorosurfactant, a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound may be used.

[0173] As the fluorosurfactant, a block polymer may be used.

[0174] As the fluorosurfactant, a fluorine-containing polymer compound containing a structural unit derived from a (meth)acrylate compound containing a fluorine atom and a structural unit derived from a (meth)acrylate compound containing two or more (preferably five or more) alkyleneoxy groups (preferably an ethyleneoxy group or a propyleneoxy group) may be used.

[0175] As the fluorosurfactant, a fluorine-containing polymer having a group containing an ethylenic unsaturated bond in the side chain may be used. Examples of commercially available products of the fluorosurfactant as described above include Megafac (for example, RS-101, RS-102, RS-718K, and RS-72-K, DIC Corporation).

[0176] As the fluorosurfactant, from the viewpoint of improving environmental suitability, it is preferably a surfactant derived from a substitute material for compounds having a linear perfluoroalkyl group with 7 or more carbon atoms such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS).

[0177] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates (e.g., glycerol ethoxylate) and propoxylates (e.g., glycerol propoxylate). Also, examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, pluronic (e.g., L10, L31, L61, L62, 10R5, 17R2, and 25R2, HYDROPALAT WE 3323, BASF), tetronic (e.g., 304, 701, 704, 901, 904, and 150R1, BASF), Solsperse 20000 (Lubrizol Japan Ltd.), NCW-101 (FUJIFILM Wako Pure Chemical Corporation), NCW-1001 (FUJIFILM Wako Pure Chemical Corporation), NCW-1002 (FUJIFILM Wako Pure Chemical Corporation), pionin (e.g., D-1105, D-6112, D-6112-W, and D-6315, Takemoto Yushi Co., Ltd.), Orfin E1010 (Nissin Chemical Industry Co., Ltd.), and Surfynol (e.g., 104, 400, and 440, Nissin Chemical Industry Co., Ltd.).

[0178] Examples of silicone surfactants include linear polymers composed of siloxane bonds and modified silicone polymers with organic groups introduced into the side chains or terminals.

[0179] Examples of surfactants include DOWSIL 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 (Toray Dow Corning Co., Ltd.).

[0180] Examples of the surfactant include EXP.S-309-2, EXP.S-315, EXP.S-503-2, and EXP.S-505-2 (manufactured by DIC Corporation).

[0181] Examples of the surfactant include 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, and KF-6002 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0182] Examples of the surfactant include KP-101, KP-103, KP-104, KP-105, KP-106, KP-109, KP-109, KP-112, KP-120, KP-121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, and KP-652 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0183] Examples of the surfactant include F-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (manufactured by Momentive Performance Materials).

[0184] Examples of the surfactant include BYK307, BYK323, and BYK330 (manufactured by BYK-Chemie) and the like.

[0185] Examples of the surfactant include BYK300, BYK306, BYK310, BYK320, BYK325, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, and BYK323 (manufactured by BYK-Chemie) and the like.

[0186] The photosensitive resin layer may contain one or more surfactants.

[0187] The content of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass, based on the total mass of the photosensitive resin layer.

[0188] (Additive) In addition to the above components, the photosensitive resin layer may contain known additives as necessary. Examples of the additives include thermally crosslinkable compounds, radical polymerization inhibitors, benzotriazoles, carboxybenzotriazoles, sensitizers, plasticizers, heterocyclic compounds, and solvents. The photosensitive resin layer may contain one or more additives.

[0189] From the viewpoints of the strength of the resulting cured film and the adhesiveness of the resulting uncured film, the photosensitive resin layer preferably contains a thermally crosslinkable compound. In this specification, the thermally crosslinkable compound having an ethylenically unsaturated group described later is treated as a thermally crosslinkable compound, not as an ethylenically unsaturated compound. Examples of the thermally crosslinkable compound include methylol compounds and blocked isocyanate compounds. Among them, from the viewpoints of the strength of the resulting cured film and the adhesiveness of the resulting uncured film, blocked isocyanate compounds are preferable. Since the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when the polymer A and / or the ethylenically unsaturated compound has at least one of a hydroxy group and a carboxy group, the hydrophilicity of the formed film decreases, and the function when the film obtained by curing the photosensitive resin layer is used as a protective film tends to be enhanced. Note that the blocked isocyanate compound refers to a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) with a blocking agent.

[0190] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100°C to 160°C, more preferably 130°C to 150°C. The dissociation temperature of the blocked isocyanate means "the temperature of the endothermic peak associated with the deprotection reaction of the blocked isocyanate when measured by DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter." As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be preferably used. However, the differential scanning calorimeter is not limited thereto.

[0191] Examples of the blocking agent having a dissociation temperature of 100°C to 160°C include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)], oxime compounds (formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketoxime, and compounds having a structure represented by -C(=N-OH)- in the molecule such as cyclohexanone oxime). Among these, as the blocking agent having a dissociation temperature of 100°C to 160°C, for example, from the viewpoint of storage stability, it is preferable to contain an oxime compound.

[0192] The blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoints of improving the brittleness of the film and enhancing the adhesion to the transfer target. The blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by isocyanurating and protecting hexamethylene diisocyanate. Among the blocked isocyanate compounds having an isocyanurate structure, a compound having an oxime structure using an oxime compound as a blocking agent is preferable from the viewpoints that it is easier to make the dissociation temperature in a preferable range than a compound having no oxime structure and that it is easier to reduce the development residue.

[0193] The blocked isocyanate compound may have a polymerizable group. The polymerizable group is not particularly limited, and known polymerizable groups can be used, and a radical polymerizable group is preferable. Examples of the polymerizable group include ethylenically unsaturated groups such as (meth)acryloxy group, (meth)acrylamide group, and styryl group, and groups having an epoxy group such as glycidyl group. Among them, as the polymerizable group, an ethylenically unsaturated group is preferable, a (meth)acryloxy group is more preferable, and an acryloxy group is still more preferable.

[0194] Commercially available products can be used as the blocked isocyanate compound. Examples of commercially available products of the blocked isocyanate compound include Calenz (registered trademark) AOI-BM, Calenz (registered trademark) MOI-BM, Calenz (registered trademark) MOI-BP, etc. (manufactured by Showa Denko K.K.), and blocked Duranate series (for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation). In addition, a compound having the following structure can also be used as the blocked isocyanate compound.

[0195] [Chemical formula]

[0196] The thermally crosslinkable compound may be used alone or in combination of two or more. When the photosensitive resin layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass, based on the total mass of the photosensitive resin layer.

[0197] Examples of the radical polymerization inhibitor include, for example, the thermal polymerization inhibitors described in paragraph 0018 of Japanese Patent No. 4502784. The radical polymerization inhibitor is preferably phenothiazine, phenoxazine or 4-methoxyphenol. Examples of the radical polymerization inhibitor also include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt and diphenylnitrosamine. In order not to impair the sensitivity of the photosensitive resin layer, it is preferable to use nitrosophenylhydroxyamine aluminum salt as the radical polymerization inhibitor.

[0198] Examples of the benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.

[0199] Examples of the carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylene carboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylene carboxybenzotriazole and N-(N,N-di-2-ethylhexyl)aminoethylene carboxybenzotriazole. Examples of commercially available products of carboxybenzotriazoles include, for example, CBT-1 (Joho Chemical Industry Co., Ltd.).

[0200] The total content of the radical polymerization inhibitor, benzotriazoles, and carboxybenzotriazoles is preferably 0.01% by mass to 3% by mass, more preferably 0.05% by mass to 1% by mass, based on the total mass of the photosensitive resin layer. Setting the total content of the above-mentioned additives to 0.01% by mass or more is preferable from the viewpoint of imparting storage stability to the photosensitive resin layer. On the other hand, setting the total content of the above-mentioned additives to 3% by mass or less is preferable from the viewpoints of maintaining sensitivity and suppressing decolorization of the dye.

[0201] The type of the sensitizer is not limited. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (for example, 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

[0202] From the viewpoints of improving the sensitivity to the light source and improving the curing rate by the balance between the polymerization rate and the chain transfer, when the photosensitive resin layer contains a sensitizer, the content of the sensitizer is preferably 0.01% by mass to 5% by mass, more preferably 0.05% by mass to 1% by mass, based on the total mass of the photosensitive resin layer.

[0203] Examples of the plasticizer and the heterocyclic compound include the compounds described in paragraphs 0097 to 0103 and paragraphs 0111 to 0118 of International Publication No. 2018 / 179640.

[0204] Examples of the solvent include the solvents described in the section of "Method for forming the photosensitive resin layer" below. For example, when a photosensitive resin layer is formed using a composition for forming a photosensitive resin layer containing a solvent, the solvent may remain in the photosensitive resin layer.

[0205] The photosensitive resin layer may further contain at least one selected from the group consisting of metal oxide particles, antioxidants, dispersants, acid generators, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, organic precipitation inhibitors, and inorganic precipitation inhibitors.

[0206] Regarding the additives contained in the photosensitive resin layer, they are described in paragraphs 0165 to 0184 of JP-A-2014-85643. The content of the above-mentioned publication is incorporated herein by reference.

[0207] (Impurities) The photosensitive resin layer may contain impurities. Examples of the impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and their ions. Since halide ions, sodium ions, and potassium ions are likely to be mixed in as impurities, the content rates of halide ions, sodium ions, and potassium ions are preferably within the following ranges.

[0208] The content rate of impurities in the photosensitive resin layer is preferably 80 ppm or less, more preferably 10 ppm or less, and particularly preferably 2 ppm or less with respect to the total mass of the photosensitive resin layer. The content rate of impurities in the photosensitive resin layer may be 1 ppb or more or 0.1 ppm or more with respect to the total mass of the photosensitive resin layer. As methods for setting the content rate of impurities within the above ranges, selecting raw materials with a low content of impurities, preventing the mixing of impurities during the formation of the photosensitive resin layer, and washing and removing them can be mentioned. Impurities are quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, and ion chromatography.

[0209] In the photosensitive resin layer, the content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane is preferably low. The content of the above compounds in the photosensitive resin layer is preferably 100 ppm or less, more preferably 20 ppm or less, and particularly preferably 4 ppm or less with respect to the total mass of the photosensitive resin layer. The content of the above compounds in the photosensitive resin layer may be 10 ppb or more or 100 ppb or more with respect to the total mass of the photosensitive resin layer. The content of the above compounds is adjusted by the same method as the method for adjusting the content of the above impurities. Further, the above compounds are quantified by known measurement methods.

[0210] From the viewpoints of improving reliability and laminatability, the water content in the photosensitive resin layer is preferably 0.01% by mass to 1.0% by mass, more preferably 0.05% by mass to 0.5% by mass with respect to the total mass of the photosensitive resin layer.

[0211] (Residual monomer) The photosensitive resin layer may contain residual monomers, for example, residual monomers corresponding to each structural unit of the above-described polymer A. From the viewpoints of patterning properties and reliability, the content of the residual monomer is preferably 5,000 ppm by mass or less, more preferably 2,000 ppm by mass or less, and still more preferably 500 ppm by mass or less with respect to the total mass of polymer A. The lower limit of the content of the residual monomer is not particularly limited, but is preferably 1 ppm by mass or more, more preferably 10 ppm by mass or more with respect to the total mass of polymer A. From the viewpoints of patterning properties and reliability, the content of the residual monomer corresponding to each structural unit of polymer A is preferably 3,000 ppm by mass or less, more preferably 600 ppm by mass or less, and still more preferably 100 ppm by mass or less with respect to the total mass of the photosensitive resin layer. The lower limit of the content of the residual monomer corresponding to each structural unit of polymer A is not particularly limited, but is preferably 0.1 ppm by mass or more, more preferably 1 ppm by mass or more with respect to the total mass of the photosensitive resin layer.

[0212] When synthesizing polymer A by a polymer reaction, the amount of residual monomers of the monomers is also preferably within the above range. For example, when synthesizing polymer A by reacting glycidyl acrylate with a carboxylic acid side chain, it is preferable to make the content of glycidyl acrylate within the above range. The amount of residual monomers can be measured by known methods such as liquid chromatography and gas chromatography.

[0213] (Thickness) The thickness of the photosensitive resin layer is not limited. The thickness of the photosensitive resin layer is determined, for example, in the range of 0.1 μm to 100 μm. From the viewpoints of developability and resolution, the thickness of the photosensitive resin layer is preferably 50 μm or less, more preferably 30 μm or less, and particularly preferably 20 μm or less. Further, the thickness of the photosensitive resin layer is preferably 10 μm or less, more preferably 5 μm or less. From the viewpoint of the resistance to treatment liquids such as developing solutions, the thickness of the photosensitive resin layer is preferably 0.1 μm or more, more preferably 0.2 μm or more, and particularly preferably 0.5 μm or more. Further, the thickness of the photosensitive resin layer is preferably 0.5 μm to 10 μm, more preferably 0.5 μm to 5 μm. Also, the thickness of the photosensitive resin layer is preferably 1 μm to 10 μm, and particularly preferably 0.5 μm to 4 μm. The thickness of the photosensitive resin layer is measured by a method conforming to the method for measuring the thickness of the temporary support.

[0214] (Transmittance) From the point of excellent adhesion, the transmittance of the photosensitive resin layer at a wavelength of 365 nm is preferably 10% or more, more preferably 30% or more, and particularly preferably 50% or more. The upper limit of the transmittance of the photosensitive resin layer at a wavelength of 365 nm is not limited. The transmittance of the photosensitive resin layer at a wavelength of 365 nm is preferably 99.9% or less.

[0215] (Method for forming the photosensitive resin layer) The method for forming the photosensitive resin layer is not limited as long as it can form a layer containing the above components. The photosensitive resin layer is formed, for example, by preparing a composition for forming a photosensitive resin layer, applying the composition for forming a photosensitive resin layer onto the second surface of a temporary support, and drying the applied composition for forming a photosensitive resin layer.

[0216] Examples of the composition for forming a photosensitive resin layer include a composition containing polymer A, polymerizable compound B, and a photopolymerization initiator. In order to adjust the viscosity of the composition for forming a photosensitive resin layer and facilitate the formation of the photosensitive resin layer, the composition for forming a photosensitive resin layer preferably contains a solvent.

[0217] The solvent is not limited as long as it can dissolve or disperse the components of the photosensitive resin layer. Examples of the solvent include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (e.g., methanol and ethanol), ketone solvents (e.g., acetone and methyl ethyl ketone), aromatic hydrocarbon solvents (e.g., toluene), aprotic polar solvents (e.g., N,N-dimethylformamide), cyclic ether solvents (e.g., tetrahydrofuran), ester solvents, amide solvents, and lactone solvents.

[0218] Examples of the alkylene glycol ether solvent include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether.

[0219] Examples of the alkylene glycol ether acetate solvent include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.

[0220] Examples of the solvent include the solvents described in paragraphs 0092 to 0094 of WO2018 / 179640 and the solvents described in paragraph 0014 of JP2018-177889A. The contents of these publications are incorporated herein by reference.

[0221] The composition for forming a photosensitive resin layer may contain one or more solvents. The composition for forming a photosensitive resin layer preferably contains at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, more preferably contains at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one selected from the group consisting of ketone solvents and cyclic ether solvents, and particularly preferably contains at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, a ketone solvent, and a cyclic ether solvent.

[0222] The content of the solvent in the composition for forming a photosensitive resin layer is preferably 50 parts by mass to 1,900 parts by mass, more preferably 100 parts by mass to 900 parts by mass, based on 100 parts by mass of the total solid content in the composition for forming a photosensitive resin layer.

[0223] The method for preparing the composition for forming a photosensitive resin layer is not limited. The composition for forming a photosensitive resin layer is prepared, for example, by previously preparing a solution in which each component is dissolved in a solvent and mixing the obtained solutions at a predetermined ratio. Before forming the photosensitive resin layer, it is preferable to filter the composition for forming a photosensitive resin layer using a filter having a pore size of 0.2 μm to 30 μm.

[0224] Examples of the coating method of the composition for forming a photosensitive resin layer include slit coating, spin coating, curtain coating, and inkjet coating.

[0225] <<Thermoplastic resin layer>> The photosensitive transfer material according to the present disclosure may include a thermoplastic resin layer. By including a thermoplastic resin layer in the photosensitive transfer material, the followability of the photosensitive transfer material to the substrate is improved when the photosensitive transfer material is bonded to the substrate, and the entry of air bubbles between the photosensitive transfer material and the substrate is suppressed. Further, by including a thermoplastic resin layer in the photosensitive transfer material, the adhesion between layers is improved. The photosensitive transfer material according to the present disclosure preferably includes a thermoplastic resin layer between the temporary support and the photosensitive resin layer. Regarding the thermoplastic resin layer, for example, it is described in paragraphs 0189 to 0193 of JP-A-2014-85643. The content of the above publication is incorporated herein by reference.

[0226] (Alkali-soluble resin) The thermoplastic resin layer preferably contains an alkali-soluble resin as the thermoplastic resin. Examples of the alkali-soluble resin include acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine, and polyalkylene glycol.

[0227] From the viewpoints of developability and adhesion to an adjacent layer, the alkali-soluble resin is preferably an acrylic resin. Here, the acrylic resin means a resin containing at least one selected from the group consisting of a structural unit derived from (meth)acrylic acid, a structural unit derived from (meth)acrylic acid ester, and a structural unit derived from (meth)acrylamide. From the viewpoints of developability and adhesion to an adjacent layer, an acrylic resin having a structural unit derived from (meth)acrylic acid is particularly preferable as the alkali-soluble resin.

[0228] The total content ratio of the structural units derived from (meth)acrylic acid, the structural units derived from (meth)acrylic acid ester, and the structural units derived from (meth)acrylamide is preferably 50% by mass or more based on the total mass of the acrylic resin. The total content ratio of the structural units derived from (meth)acrylic acid and the structural units derived from (meth)acrylic acid ester is preferably 30% by mass to 100% by mass, more preferably 50% by mass to 100% by mass, based on the total mass of the acrylic resin.

[0229] The alkali-soluble resin preferably contains an acid group. Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group. The acid group is preferably a carboxy group.

[0230] From the viewpoint of developability, the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more, more preferably a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more. The acid value of the alkali-soluble resin is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less.

[0231] Examples of the carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more include the carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the polymers described in paragraph 0025 of JP-A-2011-95716, the carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the polymers described in paragraphs 0033 to 0052 of JP-A-2010-237589, and the carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the binder polymers described in paragraphs 0053 to 0068 of JP-A-2016-224162.

[0232] The content ratio of the structural unit having a carboxy group in the carboxy group-containing acrylic resin is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, particularly preferably 12% by mass to 30% by mass, based on the total mass of the acrylic resin.

[0233] The alkali-soluble resin may contain a reactive group. Examples of the reactive group include an ethylenically unsaturated group, a polycondensable group (e.g., a hydroxy group and a carboxy group), and a polyaddition-reactive group (e.g., an epoxy group and a (block) isocyanate group).

[0234] The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably from 10,000 to 100,000, and particularly preferably from 20,000 to 50,000.

[0235] The thermoplastic resin layer may contain one or more alkali-soluble resins.

[0236] From the viewpoints of developability and adhesion to an adjacent layer, the content of the alkali-soluble resin is preferably from 10% by mass to 99% by mass, more preferably from 20% by mass to 90% by mass, still more preferably from 40% by mass to 80% by mass, and particularly preferably from 50% by mass to 70% by mass, based on the total mass of the thermoplastic resin layer.

[0237] (Dye) The thermoplastic resin layer preferably contains a dye (hereinafter sometimes referred to as "dye B") having a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 to 780 nm, which is the wavelength range at the time of color development, and the maximum absorption wavelength of which changes due to an acid, a base, or a radical. The preferred embodiments of dye B are the same as the preferred embodiments of dye N, except for the matters shown below.

[0238] From the viewpoints of visibility of the exposed portion, visibility of the non-exposed portion, and resolution, dye B is preferably a dye whose maximum absorption wavelength changes due to an acid or a radical, and more preferably a dye whose maximum absorption wavelength changes due to an acid.

[0239] The thermoplastic resin layer may contain one or more dyes B.

[0240] From the viewpoints of the visibility of the exposed portion and the visibility of the unexposed portion, the content rate of the dye B is preferably 0.2% by mass or more, more preferably 0.2% by mass to 6% by mass, still more preferably 0.2% by mass to 5% by mass, and particularly preferably 0.25% by mass to 3.0% by mass with respect to the total mass of the thermoplastic resin layer. Here, the content of the dye B means the content of the dye when all the dye B contained in the thermoplastic resin layer is in a colored state. Hereinafter, taking the dye that develops color by radicals as an example, the method for quantifying the dye will be described. Prepare a solution of dye B (0.001 g) dissolved in methyl ethyl ketone (100 mL) and a solution of dye B (0.01 g) dissolved in methyl ethyl ketone (100 mL). Add a photoinitiator (Irgacure OXE01, BASF) to each solution, and then irradiate with light of 365 nm to generate radicals and bring all the dyes into a colored state. Under an air atmosphere, using a spectrophotometer (UV3100, Shimadzu Corporation), measure the absorbance of each solution at a liquid temperature of 25°C and create a calibration curve. Next, measure the absorbance of the solution in which all the dyes are colored by the same method as described above except that the thermoplastic resin layer (0.1 g) is dissolved in methyl ethyl ketone instead of the dye. Calculate the amount of the dye contained in the thermoplastic resin layer from the absorbance of the solution containing the thermoplastic resin layer based on the calibration curve.

[0241] From the viewpoints of the visibility of the exposed portion, the visibility of the unexposed portion, and the resolution, it is preferable that the thermoplastic resin layer contains a dye whose maximum absorption wavelength changes due to an acid as the dye B and a compound that generates an acid by light. The compound that generates an acid by light will be described later.

[0242] (Compound that generates an acid, a base, or a radical by light) The thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical upon exposure to light (hereinafter sometimes referred to as "Compound C"). Compound C is preferably a compound that generates an acid, a base, or a radical upon receiving actinic rays (e.g., ultraviolet rays and visible light). Examples of Compound C include photoacid generators, photobase generators, and photo radical polymerization initiators (photo radical generators). Among these, photoacid generators are preferred.

[0243] From the viewpoint of resolution, the thermoplastic resin layer preferably contains a photoacid generator. Examples of the photoacid generator include the photo cationic polymerization initiators described in the section on the "photosensitive resin layer" above. The preferred embodiments of the photoacid generator are the same as the preferred embodiments of the photo cationic polymerization initiators described in the section on the "photosensitive resin layer" except for the matters shown below. From the viewpoints of sensitivity and resolution, the photoacid generator preferably contains at least one selected from the group consisting of onium salt compounds and oxime sulfonate compounds. From the viewpoints of sensitivity, resolution, and adhesion, the photoacid generator preferably contains an oxime sulfonate compound. Specific examples of preferred photoacid generators are shown below.

[0244]

Chemical formula

[0245] The thermoplastic resin layer may contain a photo-base generator. Examples of the photo-base generator include 2-nitrobenzyl cyclohexylcarbamate, triphenylmethanol, O-carbamoyl hydroxylamine, O-carbamoyl oxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt(III) tris(triphenylmethyl borate), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2,6-dimethyl-3,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine, and 2,6-dimethyl-3,5-diacetyl-4-(2,4-dinitrophenyl)-1,4-dihydropyridine.

[0246] The thermoplastic resin layer may contain a photo radical polymerization initiator. Examples of the photo radical polymerization initiator include the photo radical polymerization initiators described in the section of "photosensitive resin layer" above. The preferred embodiments of the photo radical polymerization initiator are the same as the preferred embodiments of the photo radical polymerization initiators described in the section of "photosensitive resin layer" above.

[0247] The thermoplastic resin layer may contain one or more compounds C.

[0248] From the viewpoints of visibility of the exposed portion, visibility of the unexposed portion, and resolution, the content of compound C in the thermoplastic resin layer is preferably 0.1% by mass to 10% by mass, and more preferably 0.5% by mass to 5% by mass, based on the total mass of the thermoplastic resin layer.

[0249] (Plasticizer) From the viewpoints of resolution, adhesion to an adjacent layer, and developability, the thermoplastic resin layer preferably contains a plasticizer.

[0250] The molecular weight of the plasticizer (when the plasticizer has a molecular weight distribution, the weight average molecular weight (Mw)) is preferably smaller than the molecular weight of the alkali-soluble resin. The molecular weight of the plasticizer is preferably from 200 to 2,000.

[0251] Examples of the plasticizer include compounds that are compatible with the alkali-soluble resin and exhibit plasticity. From the viewpoint of imparting plasticity, the plasticizer is preferably a compound containing an alkyleneoxy group in the molecule, more preferably a polyalkylene glycol compound. The alkyleneoxy group contained in the plasticizer more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.

[0252] From the viewpoints of resolution and storage stability, the plasticizer preferably contains a (meth)acrylate compound. From the viewpoints of compatibility, resolution, and adhesion to an adjacent layer, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound. Examples of the (meth)acrylate compound used as the plasticizer include the (meth)acrylate compounds described in the section of "Polymerizable Compound B" above. When the thermoplastic resin layer is in contact with the photosensitive resin layer in the photosensitive transfer material, the thermoplastic resin layer and the photosensitive resin layer preferably contain the same (meth)acrylate compound. By having the thermoplastic resin layer and the photosensitive resin layer contain the same (meth)acrylate compound, component diffusion between the layers is suppressed and storage stability is improved.

[0253] From the viewpoint of adhesion to an adjacent layer, the (meth)acrylate compound used as the plasticizer preferably does not polymerize even in the exposed area after exposure.

[0254] From the viewpoints of resolution, adhesion to an adjacent layer, and developability, the (meth)acrylate compound used as the plasticizer is preferably a (meth)acrylate compound having two or more (meth)acryloyl groups in one molecule.

[0255] The (meth)acrylate compound used as a plasticizer is preferably a (meth)acrylate compound having an acid group or a urethane (meth)acrylate compound.

[0256] The thermoplastic resin layer may contain one or more plasticizers.

[0257] From the viewpoints of resolution, adhesion to an adjacent layer, and developability, the content of the plasticizer in the thermoplastic resin layer is preferably 1% by mass to 70% by mass, more preferably 10% by mass to 60% by mass, and particularly preferably 20% by mass to 50% by mass with respect to the total mass of the thermoplastic resin layer.

[0258] (Surfactant) From the viewpoint of thickness uniformity, the thermoplastic resin layer preferably contains a surfactant. Examples of the surfactant include the surfactants described in the section of the above "photosensitive resin layer". The preferred embodiments of the surfactant are the same as the preferred embodiments of the surfactants described in the section of the above "photosensitive resin layer".

[0259] The thermoplastic resin layer may contain one or more surfactants.

[0260] The content of the surfactant in the thermoplastic resin layer is preferably 0.001% by mass to 10% by mass, and more preferably 0.01% by mass to 3% by mass with respect to the total mass of the thermoplastic resin layer.

[0261] (Sensitizer) The thermoplastic resin layer may contain a sensitizer. Examples of the sensitizer include the sensitizers described in the section of the above "photosensitive resin layer".

[0262] The thermoplastic resin layer may contain one or more sensitizers.

[0263] From the viewpoints of improving the sensitivity to light sources and the visibility of the exposed and non-exposed portions, the content of the sensitizer is preferably 0.01% by mass to 5% by mass, and more preferably 0.05% by mass to 1% by mass, based on the total mass of the thermoplastic resin layer.

[0264] (Additive) In addition to the above-described components, the thermoplastic resin layer may contain known additives as necessary.

[0265] (Thickness) The thickness of the thermoplastic resin layer is not limited. From the viewpoint of adhesion to the adjacent layer, the thickness of the thermoplastic resin layer is preferably 1 μm or more, and more preferably 2 μm or more. From the viewpoints of developability and resolution, the thickness of the thermoplastic resin layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less. The thickness of the thermoplastic resin layer is measured by a method conforming to the method for measuring the thickness of the temporary support.

[0266] (Method for forming the thermoplastic resin layer) The method for forming the thermoplastic resin layer is not limited as long as it can form a layer containing the above components. The thermoplastic resin layer is formed, for example, by preparing a composition for forming the thermoplastic resin layer, applying the composition for forming the thermoplastic resin layer onto an object (for example, a photosensitive resin layer), and drying the applied composition for forming the thermoplastic resin layer.

[0267] In order to adjust the viscosity of the composition for forming the thermoplastic resin layer and facilitate the formation of the thermoplastic resin layer, the composition for forming the thermoplastic resin layer preferably contains a solvent. The solvent is not limited as long as it can dissolve or disperse the components of the thermoplastic resin layer. Examples of the solvent include the solvents described in the section on the "photosensitive resin layer" above. The preferred embodiments of the solvent are the same as the preferred embodiments of the solvents described in the section on the "photosensitive resin layer" above.

[0268] The composition for forming the thermoplastic resin layer may contain one or more solvents.

[0269] The content rate of the solvent in the composition for forming a thermoplastic resin layer is preferably 50 parts by mass to 1,900 parts by mass, more preferably 100 parts by mass to 900 parts by mass, with respect to 100 parts by mass of the total solid content in the composition for forming a thermoplastic resin layer.

[0270] The composition for forming a thermoplastic resin layer is prepared, for example, by a method according with the method for preparing a composition for forming a photosensitive resin layer. The composition for forming a thermoplastic resin layer is applied, for example, by a method according with the coating method of the composition for forming a photosensitive resin layer.

[0271] <<Intermediate layer>> The photosensitive transfer material according to the present disclosure preferably includes an intermediate layer between the photosensitive resin layer and the thermoplastic resin layer. By including the intermediate layer in the photosensitive transfer material, mixing of components occurring between layers in the formation or storage of the photosensitive transfer material can be suppressed. From the viewpoints of developability and suppression of mixing of components occurring between layers in the formation or storage of the photosensitive transfer material, the intermediate layer is preferably a water-soluble layer. In the present disclosure, "water-soluble" means a property that the solubility in water (100 g) at pH 7.0 with a liquid temperature of 22°C is 0.1 g or more.

[0272] Examples of the intermediate layer include an oxygen barrier layer having an oxygen barrier function described as a "separation layer" in JP-A-5-72724. The oxygen barrier layer is preferable in that the sensitivity during exposure is improved, the time load on the exposure machine is reduced, and productivity is improved. The oxygen barrier layer preferably exhibits low oxygen permeability and is an oxygen barrier layer dispersed or dissolved in water or an aqueous alkali solution (1 mass% aqueous sodium carbonate solution, liquid temperature: 22°C).

[0273] The intermediate layer preferably contains a resin. Examples of the resin include polyvinyl alcohol-based resins, polyvinyl pyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, and polyamide resins. The resin may be a homopolymer or a copolymer. The resin is preferably a water-soluble resin.

[0274] From the viewpoint of suppressing the mixing of components occurring between layers in the formation of an oxygen-barrier and photosensitive transfer material or the storage of a photosensitive transfer material, the intermediate layer preferably contains polyvinyl alcohol, and more preferably contains polyvinyl alcohol and polyvinyl pyrrolidone.

[0275] From the viewpoint of suppressing the mixing of components occurring between layers, the resin contained in the intermediate layer is preferably a resin different from polymer A contained in the photosensitive resin layer and also preferably a resin different from the thermoplastic resin (e.g., an alkali-soluble resin) contained in the thermoplastic resin layer.

[0276] The intermediate layer may contain one or more resins.

[0277] From the viewpoint of suppressing the mixing of components occurring between layers in the formation of an oxygen-barrier and photosensitive transfer material or the storage of a photosensitive transfer material, the content of the resin in the intermediate layer is preferably 50% to 100% by mass, more preferably 70% to 100% by mass, still more preferably 80% to 100% by mass, and particularly preferably 90% to 100% by mass based on the total mass of the intermediate layer.

[0278] The intermediate layer may contain additives such as a surfactant as required. Examples of the surfactant include the surfactants described in the section of the "photosensitive resin layer" above. The preferred embodiments of the surfactant are the same as the preferred embodiments of the surfactants described in the section of the "photosensitive resin layer" above.

[0279] The thickness of the intermediate layer is not limited. The thickness of the intermediate layer is preferably 0.1 μm to 5 μm, and more preferably 0.5 μm to 3 μm. When the thickness of the intermediate layer is within the above range, the oxygen barrier property is not deteriorated, the mixing of components occurring between layers in the formation of a photosensitive transfer material or the storage of a photosensitive transfer material can be suppressed, and an increase in the removal time of the intermediate layer in the development process can be suppressed. The thickness of the intermediate layer is measured by a method conforming to the method for measuring the thickness of the temporary support.

[0280] The method for forming the intermediate layer is not limited. The intermediate layer is formed, for example, by preparing a composition for forming an intermediate layer containing a resin and any additives, applying the composition for forming an intermediate layer to the surface of a thermoplastic resin layer or a photosensitive resin layer, and drying the applied composition for forming an intermediate layer.

[0281] In order to adjust the viscosity of the composition for forming an intermediate layer and facilitate the formation of the intermediate layer, the composition for forming an intermediate layer preferably contains a solvent. The solvent is not limited as long as it can dissolve or disperse the resin. The solvent is preferably at least one selected from the group consisting of water and water-miscible organic solvents, and more preferably water or a mixed solvent of water and a water-miscible organic solvent. Examples of water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin. The water-miscible organic solvent is preferably an alcohol having 1 to 3 carbon atoms, and more preferably methanol or ethanol.

[0282] <<Protective film>> The photosensitive transfer material according to the present disclosure preferably includes a protective film. The photosensitive transfer material according to the present disclosure preferably includes a temporary support, a photosensitive resin layer, and a protective film in this order. The protective film is preferably the outermost layer of the photosensitive transfer material.

[0283] Examples of the protective film include a resin film and paper. From the viewpoints of strength and flexibility, a resin film is preferred. Examples of the resin film include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among the above, a polyethylene film, a polypropylene film, or a polyethylene terephthalate film is preferred.

[0284] The thickness of the protective film is not limited. The thickness of the protective film is preferably 5 μm to 100 μm, and more preferably 10 μm to 50 μm. The thickness of the protective film is measured by a method conforming to the method for measuring the thickness of the temporary support.

[0285] From the viewpoint of excellent resolution, the arithmetic mean roughness Ra of the surface on the photosensitive resin layer side of the protective film (hereinafter, may be simply referred to as "the surface of the protective film") is preferably 0.3 μm or less, more preferably 0.1 μm or less, and particularly preferably 0.05 μm or less. It is considered that when the arithmetic mean roughness Ra of the surface of the protective film is within the above range, the uniformity of the thickness of the photosensitive resin layer and the formed resin pattern is improved. The lower limit of the arithmetic mean roughness Ra of the protective film is preferably 0.001 μm or more.

[0286] The arithmetic mean roughness Ra of the surface of the protective film is measured by the following method. Using a three-dimensional optical profiler (New View7300, Zygo), obtain the surface profile of the protective film under the following conditions. As measurement and analysis software, use the Microscope Application of MetroPro ver8.3.2. Next, display the Surface Map screen using the above analysis software, and obtain histogram data in the Surface Map screen. Calculate the arithmetic mean roughness Ra from the obtained histogram data. In the measurement of the arithmetic mean roughness Ra of the surface of the protective film included in the photosensitive transfer material, the arithmetic mean roughness Ra of the surface of the protective film revealed by peeling the protective film from the photosensitive transfer material may be measured.

[0287] <<Relationship between the temporary support, the photosensitive resin layer, and the protective film>> In the photosensitive transfer material according to the present disclosure, the elongation at break at 120 °C of the cured film obtained by curing the photosensitive resin layer is 15% or more, the arithmetic mean roughness Ra of the surface on the photosensitive resin layer side of the temporary support is 50 nm or less, and the arithmetic mean roughness Ra of the surface on the photosensitive resin layer side of the protective film is preferably 150 nm or less.

[0288] Further, the photosensitive transfer material according to the present disclosure preferably satisfies the following formula (R1). X × Y < 1,500: Formula (R1) Here, in the above formula (R1), X represents the value (%) of the elongation at break at 120°C of the cured film obtained by curing the photosensitive resin layer, and Y represents the value (nm) of the arithmetic mean roughness Ra of the surface on the photosensitive resin layer side of the temporary support. It is more preferable that X × Y is 750 or less.

[0289] Preferably, the elongation at break at 120°C is at least twice as large as the elongation at break at 23°C of the cured film obtained by curing the photosensitive resin layer. The elongation at break is measured by a tensile test using a cured film obtained by exposing a photosensitive resin layer with a thickness of 20 μm to light at 120 mJ / cm 2 by an ultra-high pressure mercury lamp for curing, then additionally exposing it with a high pressure mercury lamp at 400 mJ / cm 2 and heating it at 145°C for 30 minutes.

[0290] Further, the photosensitive transfer material according to the present disclosure preferably satisfies the following formula (R2). Y ≤ Z: Formula (R2) Here, in the above formula (R2), Y represents the value (nm) of the arithmetic mean roughness Ra of the surface on the photosensitive resin layer side of the temporary support, and Z represents the value (nm) of the arithmetic mean roughness Ra of the surface on the photosensitive resin layer side of the protective film.

[0291] <<Other Layers>> The photosensitive transfer material according to the present disclosure may include layers other than the above-described layers (hereinafter referred to as "other layers" in this paragraph). Examples of other layers include a contrast enhancement layer (also referred to as a refractive index adjustment layer). The contrast enhancement layer is described in paragraph 0134 of International Publication No. 2018 / 179640. Further, other layers are described in paragraphs 0194 to 0196 of JP-A-2014-85643. The contents of these publications are incorporated herein by reference.

[0292] <<Method for manufacturing a photosensitive transfer material>> The method for manufacturing a photosensitive transfer material according to the present disclosure is not limited. The photosensitive transfer material is manufactured, for example, by using the formation methods of the respective layers described above. Hereinafter, the method for manufacturing a photosensitive transfer material will be described with reference to FIGS. 1 and 2. FIG. 1 is a schematic diagram showing the configuration of a photosensitive transfer material according to the present disclosure. FIG. 2 is a schematic diagram showing the configuration of a photosensitive transfer material according to another embodiment of the present disclosure. FIG. 3 is a schematic diagram showing the configuration of a photosensitive transfer material according to another embodiment of the present disclosure.

[0293] The photosensitive transfer material 100 shown in FIG. 1 includes a temporary support 10, a photosensitive resin layer 20, and a protective film 30 in this order. The photosensitive transfer material 100 is manufactured, for example, by the following method. Prepare a temporary support 10 having a first surface 10a and a second surface 10b on the opposite side of the first surface 10a. The L * value measured by the SCE method of the second surface 10b of the temporary support 10 is 1.5 or less. A composition for forming a photosensitive resin layer is applied on the second surface 10b of the temporary support 10, and the applied composition for forming a photosensitive resin layer is dried to form a photosensitive resin layer 20. A protective film 30 is disposed on the photosensitive resin layer 20. By winding up the photosensitive transfer material 100 manufactured by the above method, the photosensitive transfer material 100 in a roll form may be produced and stored. The photosensitive transfer material 100 in a roll form is used, for example, for bonding to a substrate by a roll-to-roll method.

[0294] The photosensitive transfer material 110 shown in Fig. 2 includes a temporary support 11, a photosensitive resin layer 20, and a protective film 30 in this order. The temporary support 11 includes a particle-containing layer 11-1 and a base material 11-2 in this order in the lamination direction from the temporary support 11 toward the photosensitive resin layer 20. In the temporary support 11, the particle-containing layer 11-1 is disposed as the outermost layer on the first surface 11a side of the temporary support 11. In the temporary support 11, the base material 11-2 is disposed as the outermost layer on the second surface 11b side of the temporary support 11. The photosensitive transfer material 110 is manufactured by the same method as the manufacturing method of the above-described photosensitive transfer material 100, for example, except that the temporary support 11 is prepared instead of the temporary support 10.

[0295] The photosensitive transfer material 120 shown in Fig. 3 includes a temporary support 10, a thermoplastic resin layer 40, an intermediate layer 50, a photosensitive resin layer 20, and a protective film 30 in this order. As a manufacturing method of the photosensitive transfer material 120, for example, a method of forming the thermoplastic resin layer 40, the intermediate layer 50, the photosensitive resin layer 20, and the protective film 30 in this order on the second surface 10b of the temporary support according to the above-described method can be mentioned.

[0296] The manufacturing method of the photosensitive transfer material according to the present disclosure is not limited to the above-described method. For example, the photosensitive transfer material may be manufactured by forming each layer on the protective film instead of the temporary support.

[0297] <<Use of Photosensitive Transfer Material>> The photosensitive transfer material according to the present disclosure is suitably used, for example, in various applications that require precision microfabrication by photolithography. For example, after patterning the photosensitive resin layer, etching may be performed using the photosensitive resin layer or a cured product thereof as a film, or electroforming mainly based on electroplating may be performed. The cured product obtained by patterning may be used as a permanent film. The cured product obtained by patterning may be used, for example, as an interlayer insulating film, a wiring protection film, or a wiring protection film having an index matching layer. The photosensitive transfer material according to the present disclosure is suitably used, for example, in a method for forming wiring in a semiconductor package, a printed circuit board, or a sensor substrate. The photosensitive transfer material according to the present disclosure is suitably used, for example, in a method for forming a conductive film such as a touch panel, an electromagnetic wave shielding material, and a film heater. The photosensitive transfer material according to the present disclosure is suitably used, for example, in a method for forming a structure in the fields of liquid crystal sealing materials, micromachines, and microelectronics.

[0298] The photosensitive transfer material according to the present disclosure may be used, for example, as a photosensitive transfer material for a wiring protection film. Examples of the layer configuration of the photosensitive transfer material preferably used as the photosensitive transfer material for a wiring protection film include the following (1) and (2). (1) Temporary support / Photosensitive resin layer / Refractive index adjustment layer / Protective film (2) Temporary support / Photosensitive resin layer / Protective film

[0299] Hereinafter, the components of the photosensitive transfer material preferably used as the photosensitive transfer material for a wiring protection film will be described. However, the components of the photosensitive transfer material preferably used as the photosensitive transfer material for a wiring protection film are not limited to the components shown below.

[0300] (Temporary support) Examples of the temporary support include the temporary supports described in the section of the above "temporary support". The preferred embodiments of the temporary support are the same as the preferred embodiments of the temporary support described in the section of the above "temporary support".

[0301] (Protective film) Examples of the protective film include the protective films described in the section of "Protective film" above. Preferred embodiments of the protective film are the same as the preferred embodiments of the protective films described in the section of "Protective film" above.

[0302] (Photosensitive resin layer) -Alkali-soluble resin- The photosensitive resin layer preferably contains an alkali-soluble resin. Examples of the alkali-soluble resin include (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenol resins, ester resins, urethane resins, epoxy acrylate resins obtained by the reaction of epoxy resins and (meth)acrylic acid, and acid-modified epoxy acrylate resins obtained by the reaction of epoxy acrylate resins and acid anhydrides.

[0303] One of the preferred embodiments of the alkali-soluble resin is a (meth)acrylic resin in terms of excellent alkali developability and film-forming properties. In this specification, the (meth)acrylic resin means a resin having a structural unit derived from a (meth)acrylic compound. The content of the structural unit derived from the (meth)acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more based on all the structural units of the (meth)acrylic resin. The (meth)acrylic resin may be composed only of structural units derived from a (meth)acrylic compound, or may have structural units derived from polymerizable monomers other than the (meth)acrylic compound. That is, the upper limit of the content of the structural unit derived from the (meth)acrylic compound is 100% by mass or less based on all the structural units of the (meth)acrylic resin.

[0304] Examples of the (meth)acrylic compound include (meth)acrylic acid, (meth)acrylic acid ester, (meth)acrylamide, and (meth)acrylonitrile. Examples of the (meth)acrylic acid ester include alkyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, benzyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, and alkyl (meth)acrylate is preferred. Examples of the (meth)acrylamide include acrylamides such as diacetoneacrylamide.

[0305] Examples of the alkyl (meth)acrylate include alkyl (meth)acrylates having an alkyl group with 1 to 12 carbon atoms such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, and dodecyl (meth)acrylate. As the (meth)acrylic acid ester, an alkyl (meth)acrylate having an alkyl group with 1 to 4 carbon atoms is preferred, and methyl (meth)acrylate or ethyl (meth)acrylate is more preferred.

[0306] The (meth)acrylic resin may have a structural unit other than the structural unit derived from the (meth)acrylic compound. The polymerizable monomer forming the above-mentioned structural unit is not particularly limited as long as it is a compound other than (meth)acrylic compounds copolymerizable with (meth)acrylic compounds. For example, styrene compounds which may have substituents at the α-position or aromatic ring such as styrene, vinyltoluene, and α-methylstyrene, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, and monoisopropyl maleate, maleic acid monoester, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, and crotonic acid. These polymerizable monomers may be used alone or in combination of two or more.

[0307] Further, from the viewpoint of making the alkali developability better, the (meth)acrylic resin preferably has a structural unit having an acid group. Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group. Among them, the (meth)acrylic resin more preferably has a structural unit having a carboxy group, and further preferably has a structural unit derived from the above-mentioned (meth)acrylic acid.

[0308] The content of the structural unit having an acid group (preferably the structural unit derived from (meth)acrylic acid) in the (meth)acrylic resin is preferably 10% by mass or more based on the total mass of the (meth)acrylic resin in terms of excellent developability. The upper limit is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less in terms of excellent alkali resistance.

[0309] Further, the (meth)acrylic resin more preferably has a structural unit derived from the above-mentioned (meth)acrylic acid alkyl ester. The content of the structural unit derived from the (meth)acrylic acid alkyl ester in the (meth)acrylic resin is preferably 50% by mass to 90% by mass, more preferably 60% by mass to 90% by mass, and still more preferably 65% by mass to 90% by mass based on all the structural units of the (meth)acrylic resin.

[0310] As the (meth)acrylic resin, a resin having both a structural unit derived from (meth)acrylic acid and a structural unit derived from an alkyl (meth)acrylate is preferable, and a resin composed only of a structural unit derived from (meth)acrylic acid and a structural unit derived from an alkyl (meth)acrylate is more preferable. In addition, as the (meth)acrylic resin, an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate is also preferable.

[0311] From the viewpoint of resolution, the (meth)acrylic resin preferably has at least one selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from an alkyl methacrylate, and preferably has both a structural unit derived from methacrylic acid and a structural unit derived from an alkyl methacrylate. From the viewpoint of resolution, the total content of the structural unit derived from methacrylic acid and the structural unit derived from an alkyl methacrylate in the (meth)acrylic resin is preferably 40% by mass or more, more preferably 60% by mass or more, based on all the structural units of the (meth)acrylic resin. The upper limit is not particularly limited and may be 100% by mass or less, preferably 80% by mass or less.

[0312] From the viewpoint of resolution, the (meth)acrylic resin preferably has at least one selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from an alkyl methacrylate, and at least one selected from the group consisting of a structural unit derived from acrylic acid and a structural unit derived from an alkyl acrylate. From the viewpoint of resolution, the mass ratio of the total content of the structural unit derived from methacrylic acid and the structural unit derived from an alkyl methacrylate to the total content of the structural unit derived from acrylic acid and the structural unit derived from an alkyl acrylate is preferably 60 / 40 to 80 / 20.

[0313] (Meta)acrylic resins preferably have an ester group at the terminal in terms of excellent developability of the photosensitive resin layer after transfer. Note that the terminal portion of the (meta)acrylic resin is composed of a site derived from the polymerization initiator used in the synthesis. The (meta)acrylic resin having an ester group at the terminal can be synthesized by using a polymerization initiator that generates a radical having an ester group.

[0314] In addition, the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more, for example, from the viewpoint of developability. Further, the alkali-soluble resin is more preferably a resin having a carboxy group with an acid value of 60 mgKOH / g or more (so-called carboxy group-containing resin), for example, from the viewpoint of easily forming a strong film by thermally crosslinking with a crosslinking component by heating. It is even more preferably a (meta)acrylic resin having a carboxy group with an acid value of 60 mgKOH / g or more (so-called carboxy group-containing (meta)acrylic resin). When the alkali-soluble resin is a resin having a carboxy group, for example, the three-dimensional crosslink density can be increased by adding a thermally crosslinkable compound such as a blocked isocyanate compound and performing thermal crosslinking. Further, when the carboxy group of the resin having a carboxy group is anhydrified and hydrophobized, the wet heat resistance can be improved.

[0315] The carboxy group-containing (meta)acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited as long as it satisfies the above acid value conditions, and can be appropriately selected from known (meta)acrylic resins. For example, among the polymers described in paragraph 0025 of JP-A-2011-095716, a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more, and among the polymers described in paragraphs 0033 to 0052 of JP-A-2010-237589, a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more can be preferably used.

[0316] As another preferred embodiment of the alkali-soluble resin, a styrene-acrylic copolymer can be mentioned. In the present specification, the styrene-acrylic copolymer refers to a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth)acrylic compound. The total content of the structural unit derived from the styrene compound and the structural unit derived from the (meth)acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, based on all the structural units of the copolymer. In addition, the content of the structural unit derived from the styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 5% by mass to 80% by mass, based on all the structural units of the copolymer. In addition, the content of the structural unit derived from the (meth)acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass to 95% by mass, based on all the structural units of the copolymer.

[0317] From the viewpoints of the moisture permeability and strength of the resulting cured film, the alkali-soluble resin preferably has an aromatic ring structure, and more preferably has a structural unit having an aromatic ring structure. Examples of the monomer that forms the structural unit having an aromatic ring structure include styrene compounds such as styrene, tert-butoxystyrene, methylstyrene, and α-methylstyrene, and benzyl (meth)acrylate. Among them, styrene compounds are preferred, and styrene is more preferred. In addition, from the viewpoints of the moisture permeability and strength of the resulting cured film, the alkali-soluble resin more preferably has a structural unit represented by the following formula (S) (a structural unit derived from styrene).

[0318]

Chemical formula

[0319] When the alkali-soluble resin has a structural unit having an aromatic ring structure, the content of the structural unit having an aromatic ring structure is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 70% by mass, and still more preferably 20% by mass to 60% by mass, based on all the structural units of the alkali-soluble resin, from the viewpoints of the moisture permeability and strength of the resulting cured film. Further, the content of the structural unit having an aromatic ring structure in the alkali-soluble resin is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, and still more preferably 20 mol% to 60 mol%, based on all the structural units of the alkali-soluble resin, from the viewpoints of the moisture permeability and strength of the resulting cured film. Furthermore, the content of the structural unit represented by the above formula (S) in the alkali-soluble resin is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, still more preferably 20 mol% to 60 mol%, and particularly preferably 20 mol% to 50 mol%, based on all the structural units of the alkali-soluble resin, from the viewpoints of the moisture permeability and strength of the resulting cured film. In the present specification, when the content of the "structural unit" is defined as a molar ratio, the above "structural unit" shall be synonymous with the "monomer unit". Further, in the present specification, the above "monomer unit" may be modified after polymerization by a polymer reaction or the like. The same applies hereinafter.

[0320] The alkali-soluble resin preferably has an aliphatic hydrocarbon ring structure from the viewpoints of suppressing development residues, the strength of the resulting cured film, and the adhesiveness of the resulting uncured film. That is, the alkali-soluble resin preferably has a structural unit having an aliphatic hydrocarbon ring structure. Among them, the alkali-soluble resin more preferably has a ring structure in which two or more aliphatic hydrocarbon rings are fused.

[0321] Examples of the ring constituting the aliphatic hydrocarbon ring structure in the structural unit having an aliphatic hydrocarbon ring structure include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, and an isophorone ring. Among them, from the viewpoints of suppressing development residues, the strength of the resulting cured film, and the adhesiveness of the resulting uncured film, a ring formed by condensing an aliphatic hydrocarbon ring having two or more rings is preferable, and a tetrahydrodicyclopentadiene ring (tricyclo[5.2.1.0 2,6 decane ring) is more preferable. Examples of the monomer that forms a structural unit having an aliphatic hydrocarbon ring structure include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate. Further, from the viewpoints of suppressing development residues, the strength of the resulting cured film, and the adhesiveness of the resulting uncured film, the alkali-soluble resin preferably has a structural unit represented by the following formula (Cy), and more preferably has a structural unit represented by the above formula (S) and a structural unit represented by the following formula (Cy).

[0322]

Chemical formula

[0323] In formula (Cy), R M represents a hydrogen atom or a methyl group, and R Cy represents a monovalent group having an aliphatic hydrocarbon ring structure.

[0324] R M in formula (Cy) is preferably a methyl group. R Cy in formula (Cy) is preferably a monovalent group having an aliphatic hydrocarbon ring structure with 5 to 20 carbon atoms, more preferably a monovalent group having an aliphatic hydrocarbon ring structure with 6 to 16 carbon atoms, and even more preferably a monovalent group having an aliphatic hydrocarbon ring structure with 8 to 14 carbon atoms, from the viewpoints of suppressing development residues, the strength of the resulting cured film, and the adhesiveness of the resulting uncured film. The aliphatic hydrocarbon ring structure in R Cy of formula (Cy) may be a monocyclic structure or a polycyclic structure. Further, R CyThe aliphatic hydrocarbon ring structure in [the compound] is preferably a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure, or an isobornyl ring structure from the viewpoints of development residue suppression property, strength of the resulting cured film, and adhesiveness of the resulting uncured film. More preferably, it is a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, and even more preferably, it is a tetrahydrodicyclopentadiene ring structure. Furthermore, R in formula (Cy) Cy The aliphatic hydrocarbon ring structure in [the compound] is preferably a ring structure in which two or more aliphatic hydrocarbon rings are fused from the viewpoints of development residue suppression property, strength of the resulting cured film, and adhesiveness of the resulting uncured film. More preferably, it is a ring in which 2 to 4 aliphatic hydrocarbon rings are fused. Furthermore, R in formula (Cy) Cy is preferably a group in which the oxygen atom of -C(=O)O- in formula (Cy) is directly bonded to the aliphatic hydrocarbon ring structure, that is, an aliphatic hydrocarbon ring group, more preferably a cyclohexyl group or a dicyclopentanyl group, and even more preferably a dicyclopentanyl group from the viewpoints of development residue suppression property, strength of the resulting cured film, and adhesiveness of the resulting uncured film.

[0325] The alkali-soluble resin may have one kind or two or more kinds of structural units having an aliphatic hydrocarbon ring structure. When the alkali-soluble resin has a structural unit having an aliphatic hydrocarbon ring structure, the content of the structural unit having an aliphatic hydrocarbon ring structure is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 80% by mass, and even more preferably 20% by mass to 70% by mass based on all the structural units of the alkali-soluble resin from the viewpoints of development residue suppression property, strength of the resulting cured film, and adhesiveness of the resulting uncured film. In addition, from the viewpoints of development residue suppressibility, the strength of the resulting cured film, and the adhesiveness of the resulting uncured film, the content of the structural unit having an aliphatic hydrocarbon ring structure in the alkali-soluble resin is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, and still more preferably 20 mol% to 50 mol% with respect to all the structural units of the alkali-soluble resin. Furthermore, from the viewpoints of development residue suppressibility, the strength of the resulting cured film, and the adhesiveness of the resulting uncured film, the content of the structural unit represented by the above formula (Cy) in the alkali-soluble resin is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, and still more preferably 20 mol% to 50 mol% with respect to all the structural units of the alkali-soluble resin.

[0326] When the alkali-soluble resin has a structural unit having an aromatic ring structure and a structural unit having an aliphatic hydrocarbon ring structure, from the viewpoints of development residue suppressibility, the strength of the resulting cured film, and the adhesiveness of the resulting uncured film, the total content of the structural unit having an aromatic ring structure and the structural unit having an aliphatic hydrocarbon ring structure is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and still more preferably 40% by mass to 75% by mass with respect to all the structural units of the alkali-soluble resin. In addition, from the viewpoints of development residue suppressibility, the strength of the resulting cured film, and the adhesiveness of the resulting uncured film, the total content of the structural unit having an aromatic ring structure and the structural unit having an aliphatic hydrocarbon ring structure in the alkali-soluble resin is preferably 10 mol% to 80 mol%, more preferably 20 mol% to 70 mol%, and still more preferably 40 mol% to 60 mol% with respect to all the structural units of the alkali-soluble resin. Furthermore, from the viewpoints of the present development residue suppressibility, the strength of the resulting cured film, and the adhesiveness of the resulting uncured film, the total content of the structural unit represented by the above formula (S) and the structural unit represented by the above formula (Cy) in the alkali-soluble resin is preferably 10 mol% to 80 mol%, more preferably 20 mol% to 70 mol%, and still more preferably 40 mol% to 60 mol% with respect to all the structural units of the alkali-soluble resin. Further, from the viewpoints of development residue suppression, the strength of the resulting cured film, and the adhesiveness of the resulting uncured film, the molar amount nS of the structural unit represented by the above formula (S) and the molar amount nCy of the structural unit represented by the above formula (Cy) in the alkali-soluble resin preferably satisfy the relationship shown in the following formula (SCy), more preferably satisfy the following formula (SCy-1), and even more preferably satisfy the following formula (SCy-2). 0.2 ≦ nS / (nS + nCy) ≦ 0.8: Formula (SCy) 0.30 ≦ nS / (nS + nCy) ≦ 0.75: Formula (SCy-1) 0.40 ≦ nS / (nS + nCy) ≦ 0.70: Formula (SCy-2)

[0327] The alkali-soluble resin preferably has a structural unit having an acid group from the viewpoints of developability and adhesion to the substrate. Examples of the acid group include a carboxy group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, and a carboxy group is preferred. As the structural unit having the acid group, the structural unit derived from (meth)acrylic acid shown below is preferred, and the structural unit derived from methacrylic acid is more preferred.

[0328]

Chemical formula

[0329] The alkali-soluble resin may have one kind of the structural unit having an acid group alone or two or more kinds thereof. When the alkali-soluble resin has a structural unit having an acid group, the content of the structural unit having an acid group is preferably 5% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and even more preferably 10% by mass to 30% by mass, based on all the structural units of the alkali-soluble resin, from the viewpoints of developability and adhesion to the substrate. In addition, from the viewpoints of developability and adhesion to a substrate, the content of the structural unit having an acid group in the alkali-soluble resin is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 50 mol%, and still more preferably 20 mol% to 40 mol% with respect to all the structural units of the alkali-soluble resin. Furthermore, from the viewpoints of developability and adhesion to a substrate, the content of the structural unit derived from (meth)acrylic acid in the alkali-soluble resin is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 50 mol%, and still more preferably 20 mol% to 40 mol% with respect to all the structural units of the alkali-soluble resin.

[0330] From the viewpoints of curability and the strength of the resulting cured film, the alkali-soluble resin preferably has a reactive group, and more preferably has a structural unit having a reactive group. As the reactive group, a radically polymerizable group is preferable, and an ethylenically unsaturated group is more preferable. When the alkali-soluble resin has an ethylenically unsaturated group, the alkali-soluble resin preferably has a structural unit having an ethylenically unsaturated group in a side chain. In the present specification, the "main chain" represents the relatively longest bond chain in the molecule of the polymer compound constituting the resin, and the "side chain" represents an atomic group branched from the main chain. As the ethylenically unsaturated group, an allyl group or a (meth)acryloxy group is more preferable. Examples of the structural unit having a reactive group include, but are not limited to, those shown below.

[0331]

Chemical formula

[0332] The alkali-soluble resin may have one kind of the structural unit having a reactive group alone or two or more kinds thereof. When the alkali-soluble resin has a structural unit having a reactive group, the content of the structural unit having a reactive group is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 50% by mass, and still more preferably 20% by mass to 40% by mass with respect to all the structural units of the alkali-soluble resin from the viewpoints of curability and the strength of the obtained cured film. Also, the content of the structural unit having a reactive group in the alkali-soluble resin is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, and still more preferably 20 mol% to 50 mol% with respect to all the structural units of the alkali-soluble resin from the viewpoints of curability and the strength of the obtained cured film.

[0333] Examples of the means for introducing a reactive group into the alkali-soluble resin include methods of reacting functional groups such as a hydroxy group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, and a sulfo group with compounds such as an epoxy compound, a blocked isocyanate compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, and a carboxylic anhydride. A preferred example of the means for introducing a reactive group into the alkali-soluble resin is a means of synthesizing a polymer having a carboxy group by a polymerization reaction and then reacting glycidyl (meth) acrylate with a part of the carboxy groups of the obtained resin by a polymer reaction to introduce a (meth) acryloxy group into the polymer. By this means, an alkali-soluble resin having a (meth) acryloxy group in the side chain can be obtained. The above polymerization reaction is preferably carried out under temperature conditions of 70°C to 100°C, and more preferably under temperature conditions of 80°C to 90°C. As the polymerization initiator used in the above polymerization reaction, an azo-based initiator is preferred, and for example, V-601 (trade name) or V-65 (trade name) manufactured by Fujifilm Wako Pure Chemical Corporation is more preferred. The above polymer reaction is preferably carried out under temperature conditions of 80°C to 110°C. In the above polymer reaction, it is preferable to use a catalyst such as an ammonium salt.

[0334] As the alkali-soluble resin, the resins shown below are preferable from the viewpoint of more excellent effects in the present disclosure. The content ratios (a to d) of each constitutional unit shown below, the weight average molecular weight Mw, etc. can be appropriately changed according to the purpose.

[0335]

Chemical formula

[0336] In the above resin, it is preferable that a is 20% by mass to 60% by mass, b is 10% by mass to 50% by mass, c is 5.0% by mass to 25% by mass, and d is 10% by mass to 50% by mass.

[0337]

Chemical formula

[0338] In the above resin, it is preferable that a is 20% by mass to 60% by mass, b is 10% by mass to 50% by mass, c is 5.0% by mass to 25% by mass, and d is 10% by mass to 50% by mass.

[0339]

Chemical formula

[0340] In the above resin, it is preferable that a is 30% by mass to 65% by mass, b is 1.0% by mass to 20% by mass, c is 5.0% by mass to 25% by mass, and d is 10% by mass to 50% by mass.

[0341]

Chemical formula

[0342] In the above resin, it is preferable that a is 1.0% by mass to 20% by mass, b is 20% by mass to 60% by mass, c is 5.0% by mass to 25% by mass, and d is 10% by mass to 50% by mass.

[0343] Further, the alkali-soluble resin may contain a polymer having a structural unit having a carboxylic acid anhydride structure (hereinafter, also referred to as "polymer X"). The carboxylic acid anhydride structure may be either a chain carboxylic acid anhydride structure or a cyclic carboxylic acid anhydride structure, but is preferably a cyclic carboxylic acid anhydride structure. As the ring of the cyclic carboxylic acid anhydride structure, a 5- to 7-membered ring is preferable, a 5- or 6-membered ring is more preferable, and a 5-membered ring is even more preferable.

[0344] The structural unit having a carboxylic acid anhydride structure is preferably a structural unit containing a divalent group obtained by removing two hydrogen atoms from the compound represented by the following formula P-1 in the main chain, or a structural unit in which a monovalent group obtained by removing one hydrogen atom from the compound represented by the following formula P-1 is bonded to the main chain directly or via a divalent linking group.

[0345]

Chemical formula

[0346] In formula P-1, R A1a represents a substituent, and n 1a number of R A1a may be the same or different, and Z 1a represents a divalent group that forms a ring containing -C(=O)-O-C(=O)-, and n 1a represents an integer of 0 or more.

[0347] R A1a Examples of the substituent represented by 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 of 0 or more. 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. n 1a When n represents an integer of 2 or more, a plurality of R's A1a may be the same or different. Also, a plurality of R's A1a may combine with each other to form a ring, but it is preferably that they do not combine with each other to form a ring.

[0348] As the structural unit having a carboxylic anhydride structure, a structural unit derived from an unsaturated carboxylic anhydride is preferable, a structural unit derived from an unsaturated cyclic carboxylic anhydride is more preferable, a structural unit derived from an unsaturated aliphatic cyclic carboxylic anhydride is still more preferable, a structural unit derived from maleic anhydride or itaconic anhydride is particularly preferable, and a structural unit derived from maleic anhydride is most preferable.

[0349] Hereinafter, specific examples of the structural unit having a carboxylic anhydride structure will be given, but the structural unit having a carboxylic anhydride structure is not limited to these specific examples. In the following structural units, Rx represents a hydrogen atom, a methyl group, a CH2OH group, or a CF3 group, and Me represents a methyl group.

[0350]

Chemical formula

[0351]

Chemical formula

[0352] The structural unit having a carboxylic anhydride structure in the polymer X may be a single type or two or more types.

[0353] The total content of the structural unit having a carboxylic anhydride structure is preferably 0 mol% to 60 mol%, more preferably 5 mol% to 40 mol%, still more preferably 10 mol% to 35 mol% with respect to all the structural units of the polymer X.

[0354] The photosensitive resin layer may contain only one type of the polymer X or may contain two or more types. When the photosensitive resin layer contains polymer X, from the viewpoints of resolution and developability, the content of polymer X is preferably 0.1% by mass to 30% by mass, more preferably 0.2% by mass to 20% by mass, still more preferably 0.5% by mass to 20% by mass, and still more preferably 1% by mass to 20% by mass, based on the total mass of the photosensitive resin layer.

[0355] From the viewpoints of improving resolution and developability, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 10,000 to 50,000, and particularly preferably 20,000 to 30,000.

[0356] The acid value of the alkali-soluble resin is preferably 10 mgKOH / g to 200 mgKOH / g, more preferably 60 mgKOH / g to 200 mgKOH / g, still more preferably 60 mgKOH / g to 150 mgKOH / g, and particularly preferably 60 mgKOH / g to 110 mgKOH / g. Note that the acid value of the alkali-soluble resin is a value measured according to the method described in JIS K0070:1992. From the viewpoint of developability, the dispersity (weight average molecular weight / number average molecular weight) of the alkali-soluble resin is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

[0357] The photosensitive resin layer may contain only one kind of alkali-soluble resin or may contain two or more kinds of alkali-soluble resins. From the viewpoints of photosensitivity, resolution, and developability, the content of the alkali-soluble resin is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and still more preferably 30% by mass to 70% by mass, based on the total mass of the photosensitive resin layer.

[0358] -Polymerizable compound- The photosensitive resin layer may contain a polymerizable compound. The polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include a radical polymerizable group and a cationic polymerizable group, and the radical polymerizable group is preferred.

[0359] The polymerizable compound preferably contains a polymerizable compound having an ethylenically unsaturated group (hereinafter, also simply referred to as "ethylenically unsaturated compound"). As the ethylenically unsaturated group, a (meth)acryloxy group is preferred. Note that the ethylenically unsaturated compound in this specification is a compound other than the above binder polymer, and preferably has a molecular weight of less than 5,000. A preferred embodiment of the ethylenically unsaturated compound is the same as the preferred embodiment of the ethylenically unsaturated compound described in the section of the "photosensitive resin layer" above.

[0360] As one of the preferred embodiments of the ethylenically unsaturated compound, a compound represented by the following formula (M) (simply also referred to as "compound M") can be mentioned. Q 2 -R 1 -Q 1 : Formula (M) In formula (M), Q 1 and Q 2 each independently represent a (meth)acryloyloxy group, and R 1 represents a divalent linking group having a chain structure.

[0361] Q 1 and Q 2 in formula (M) are preferably the same group from the viewpoint of ease of synthesis. 1 and Q 2 in formula (M) are preferably the same group. Also, Q 1 and Q 2 in formula (M) are preferably acryloyloxy groups from the viewpoint of reactivity. As R 1 in formula (M), from the viewpoints of development residue suppression property, rust prevention property, and bending resistance of the obtained cured film, an alkylene group, an alkyleneoxyalkylene group (-L 1 -O-L 1-), or a polyalkyleneoxyalkylene group (-(L 1 -O) p -L 1 -) is preferred, a hydrocarbon group having 2 to 20 carbon atoms, or a polyalkyleneoxyalkylene group is more preferred, an alkylene group having 4 to 20 carbon atoms is still more preferred, and a linear alkylene group having 6 to 18 carbon atoms is particularly preferred. The hydrocarbon group may have a chain structure in at least a part thereof, and there is no particular limitation on the part other than the chain structure. For example, it may be a branched chain, cyclic, or a linear alkylene group having 1 to 5 carbon atoms, an arylene group, an ether bond, or any combination thereof. A group formed by combining an alkylene group or two or more alkylene groups and one or more arylene groups is preferred, an alkylene group is more preferred, and a linear alkylene group is still more preferred. In addition, each of the above L 1 independently represents an alkylene group, and an ethylene group, a propylene group, or a butylene group is preferred, and an ethylene group or a 1,2-propylene group is more preferred. p represents an integer of 2 or more, and is preferably an integer of 2 to 10.

[0362] In addition, the number of atoms of the shortest linking chain connecting between Q 1 and Q 2 in the compound M is preferably 3 to 50, more preferably 4 to 40, still more preferably 6 to 20, and particularly preferably 8 to 12 from the viewpoints of development residue suppressibility, rust prevention property, and bending resistance of the obtained cured film. In this specification, the "number of atoms of the shortest linking chain connecting between Q 1 and Q 2 " means the shortest number of atoms connecting from the atom in R 1 connected to Q 1 to the atom in R 2 connected to Q 1

[0363] ​Specific examples of Compound M include 1,3 - butanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6 - hexanediol di(meth)acrylate, 1,7 - heptanediol di(meth)acrylate, 1,8 - octanediol di(meth)acrylate, 1,9 - nonanediol di(meth)acrylate, 1,10 - decanediol di(meth)acrylate, di(meth)acrylate of hydrogenated bisphenol A, di(meth)acrylate of hydrogenated bisphenol F, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene glycol / propylene glycol) di(meth)acrylate, and polybutylene glycol di(meth)acrylate. The above ester monomers can also be used as a mixture. Among the above compounds, from the viewpoints of development residue suppression property, rust prevention property, and bending resistance of the obtained cured film, it is preferably at least one compound selected from the group consisting of 1,6 - hexanediol di(meth)acrylate, 1,9 - nonanediol di(meth)acrylate, 1,10 - decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate; more preferably at least one compound selected from the group consisting of 1,6 - hexanediol di(meth)acrylate, 1,9 - nonanediol di(meth)acrylate, and 1,10 - decanediol di(meth)acrylate; and even more preferably at least one compound selected from the group consisting of 1,9 - nonanediol di(meth)acrylate and 1,10 - decanediol di(meth)acrylate.

[0364] Also, as one of the preferred embodiments of the ethylenically unsaturated compound, a polyfunctional ethylenically unsaturated compound is exemplified. In this specification, the "polyfunctional ethylenically unsaturated compound" means a compound having two or more ethylenically unsaturated groups in one molecule. As the ethylenically unsaturated group in the ethylenically unsaturated compound, a (meth)acryloyl group is preferred. As the ethylenically unsaturated compound, a (meth)acrylate compound is preferred.

[0365] There is no particular limitation on the bifunctional ethylenically unsaturated compound, and it can be appropriately selected from known compounds. Examples of the bifunctional ethylenically unsaturated compound other than the above compound M include tricyclodecane dimethanol di(meth)acrylate and 1,4-cyclohexanediol di(meth)acrylate.

[0366] Examples of commercially available bifunctional ethylenically unsaturated compounds include tricyclodecane dimethanol diacrylate (trade name: NK Ester A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (trade name: NK Ester DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (trade name: NK Ester A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), and 1,6-hexanediol diacrylate (trade name: NK Ester A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0367] There is no particular limitation on the ethylenically unsaturated compound having three or more functional groups, and it can be appropriately selected from known compounds. Examples of the ethylenically unsaturated compound having three or more functional groups include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerin tri(meth)acrylate skeleton.

[0368] Examples of ethylenically unsaturated compounds include caprolactone-modified compounds of (meth)acrylate compounds (such as 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 (such as KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 of Daicel Ornex Co., etc.), and ethoxylated glycerol triacrylate (such as NK Ester A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0369] Examples of ethylenically unsaturated compounds also include urethane (meth)acrylate compounds. Examples of urethane (meth)acrylate include urethane di(meth)acrylate, such as propylene oxide-modified urethane di(meth)acrylate, and ethylene oxide and propylene oxide-modified urethane di(meth)acrylate. In addition, examples of urethane (meth)acrylate also include urethane (meth)acrylate having 3 or more functional groups. The lower limit of the number of functional groups is more preferably 6 or more, and even more preferably 8 or more. The upper limit of the number of functional groups is preferably 20 or less. Examples of urethane (meth)acrylate having 3 or more functional groups include 8UX-015A (manufactured by Dainippon Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), AH-600 (trade name) manufactured by Kyoeisha Chemical Co., Ltd., and UA-306H, UA-306T, UA-306I, UA-510H, and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).

[0370] One preferred embodiment of the ethylenically unsaturated compound is an ethylenically unsaturated compound having an acid group. Examples of the acid group include a phosphate group, a sulfo group, and a carboxy group. Among these, as the acid group, a carboxy group is preferred. Examples of the ethylenically unsaturated compound having an acid group include trifunctional to tetrafunctional ethylenically unsaturated compounds having an acid group (compounds in which a carboxy group is introduced into a pentaerythritol tri- and tetraacrylate (PETA) skeleton (acid value: 80 mgKOH / g to 120 mgKOH / g)), pentafunctional to hexafunctional ethylenically unsaturated compounds having an acid group (compounds in which a carboxy group is introduced into a dipentaerythritol penta- and hexaacrylate (DPHA) skeleton (acid value: 25 mgKOH / g to 70 mgKOH / g)), and the like. These ethylenically unsaturated compounds having 3 or more functional groups with an acid group may be used in combination with a bifunctional ethylenically unsaturated compound having an acid group, if necessary.

[0371] As the ethylenically unsaturated compound having an acid group, at least one selected from the group consisting of bifunctional or higher functional ethylenically unsaturated compounds having a carboxy group and carboxylic acid anhydrides thereof is preferable. When the ethylenically unsaturated compound having an acid group is at least one selected from the group consisting of bifunctional or higher functional ethylenically unsaturated compounds having a carboxy group and carboxylic acid anhydrides thereof, the developability and film strength are further enhanced. The bifunctional or higher functional ethylenically unsaturated compound having a carboxy group is not particularly limited and can be appropriately selected from known compounds. Examples of the bifunctional or higher functional ethylenically unsaturated compound having a carboxy 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.).

[0372] As the ethylenically unsaturated compound having an acid group, the polymerizable compound having an acid group described in paragraphs 0025 to 0030 of JP-A No. 2004-239942 is preferable, and the content described in this publication is incorporated herein.

[0373] Examples of the ethylenically unsaturated compound include compounds obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid, compounds obtained by reacting a glycidyl group-containing compound with an α,β-unsaturated carboxylic acid, urethane monomers such as (meth)acrylate compounds having a urethane bond, phthalic acid-based compounds such as γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-o-phthalate, and β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, and alkyl (meth)acrylates. These may be used alone or in combination of two or more.

[0374] Examples of the compound obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid include bisphenol A-based (meth)acrylate compounds such as 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane; polyethylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups; polypropylene glycol di(meth)acrylate having 2 to 14 propylene oxide groups; polyethylene polypropylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups and 2 to 14 propylene oxide groups; trimethylolpropane di(meth)acrylate; trimethylolpropane tri(meth)acrylate; trimethylolpropane ethoxytri(meth)acrylate; trimethylolpropane diethoxytri(meth)acrylate; trimethylolpropane triethoxytri(meth)acrylate; trimethylolpropane tetraethoxytri(meth)acrylate; trimethylolpropane pentaethoxytri(meth)acrylate; di(trimethylolpropane) tetraacrylate; pentaerythritol tri(meth)acrylate; pentaerythritol tetra(meth)acrylate; dipentaerythritol tetra(meth)acrylate; dipentaerythritol penta(meth)acrylate; and dipentaerythritol hexa(meth)acrylate. Among them, an ethylenically unsaturated compound having a pentaerythritol structure or a trimethylolpropane structure is preferable, and pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane) tetraacrylate is more preferable.

[0375] Examples of the ethylenically unsaturated compound include caprolactone-modified compounds of ethylenically unsaturated compounds (e.g., 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 ethylenically unsaturated compounds (e.g., KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Ornex Co., Ltd., etc.), ethoxylated glycerol triacrylate (e.g., A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like.

[0376] From the viewpoint of excellent developability, the ethylenically unsaturated compound preferably contains an ester bond. The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule, but from the viewpoints of excellent curability and developability, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane) tetraacrylate is more preferable. From the viewpoint of imparting reliability, the ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having an aliphatic group with 6 to 20 carbon atoms and an ethylenically unsaturated compound having the above tetramethylolmethane structure or trimethylolpropane structure. Examples of the ethylenically unsaturated compound having an aliphatic structure with 6 or more carbon atoms include 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate. [[ID=X]]

[0377] [[ID=X]] One preferred embodiment of the ethylenically unsaturated compound is an ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure (preferably a bifunctional ethylenically unsaturated compound). As the ethylenically unsaturated compound, an ethylenically unsaturated compound having a ring structure in which two or more aliphatic hydrocarbon rings are fused (preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure) is preferable, a bifunctional ethylenically unsaturated compound having a ring structure in which two or more aliphatic hydrocarbon rings are fused is more preferable, and tricyclodecane dimethanol di(meth)acrylate is even more preferable. As the aliphatic hydrocarbon ring structure, from the viewpoints of the moisture permeability and bending resistance of the obtained cured film and the adhesiveness of the obtained uncured film, a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure, or an isobornyl structure is preferable.

[0378] The molecular weight of the ethylenically unsaturated compound is preferably from 200 to 3,000, more preferably from 250 to 2,600, even more preferably from 280 to 2,200, and particularly preferably from 300 to 2,200. Among the ethylenically unsaturated compounds contained in the photosensitive resin layer, the proportion of the content of the ethylenically unsaturated compound having a molecular weight of 300 or less is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less with respect to the content of all the ethylenically unsaturated compounds contained in the photosensitive resin layer.

[0379] As one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer preferably contains an ethylenically unsaturated compound having two or more functional groups, more preferably contains an ethylenically unsaturated compound having three or more functional groups, and even more preferably contains an ethylenically unsaturated compound having three or four functional groups.

[0380] Also, as one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer preferably contains a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and an alkali-soluble resin having a structural unit having an aliphatic hydrocarbon ring.

[0381] Further, as one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer preferably contains a compound represented by formula (M) and an ethylenically unsaturated compound having an acid group, more preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, and still more preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a succinic acid-modified product of dipentaerythritol pentaacrylate.

[0382] Further, as one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer preferably contains a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a thermally crosslinkable compound described later, and more preferably contains a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a blocked isocyanate compound described later.

[0383] Further, as one of the preferred embodiments of the photosensitive resin layer, from the viewpoints of development residue suppression and rust prevention, the photosensitive resin layer preferably contains a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth)acrylate compound) and a polyfunctional ethylenically unsaturated compound having three or more functional groups (preferably a polyfunctional (meth)acrylate compound having three or more functional groups). The mass ratio of the content of the bifunctional ethylenically unsaturated compound to the content of the polyfunctional ethylenically unsaturated compound having three or more functional groups is preferably 10:90 to 90:10, and more preferably 30:70 to 70:30. The content of the bifunctional ethylenically unsaturated compound relative to the total amount of all ethylenically unsaturated compounds is preferably 20% by mass to 80% by mass, and more preferably 30% by mass to 70% by mass. The content of the bifunctional ethylenically unsaturated compound in the photosensitive resin layer is preferably 10% by mass to 60% by mass, and more preferably 15% by mass to 40% by mass, based on the total mass of the photosensitive resin layer.

[0384] Also, as one of the preferred embodiments of the photosensitive resin layer, from the viewpoint of rust prevention, the photosensitive resin layer preferably contains Compound M and a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure. Also, as one of the preferred embodiments of the photosensitive resin layer, from the viewpoints of substrate adhesion, development residue suppression, and rust prevention, the photosensitive resin layer preferably contains Compound M and an ethylenically unsaturated compound having an acid group. More preferably, it contains Compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and an ethylenically unsaturated compound having an acid group. Even more preferably, it contains Compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, an ethylenically unsaturated compound having three or more functional groups, and an ethylenically unsaturated compound having an acid group. Particularly preferably, it contains Compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, an ethylenically unsaturated compound having three or more functional groups, an ethylenically unsaturated compound having an acid group, and a urethane (meth) acrylate compound. Also, as one of the preferred embodiments of the photosensitive resin layer, from the viewpoints of substrate adhesion, development residue suppression, and rust prevention, the photosensitive resin layer preferably contains 1,9-nonanediol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group. More preferably, it contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group. Even more preferably, it contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, dipentaerythritol hexaacrylate, and an ethylenically unsaturated compound having a carboxylic acid group. Particularly preferably, it contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, an ethylenically unsaturated compound having a carboxylic acid group, and a urethane acrylate compound.

[0385] The photosensitive resin layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound. The content of the ethylenically unsaturated compound having two or more functional groups in the above-mentioned ethylenically unsaturated compound is preferably 60% by mass to 100% by mass, more preferably 80% by mass to 100% by mass, and still more preferably 90% by mass to 100% by mass, based on the total content of all the ethylenically unsaturated compounds contained in the photosensitive resin layer.

[0386] The ethylenically unsaturated compound may be used alone or in combination of two or more. The content of the ethylenically unsaturated compound in the photosensitive resin layer is preferably 1% by mass to 70% by mass, more preferably 5% by mass to 70% by mass, still more preferably 5% by mass to 60% by mass, and particularly preferably 5% by mass to 50% by mass, based on the total mass of the photosensitive resin layer.

[0387] -Polymerization initiator- The photosensitive resin layer may contain a polymerization initiator. As the polymerization initiator, a photoinitiator is preferred. The preferred embodiment of the photoinitiator is the same as the preferred embodiment of the photoinitiator described in the section of the above-mentioned "photosensitive resin layer". The polymerization initiator may be used alone or in combination of two or more. The content of the polymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1.0% by mass or more, based on the total mass of the photosensitive resin layer. Also, as the upper limit value, it is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the photosensitive resin layer.

[0388] -Heterocyclic compound- The photosensitive resin layer may contain a heterocyclic compound. The heterocyclic ring possessed by the heterocyclic compound may be either a monocyclic or polycyclic heterocyclic ring. Examples of the heteroatom possessed by the heterocyclic compound include a nitrogen atom, an oxygen atom, and a sulfur atom. The heterocyclic compound preferably has at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably has a nitrogen atom.

[0389] Examples of the heterocyclic ring compound include, for example, triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, and pyrimidine compounds. Among these, as the heterocyclic ring compound, at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzimidazole compounds, and benzoxazole compounds is preferable, and at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, and benzoxazole compounds is more preferable.

[0390] Preferable specific examples of the heterocyclic ring compound are shown below. As the triazole compound and the benzotriazole compound, the following compounds can be exemplified.

[0391]

Chemical formula

[0392]

Chemical formula

[0393] As the tetrazole compound, the following compounds can be exemplified.

[0394]

Chemical formula

[0395]

Chemical formula

[0396] Examples of the thiadiazole compound include the following compounds.

[0397] [Chemical formula]

[0398] Examples of the triazine compound include the following compounds.

[0399] [Chemical formula]

[0400] Examples of the rhodanine compound include the following compounds.

[0401] [Chemical formula]

[0402] Examples of the thiazole compound include the following compounds.

[0403] [Chemical formula]

[0404] Examples of the benzothiazole compound include the following compounds.

[0405] [Chemical formula]

[0406] Examples of the benzimidazole compound include the following compounds.

[0407] [Chemical formula]

[0408] [Chemistry]

[0409] Examples of the benzoxazole compound include the following compounds.

[0410] [Chemistry]

[0411] The heterocyclic compound may be used alone or in combination of two or more. When the photosensitive resin layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01% by mass to 20.0% by mass, more preferably 0.10% by mass to 10.0% by mass, still more preferably 0.30% by mass to 8.0% by mass, and particularly preferably 0.50% by mass to 5.0% by mass with respect to the total mass of the photosensitive resin layer.

[0412] -Aliphatic thiol compound- The photosensitive resin layer may contain an aliphatic thiol compound. When the photosensitive resin layer contains an aliphatic thiol compound, the en-thiol reaction between the aliphatic thiol compound and the ethylenically unsaturated compound suppresses the curing shrinkage of the formed film and relaxes the stress.

[0413] As the aliphatic thiol compound, a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, an aliphatic thiol compound having two or more functional groups) is preferable. Among the above, as the aliphatic thiol compound, a polyfunctional aliphatic thiol compound is more preferable from the viewpoint of the adhesion of the formed pattern (particularly, the adhesion after exposure). In this specification, the "polyfunctional aliphatic thiol compound" means an aliphatic compound having two or more thiol groups (also referred to as "mercapto groups") in the molecule.

[0414] As the polyfunctional aliphatic thiol compound, a low molecular weight compound having a molecular weight of 100 or more is preferable. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and still more preferably 150 to 1,000.

[0415] As the number of functional groups of the polyfunctional aliphatic thiol compound, for example, from the viewpoint of the adhesion of the formed pattern, 2 to 10 functional groups are preferable, 2 to 8 functional groups are more preferable, and 2 to 6 functional groups are still more preferable.

[0416] Examples of the polyfunctional aliphatic thiol compound include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolethane tris(3-mercaptobutyrate), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), ethylene glycol bisthiopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2'-(ethylenedithio)diethanethiol, meso-2,3-dimercaptosuccinic acid, and di(mercaptoethyl)ether.

[0417] Among the above, as the polyfunctional aliphatic thiol compound, at least one compound selected from the group consisting of trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione is preferable.

[0418] Examples of the monofunctional aliphatic thiol compound include 1-octanethiol, 1-dodecanethiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.

[0419] The photosensitive resin layer may contain a single aliphatic thiol compound or two or more aliphatic thiol compounds. When the photosensitive resin layer contains an aliphatic thiol compound, the content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5% to 50% by mass, still more preferably 5% to 30% by mass, and particularly preferably 8% to 20% by mass based on the total mass of the photosensitive resin layer.

[0420] -Thermally crosslinkable compound- The photosensitive resin layer preferably contains a thermally crosslinkable compound from the viewpoints of the strength of the resulting cured film and the adhesiveness of the resulting uncured film. Examples of the thermally crosslinkable compound include the thermally crosslinkable compounds described in the section of "photosensitive resin layer" above. The thermally crosslinkable compound may be used alone or in combination of two or more. When the photosensitive resin layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1% to 50% by mass, more preferably 5% to 30% by mass based on the total mass of the photosensitive resin layer.

[0421] -Surfactant- The photosensitive resin layer may contain a surfactant. Examples of the surfactant include the surfactants described in the section of "photosensitive resin layer" above. The surfactant may be used alone or in combination of two or more. When the photosensitive resin layer contains a surfactant, the content of the surfactant is preferably 0.01% by mass to 3.0% by mass, more preferably 0.01% by mass to 1.0% by mass, and still more preferably 0.05% by mass to 0.80% by mass, based on the total mass of the photosensitive resin layer.

[0422] - Radical polymerization inhibitor - The photosensitive resin layer may contain a radical polymerization inhibitor. Examples of the radical polymerization inhibitor include those described in the section of "photosensitive resin layer" above. The radical polymerization inhibitor may be used alone or in combination of two or more. When the photosensitive resin layer contains a radical polymerization inhibitor, the content of the radical polymerization inhibitor is preferably 0.01% by mass to 3% by mass, more preferably 0.05% by mass to 1% by mass, based on the total mass of the photosensitive resin layer. When the content is 0.01% by mass or more, the storage stability of the photosensitive resin layer is more excellent. On the other hand, when the content is 3% by mass or less, the maintenance of sensitivity and the suppression of decolorization of the dye are more excellent.

[0423] - Hydrogen donating compound - The photosensitive resin layer may contain a hydrogen donating compound. The hydrogen donating compound has functions such as further improving the sensitivity of the photopolymerization initiator to actinic rays and suppressing the polymerization inhibition of the polymerizable compound by oxygen. Examples of the hydrogen donating compound include amines and amino acid compounds.

[0424] Examples of amines include compounds described in "Journal of Polymer Society", Vol. 10, p. 3173 (1972) by M.R. Sander et al., Japanese Patent Publication No. Sho 44-020189, Japanese Unexamined Patent Application Publication No. Sho 51-082102, Japanese Unexamined Patent Application Publication No. Sho 52-134692, Japanese Unexamined Patent Application Publication No. Sho 59-138205, Japanese Unexamined Patent Application Publication No. Sho 60-084305, Japanese Unexamined Patent Application Publication No. Sho 62-018537, Japanese Unexamined Patent Application Publication No. Sho 64-033104, and Research Disclosure No. 33825. More specifically, 4,4'-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (alias: leuco crystal violet), triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, and p-methylthiodimethylaniline can be mentioned. Among them, from the viewpoints of sensitivity, curing rate, and curability, as amines, at least one selected from the group consisting of 4,4'-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane is preferable.

[0425] Examples of amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Among them, from the viewpoints of sensitivity, curing rate, and curability, as the amino acid compound, N-phenylglycine is preferable.

[0426] Examples of hydrogen-donating compounds also include organometallic compounds (such as tributyltin acetate) described in Japanese Patent Publication No. Sho 48-042965, hydrogen donors described in Japanese Patent Publication No. Sho 55-034414, and sulfur compounds (such as trithiane) described in Japanese Unexamined Patent Application Publication No. Hei 6-308727.

[0427] The hydrogen-donating compounds may be used alone or in combination of two or more. When the photosensitive resin layer contains a hydrogen-donating compound, the content of the hydrogen-donating compound is preferably 0.01% by mass to 10.0% by mass, more preferably 0.01% by mass to 8.0% by mass, and still more preferably 0.03% by mass to 5.0% by mass based on the total mass of the photosensitive resin layer, from the viewpoint of improving the curing rate by the balance between the polymerization growth rate and chain transfer.

[0428] -Impurities- The photosensitive resin layer may contain a predetermined amount of impurities. Examples of the impurities include the impurities described in the section of "Photosensitive resin layer" above.

[0429] -Residual monomers- The photosensitive resin layer may contain residual monomers corresponding to each structural unit of the polymer A described above. Examples of the residual monomers corresponding to each structural unit of the polymer A in the photosensitive resin layer include the residual monomers corresponding to each structural unit of the polymer A described in the section of "Photosensitive resin layer" above.

[0430] -Other components- The photosensitive resin layer may contain components other than the components described above (hereinafter also referred to as "other components"). Examples of the other components include colorants, antioxidants, and particles (for example, metal oxide particles). In addition, examples of the other components also include other additives described in paragraphs 0058 to 0071 of JP-A-2000-310706.

[0431] As the particles, metal oxide particles are preferred. The metal in the metal oxide particles also includes metalloids such as B, Si, Ge, As, Sb, and Te. The average primary particle diameter of the particles is preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm, from the viewpoint of the transparency of the cured film, for example. The average primary particle diameter of the particles is calculated by measuring the particle diameters of 200 arbitrary particles using an electron microscope and calculating the arithmetic mean of the measurement results. When the shape of the particles is not spherical, the longest side is taken as the particle diameter.

[0432] When the photosensitive resin layer contains particles, it may contain only one kind of particles different in metal species, size, etc., or may contain two or more kinds of particles. The photosensitive resin layer may not contain particles, or when the photosensitive resin layer contains particles, the content of the particles is preferably more than 0% by mass and 35% by mass or less, more preferably more than 0% by mass and 10% by mass or less, still more preferably more than 0% by mass and 5% by mass or less, still more preferably more than 0% by mass and 1% by mass or less, and particularly preferably does not contain particles, based on the total mass of the photosensitive resin layer.

[0433] The photosensitive resin layer may contain a colorant (such as a pigment or a dye), but for example, from the viewpoint of transparency, it is preferably substantially free of a colorant. When the photosensitive resin layer contains a colorant, the content of the colorant is preferably less than 1% by mass, more preferably less than 0.1% by mass, based on the total mass of the photosensitive resin layer.

[0434] Examples of the antioxidant include 3-pyrazolidones such as 1-phenyl-3-pyrazolidone (alias: phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorohydroquinone; paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, and paraphenylenediamine. Among them, from the viewpoints of storage stability and curability, 3-pyrazolidones are preferred as the antioxidant, and 1-phenyl-3-pyrazolidone is more preferred.

[0435] When the photosensitive resin layer contains an antioxidant, the content of the antioxidant is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and still more preferably 0.01% by mass or more, based on the total mass of the photosensitive resin layer. The upper limit is not particularly limited, but is preferably 1% by mass or less.

[0436] -Thickness of the photosensitive resin layer- The thickness (layer thickness) of the photosensitive resin layer is not particularly limited, but from the viewpoints of developability and resolution, it is preferably 30 μm or less, more preferably 20 μm or less, still more preferably 15 μm or less, particularly preferably 10 μm or less, and most preferably 5.0 μm or less. As the lower limit, from the viewpoint of excellent strength of the film obtained by curing the photosensitive resin layer, it is preferably 0.60 μm or more, and more preferably 1.5 μm or more.

[0437] -Refractive index of the photosensitive resin layer- The refractive index of the photosensitive resin layer is preferably from 1.47 to 1.56, and more preferably from 1.49 to 1.54.

[0438] -Color of the photosensitive resin layer- The photosensitive resin layer is preferably achromatic. Specifically, for total reflection (incident angle: 8°, light source: D-65 (2° field of view)), in the CIE1976 (L * ,a * ,b * ) color space, the L * value is preferably from 10 to 90, the a * value is preferably from -1.0 to 1.0, and the b * value is preferably from -1.0 to 1.0.

[0439] Note that the pattern obtained by curing the photosensitive resin layer (cured film of the photosensitive resin layer) is preferably achromatic. Specifically, for total reflection (incident angle: 8°, light source: D-65 (2° field of view)), in the CIE1976 (L * ,a * ,b * ) color space, the L * value of the pattern is preferably from 10 to 90, and the a *The value is preferably -1.0 to 1.0, and for pattern b * The value is preferably -1.0 to 1.0.

[0440] - Moisture permeability of the photosensitive resin layer - The moisture permeability at a layer thickness of 40 μm of the pattern (cured film of the photosensitive resin layer) obtained by curing the photosensitive resin layer is preferably 500 g / (m 2 ·24 hr) or less, more preferably 300 g / (m 2 ·24 hr) or less, and even more preferably 100 g / (m 2 ·24 hr) or less, from the viewpoint of rust prevention. The moisture permeability is measured using a cured film obtained by curing the photosensitive resin layer by performing post-baking at 145°C for 30 minutes after exposing the photosensitive resin layer to an exposure amount of 300 mJ / cm 2 with i-line.

[0441] (Refractive index adjustment layer) The photosensitive transfer material preferably has a refractive index adjustment layer. As the refractive index adjustment layer, a known refractive index adjustment layer can be applied. Examples of the materials included in the refractive index adjustment layer include alkali-soluble resins, ethylenically unsaturated compounds, metal salts, and particles. The method for controlling the refractive index of the refractive index adjustment layer is not particularly limited, and examples include a method of using a resin having a predetermined refractive index alone, a method of using a resin and particles, and a method of using a composite of a metal salt and a resin.

[0442] Examples of the alkali-soluble resin and the ethylenically unsaturated compound include the alkali-soluble resin and the ethylenically unsaturated compound described in the section of the above "photosensitive resin layer".

[0443] Examples of the particles include metal oxide particles and metal particles. The type of the metal oxide particles is not particularly limited, and known metal oxide particles can be used. The metals in the metal oxide particles also include semi-metals such as B, Si, Ge, As, Sb, and Te.

[0444] The average primary particle diameter of the particles is preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm, for example, from the viewpoint of the transparency of the cured film. The average primary particle diameter of the particles is calculated by measuring the particle diameters of 200 arbitrary particles using an electron microscope and calculating the arithmetic mean of the measurement results. When the shape of the particles is not spherical, the longest side is taken as the particle diameter.

[0445] Specifically, as the metal oxide particles, at least one selected from the group consisting of zirconium oxide particles (ZrO2 particles), Nb2O5 particles, titanium oxide particles (TiO2 particles), silicon dioxide particles (SiO2 particles), and composite particles thereof is preferable. Among these, as the metal oxide particles, for example, at least one selected from the group consisting of zirconium oxide particles and titanium oxide particles is more preferable from the viewpoint of easy adjustment of the refractive index.

[0446] Examples of commercially available metal oxide particles include fired zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F04), fired zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F74), fired zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F75), fired zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F76), zirconium oxide particles (Nano Use OZ-S30M, manufactured by Nissan Chemical Industries, Ltd.), and zirconium oxide particles (Nano Use OZ-S30K, manufactured by Nissan Chemical Industries, Ltd.).

[0447] The particles may be used alone or in combination of two or more. The content of the particles in the refractive index adjustment layer is preferably 1% by mass to 95% by mass, more preferably 20% by mass to 90% by mass, and still more preferably 4% by mass to 85% by mass based on the total mass of the refractive index adjustment layer. When titanium oxide is used as the metal oxide particles, the content of the titanium oxide particles is preferably 1% by mass to 95% by mass, more preferably 20% by mass to 90% by mass, and still more preferably 40% by mass to 85% by mass with respect to the total mass of the refractive index adjustment layer.

[0448] The refractive index of the refractive index adjustment layer is preferably higher than that of the photosensitive resin layer. The refractive index of the refractive index adjustment layer is preferably 1.50 or more, more preferably 1.55 or more, still more preferably 1.60 or more, and particularly preferably 1.65 or more. The upper limit of the refractive index of the refractive index adjustment layer is preferably 2.10 or less, more preferably 1.85 or less, and particularly preferably 1.78 or less.

[0449] The thickness of the refractive index adjustment layer is preferably 50 nm to 500 nm, more preferably 55 nm to 110 nm, and still more preferably 60 nm to 100 nm.

[0450] The refractive index adjustment layer is formed using, for example, a refractive index adjustment layer. The composition for forming the refractive index adjustment layer preferably contains various components for forming the above-described refractive index adjustment layer and a solvent. In the composition for forming the refractive index adjustment layer, the preferred range of the content of each component with respect to the total solid content of the composition is the same as the preferred range of the content of each component with respect to the total mass of the above-described refractive index adjustment layer. The solvent is not particularly limited as long as it can dissolve or disperse the components contained in the refractive index adjustment layer, and at least one selected from the group consisting of water and water-miscible organic solvents is preferred, and water or a mixed solvent of water and a water-miscible organic solvent is more preferred. Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin. Alcohols having 1 to 3 carbon atoms are preferred, and methanol or ethanol is more preferred. The solvent may be used alone or in combination of two or more. The content of the solvent is preferably 50 parts by mass to 2,500 parts by mass, more preferably 50 parts by mass to 1,900 parts by mass, and still more preferably 100 parts by mass to 900 parts by mass with respect to 100 parts by mass of the total solid content of the composition.

[0451] The method for forming the refractive index adjustment layer is not particularly limited as long as it can form a layer containing the above components. For example, known coating methods (such as slit coating, spin coating, curtain coating, and inkjet coating) can be mentioned.

[0452] (Relationship among the temporary support, photosensitive resin layer, and protective film) Even in the photosensitive transfer material preferably used as the photosensitive transfer material for the wiring protective film, it is preferable to satisfy the relationship among the temporary support, photosensitive resin layer, and protective film described above.

[0453] <Method for manufacturing a resin pattern> The method for manufacturing a resin pattern according to an embodiment of the present disclosure is a method for manufacturing a resin pattern using the photosensitive transfer material according to the present disclosure. According to an embodiment of the present disclosure, a method for manufacturing a resin pattern having high linearity is provided. The method for manufacturing a resin pattern according to an embodiment of the present disclosure preferably includes a step of preparing a substrate (hereinafter sometimes referred to as the "preparation step"), a step of bringing the photosensitive transfer material into contact with the substrate and arranging a photosensitive resin layer and a temporary support on the substrate in this order (hereinafter sometimes referred to as the "laminating step"), a step of pattern-exposing the photosensitive resin layer (hereinafter sometimes referred to as the "exposure step"), and a step of developing the exposed photosensitive resin layer to form a resin pattern (hereinafter sometimes referred to as the "development step").

[0454] <<Preparation step>> In the preparation step, a substrate is prepared. The type of the substrate is not limited. The substrate is preferably a substrate including a conductive layer. Further, the substrate is preferably a substrate including a base material and a conductive layer on the base material, and more preferably a substrate including a base material and a conductive layer in contact with the base material. The conductive layer may be disposed on one side of the base material. The conductive layer may be disposed on both sides of the base material respectively. The substrate may include a layer other than the conductive layer.

[0455] Examples of the base material include glass, silicon, and resin films. The base material is preferably transparent. In the present disclosure, "transparent" means that the transmittance at a wavelength of 400 nm to 700 nm is 80% or more. The refractive index of the base material is preferably 1.50 to 1.52.

[0456] Examples of the transparent glass include tempered glass typified by Corning's Gorilla Glass. As the transparent glass, the materials used in JP-A Nos. 2010-86684, 2010-152809, and 2010-257492 may also be used.

[0457] The resin film is preferably a resin film having little optical distortion or high transparency. Examples of the resin film as described above include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.

[0458] In the method for manufacturing a resin pattern using a roll-to-roll method, the base material is preferably a resin film.

[0459] Examples of the conductive layer include conductive layers used in general circuit wiring or touch panel wiring. The conductive layer is preferably an electrode pattern corresponding to a sensor of a visible portion used in a capacitive touch panel or wiring of a peripheral extraction portion.

[0460] From the viewpoints of conductivity and fine wire formability, the conductive layer is preferably at least one selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, more preferably a metal layer, and particularly preferably a copper layer or a silver layer.

[0461] Examples of the components of the conductive layer include metals and conductive metal oxides. Examples of the metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au. Examples of the conductive metal oxides include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO2. In the present disclosure, "conductive" means a property in which the volume resistivity is less than 1×10 6 Ω cm. The volume resistivity of the conductive metal oxide is preferably less than 1×10 4 Ω cm.

[0462] When manufacturing a resin pattern using a substrate including a plurality of conductive layers, it is preferable that at least one of the plurality of conductive layers contains a conductive metal oxide.

[0463] The substrate may include one layer or two or more layers of conductive layers. When the substrate includes two or more layers of conductive layers, it is preferable that the substrate includes two or more layers of conductive layers formed of different materials from each other.

[0464] A preferred embodiment of the conductive layer is described, for example, in paragraph 0141 of International Publication No. 2018 / 155193, and the contents of which are incorporated herein by reference.

[0465] As the substrate including the conductive layer, a substrate having at least one of a transparent electrode and a routing wiring is preferable. The substrate as described above can be suitably used as a substrate for a touch panel. The transparent electrode can preferably function as an electrode for a touch panel. The transparent electrode is preferably composed of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide), and a fine metal wire such as a metal mesh and a metal nanowire. Examples of the fine metal wire include fine wires of silver, copper, etc. Among them, silver conductive materials such as a silver mesh and silver nanowires are preferable.

[0466] As the material of the routing wiring, metal is preferred. Examples of the metal as the material of the routing wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and alloys composed of two or more of these metal elements. As the material of the routing wiring, copper, molybdenum, aluminum, or titanium is preferred, and copper is particularly preferred.

[0467] <<Laminating Process>> In the laminating process, the photosensitive transfer material is brought into contact with the substrate, and the photosensitive resin layer and the temporary support are arranged on the substrate in this order.

[0468] The photosensitive transfer material is as described in the section of "Photosensitive Transfer Material" above. The preferred embodiments of the photosensitive transfer material used in the laminating process are the same as the preferred embodiments of the photosensitive transfer material described in the section of "Photosensitive Transfer Material" above.

[0469] In the laminating process, the photosensitive resin layer and the temporary support arranged on the substrate are the photosensitive resin layer and the temporary support contained in the photosensitive transfer material, respectively. That is, depending on the layer structure of the photosensitive transfer material, the layer structure of the laminate obtained by the laminating process changes. For example, in the laminating process, when the substrate is brought into contact with a photosensitive transfer material containing a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer in this order, the photosensitive resin layer, the intermediate layer, the thermoplastic resin layer, and the temporary support are arranged on the substrate in this order. When the photosensitive transfer material includes a protective film, after removing the protective film from the photosensitive transfer material, the substrate is brought into contact with the photosensitive transfer material.

[0470] In the laminating process, it is preferable to bring the photosensitive transfer material into contact with the substrate and crimp the photosensitive transfer material to the substrate. For example, it is preferable to bring the photosensitive transfer material into contact with the substrate and apply pressure and heat to the substrate and the photosensitive transfer material using means such as a roll to crimp the photosensitive transfer material to the substrate.

[0471] In a method of bringing a photosensitive transfer material into contact with a substrate (including a method of pressing the photosensitive transfer material onto the substrate), for example, a known transfer method or a known lamination method is used. In the method of bringing the photosensitive transfer material into contact with the substrate, for example, a laminator, a vacuum laminator, or an auto-cut laminator capable of enhancing productivity more is used.

[0472] <<Exposure step>> In the exposure step, the photosensitive resin layer is pattern-exposed. The arrangement and dimensions of the pattern in the pattern exposure are not limited. At least a part of the pattern (preferably, the part corresponding to the electrode pattern or the extraction wiring of the touch panel) preferably includes a fine line having a width of 20 μm or less, and more preferably includes a fine line having a width of 10 μm or less.

[0473] As the light source in the exposure step, for example, a light source that irradiates light having a wavelength capable of exposing the photosensitive resin layer (for example, 365 nm or 405 nm) can be mentioned. Examples of the light source include an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode).

[0474] The exposure amount is preferably 5 mJ / cm 2 ~300 mJ / cm 2 and more preferably 10 mJ / cm 2 ~200 mJ / cm 2

[0475] In the exposure step, the photosensitive resin layer may be pattern-exposed after peeling off the temporary support. In the exposure step, after pattern-exposing the photosensitive resin layer through the temporary support, the temporary support may be peeled off.

[0476] ​In an exposure method using a photomask, when the temporary support is peeled off before pattern exposure, the photomask may be brought into contact with the photosensitive resin layer to expose the photosensitive resin layer, or the photosensitive resin layer may be exposed by bringing the photomask close to the photosensitive resin layer without bringing the photomask into contact with the photosensitive resin layer. In an exposure method using a photomask to expose the photosensitive resin layer via a temporary support, the photomask may be brought into contact with the temporary support to expose the photosensitive resin layer, or the photosensitive resin layer may be exposed by bringing the photomask close to the temporary support without bringing the photomask into contact with the temporary support. In order to prevent contamination of the photomask due to contact between the photosensitive resin layer and the photomask, and to avoid the influence of foreign matter attached to the photomask on the exposure, it is preferable to perform pattern exposure of the photosensitive resin layer via a temporary support.

[0477] The exposure method is not limited. Examples of the exposure method include, for example, a contact exposure method and a non-contact exposure method. Examples of the contact exposure method include, for example, a method of pattern-exposing a photosensitive resin layer using a photomask. Examples of the non-contact exposure method include, for example, a proximity exposure method, a projection exposure method using a lens system or a mirror system, and a direct exposure method using an exposure laser. In the projection exposure method using a lens system or a mirror system, an exposure machine having an appropriate numerical aperture (NA) of a lens may be used according to the required resolution and depth of focus. In the direct exposure method, direct drawing may be performed on the photosensitive layer, or reduced projection exposure may be performed on the photosensitive layer through a lens. The exposure may be performed under atmospheric pressure, reduced pressure, or vacuum. Exposure may be performed with a liquid such as water interposed between the light source and the photosensitive resin layer.

[0478] <<Development process>> In the development process, the exposed photosensitive resin layer is developed to form a resin pattern. When the photosensitive resin layer is a negative photosensitive resin layer, the unexposed portion of the photosensitive resin layer is removed, and the exposed portion of the photosensitive resin layer forms a resin pattern. When the photosensitive resin layer is a positive photosensitive resin layer, the exposed portion of the photosensitive resin layer is removed, and the unexposed portion of the photosensitive resin layer forms a resin pattern. Also, in the bonding process, the thermoplastic resin layer and the intermediate layer disposed on the substrate are removed together with the photosensitive resin layer to be removed. The thermoplastic resin layer and the intermediate layer may be removed by dissolution or dispersion in the developer.

[0479] Development is performed, for example, using a developer. The developer is not limited as long as it is a developer that removes the target photosensitive resin layer. As the developer, a known developer is used. Examples of the developer include the developer described in JP-A-5-72724. The developer is preferably an alkaline aqueous solution-based developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol / L to 5 mol / L. The developer may contain a water-soluble organic solvent and / or a surfactant. The developer described in paragraph 0194 of WO 2015 / 093271 is also preferable as the developer.

[0480] The liquid temperature of the developer is not limited. The liquid temperature of the developer is preferably 20°C to 40°C.

[0481] The development method is not limited. The development method may be, for example, paddle development, shower development, shower and spin development, or dip development. Shower development is a method of removing the target photosensitive resin layer by spraying a developer onto the photosensitive resin layer after exposure by means of a shower.

[0482] After the development process, it is preferable to spray a cleaning agent by means of a shower and remove the development residue while rubbing with a brush.

[0483] The resin pattern obtained through the above-described process may be used as a permanent film or an etching protective film.

[0484] <<Roll-to-roll method>> The method for manufacturing a resin pattern is preferably performed by a roll-to-roll method. The roll-to-roll method uses a substrate that can be wound and unwound, and before any step included in the method for manufacturing a resin pattern, a step of unwinding the substrate or a laminate including the substrate (which may be referred to as the "unwinding step"), and after any step, a step of winding the substrate or a laminate including the substrate (hereinafter, may be referred to as the "winding step"), and includes performing at least any step (preferably all steps) while transporting the substrate or a laminate including the substrate. As the unwinding method in the unwinding step and the winding method in the winding step, for example, known methods applied to the roll-to-roll method are used.

[0485] <Method for manufacturing circuit wiring> The method for manufacturing circuit wiring according to an embodiment of the present disclosure is a method for manufacturing circuit wiring using the photosensitive transfer material according to the present disclosure. According to an embodiment of the present disclosure, a method for manufacturing circuit wiring having high linearity is provided. The method for manufacturing circuit wiring according to an embodiment of the present disclosure preferably includes a step of preparing a substrate including a conductive layer (hereinafter, may be referred to as the "preparation step"), a step of bringing the photosensitive transfer material into contact with the substrate and arranging a photosensitive resin layer and a temporary support on the substrate in this order (hereinafter, may be referred to as the "laminating step"), a step of pattern-exposing the photosensitive resin layer (hereinafter, may be referred to as the "exposure step"), a step of developing the exposed photosensitive resin layer to form a resin pattern (hereinafter, may be referred to as the "development step"), and a step of etching the conductive layer not covered by the resin pattern to form circuit wiring (hereinafter, may be referred to as the "etching step").

[0486] <<Preparation step>> In the preparation step, a substrate including a conductive layer is prepared. The substrate including the conductive layer is as described in the section of "Method for manufacturing a resin pattern" above. A preferred embodiment of the substrate including the conductive layer is the same as the preferred embodiment of the substrate including the conductive layer described in the section of "Method for manufacturing a resin pattern" above. <<Lamination step>> In the lamination step, a photosensitive transfer material is brought into contact with the substrate, and a photosensitive resin layer and a temporary support are disposed on the substrate in this order. The lamination step is as described in the section of "Method for manufacturing a resin pattern" above. A preferred embodiment of the lamination step is the same as the preferred embodiment of the lamination step described in the section of "Method for manufacturing a resin pattern" above.

[0487] <<Exposure step>> In the exposure step, the photosensitive resin layer is pattern-exposed. The exposure step is as described in the section of "Method for manufacturing a resin pattern" above. A preferred embodiment of the exposure step is the same as the preferred embodiment of the exposure step described in the section of "Method for manufacturing a resin pattern" above.

[0488] <<Development step>> In the development step, the exposed photosensitive resin layer is developed to form a resin pattern. The development step is as described in the section of "Method for manufacturing a resin pattern" above. A preferred embodiment of the development step is the same as the preferred embodiment of the development step described in the section of "Method for manufacturing a resin pattern" above.

[0489] <<Etching step>> In the etching step, the conductive layer not covered by the resin pattern is etched to form circuit wiring. In the etching step, the resin pattern functions as a protective film for the conductive layer. In the etching step, the conductive layer not covered by the resin pattern is removed by the etching process, and the conductive layer covered by the resin pattern forms circuit wiring.

[0490] As an etching process method, for example, a known method is used. Examples of the etching process method include the methods described in paragraphs 0209 to 0210 of Japanese Patent Application Laid-Open No. 2017-120435, the methods described in paragraphs 0048 to 0054 of Japanese Patent Application Laid-Open No. 2010-152155, a wet etching method of immersing in an etching solution, and a dry etching method (for example, plasma etching).

[0491] Regarding the etching solution used in the wet etching method, an acidic or alkaline etching solution may be appropriately selected according to the object to be etched. Examples of the acidic etching solution include an aqueous solution containing at least one acidic component selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid. Examples of the acidic etching solution also include an aqueous solution containing the above-mentioned acidic component and at least one salt selected from the group consisting of ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component may be a component combining a plurality of acidic components. Examples of the alkaline etching solution include an aqueous solution containing at least one alkaline component selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (for example, tetramethylammonium hydroxide). Examples of the alkaline etching solution also include an aqueous solution containing the above-mentioned alkaline component and a salt (for example, potassium permanganate). The alkaline component may be a component combining a plurality of alkaline components.

[0492] <<Removal Step>> The method for manufacturing a circuit wiring according to an embodiment of the present disclosure preferably includes a step of removing the remaining resin pattern after the etching step.

[0493] As a method for removing a resin pattern, for example, a method of removing the resin pattern using chemical treatment can be mentioned. A method of removing the resin pattern using a removal liquid is preferable. As a method of removing the resin pattern using a removal liquid, for example, a method of immersing a substrate including the resin pattern in a stirred removal liquid having a liquid temperature of 30°C to 80°C (preferably 50 to 80°C) for 1 minute to 30 minutes can be mentioned.

[0494] Examples of the removal liquid include a removal liquid containing at least one selected from the group consisting of an inorganic alkali component or an organic alkali component, water, dimethyl sulfoxide, and N-methylpyrrolidone. Examples of the inorganic alkali component include sodium hydroxide and potassium hydroxide. Examples of the organic alkali component include a primary amine compound, a secondary amine compound, a tertiary amine compound, and a quaternary ammonium salt compound.

[0495] A known method such as a spray method, a shower method, and a paddle method may be used to remove the remaining resin pattern.

[0496] <<Other processes>> The method for manufacturing a circuit wiring according to an embodiment of the present disclosure may further include other processes in addition to the above-described processes. Examples of the other processes include the processes shown below. Also, for the exposure process, the development process, and other processes applicable to the method for manufacturing a circuit wiring according to an embodiment of the present disclosure, they are described in paragraphs 0035 to 0051 of JP-A-2006-23696. The content described in the above publication is incorporated herein by reference.

[0497] (Step of reducing the visible light reflectance) A method for manufacturing circuit wiring according to an embodiment of the present disclosure may include a step of performing a process for reducing the visible light reflectance of some or all of a plurality of conductive layers of a substrate. Examples of the process for reducing the visible light reflectance include an oxidation process. For example, when the conductive layer contains copper, the copper can be oxidized to form copper oxide, and by blackening the conductive layer, the visible light reflectance of the conductive layer can be reduced. The process for reducing the visible light reflectance is described in paragraphs 0017 to 0025 of JP-A-2014-150118 and paragraphs 0041, 0042, 0048, and 0058 of JP-A-2013-206315. The contents described in these publications are incorporated herein by reference.

[0498] (Step of forming an insulating film and step of forming a new conductive layer on the surface of the insulating film) A method for manufacturing circuit wiring according to an embodiment of the present disclosure preferably includes a step of forming an insulating film on the surface of the circuit wiring and a step of forming a new conductive layer on the surface of the insulating film. By the above steps, a second electrode pattern insulated from the first electrode pattern can be formed. Examples of the method for forming the insulating film include a method for forming a known permanent film. An insulating film having a desired pattern may be formed by photolithography using a photosensitive material having insulating properties. Examples of the method for forming a new conductive layer on the surface of the insulating film include forming a new conductive layer having a desired pattern by photolithography using a photosensitive material having conductivity.

[0499] In a method for manufacturing circuit wiring according to an embodiment of the present disclosure, it is also preferable to use a substrate having a plurality of conductive layers on both surfaces of a base material and to form circuits sequentially or simultaneously on the conductive layers formed on both surfaces of the base material. According to the method as described above, a first conductive pattern can be formed on one surface of the base material, and a second conductive pattern can be formed on the other surface of the base material. The conductive pattern as described above is used, for example, as circuit wiring for a touch panel. The conductive pattern as described above is preferably formed by a roll-to-roll method.

[0500] <<Roll-to-roll method>> The method for manufacturing circuit wiring according to an embodiment of the present disclosure is preferably performed by a roll-to-roll method. The roll-to-roll method is as described in the section of "Method for manufacturing resin pattern" above.

[0501] <<Applications of circuit wiring>> The circuit wiring obtained by the method for manufacturing circuit wiring according to an embodiment of the present disclosure is applied to various devices. Examples of the device including the circuit wiring include an input device, preferably a touch panel, and more preferably a capacitive touch panel. The above input device can be applied to display devices such as an organic EL display device and a liquid crystal display device.

[0502] <Method for manufacturing touch panel> The method for manufacturing a touch panel according to an embodiment of the present disclosure is a method for manufacturing a touch panel using a photosensitive transfer material according to the present disclosure. The method for manufacturing a touch panel according to an embodiment of the present disclosure preferably includes the method for manufacturing circuit wiring according to an embodiment of the present disclosure. That is, the method for manufacturing a touch panel according to an embodiment of the present disclosure preferably includes the preparation step, exposure step, development step, and etching step described in the section of "Method for manufacturing circuit wiring" above. By going through the above steps, for example, wiring for a touch panel is formed. Examples of the pattern of the photomask used for manufacturing the wiring for a touch panel include Pattern A and Pattern B described in JP-A-2019-204070. The method for manufacturing a touch panel according to an embodiment of the present disclosure may further include other steps described in the section of "Method for manufacturing circuit wiring" above. A known method for manufacturing a touch panel may be referred to for forming components of the touch panel other than the wiring.

[0503] Examples of the detection method for a touch panel include a resistive film method, a capacitive method, an ultrasonic method, an electromagnetic induction method, and an optical method. Among the above, the capacitive method is preferable.

[0504] Examples of touch panel types include in-cell type (for example, the configurations described in FIGS. 5, 6, 7, and 8 of JP-T-2012-517051), on-cell type (for example, the configurations described in FIG. 19 of JP-A-2013-168125 and FIGS. 1 and 5 of JP-A-2012-89102), OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (for example, the configuration described in FIG. 2 of JP-A-2013-54727), various out-cell types (for example, GG, G1·G2, GFF, GF2, GF1, and G1F), and other configurations (for example, the configuration described in FIG. 6 of JP-A-2013-164871).

Example

[0505] Hereinafter, the present disclosure will be described in detail based on examples. However, the present disclosure is not limited to the following examples. The content of the following examples (for example, materials, amounts used, ratios, treatment contents, and treatment procedures) may be appropriately changed within the scope of the object of the present disclosure.

[0506] <Preparation of Composition 1 for Forming Particle-Containing Layer> A mixture obtained by mixing the components shown below was filtered using a 6 μm filter (F20, Marueref Filter Systems Co., Ltd.) and then degassed by membrane using a 2x6 radial flow superformic (Polypore Co., Ltd.). By the above procedure, Composition 1 for forming a particle-containing layer was obtained.

[0507] · Acrylic polymer (AS-563A, Daicel Miraiz Co., Ltd., solid content: 27.5% by mass): 167 parts by mass · Nonionic surfactant (Nalacty CL95, Sanyo Chemical Industries, Ltd., solid content: 100% by mass): 0.7 part by mass · Anionic surfactant (Lapizol A-90, NOF Corporation, aqueous dilution with a solid content concentration of 1% by mass): 114.4 parts by mass · Carnauba wax dispersion (Cellosol 524, Chukyo Yushi Co., Ltd., solid content: 30% by mass): 7 parts by mass · Carbodiimide compound (Carbodilite V-02-L2, Nisshinbo Chemical Inc., water-diluted with a solid content concentration of 10% by mass): 20.9 parts by mass · Matting agent (Snowtex XL, Nissan Chemical Industries, Ltd., solid content: 40% by mass, average particle diameter: 50 nm): 2.8 parts by mass · Water: 690.2 parts by mass

[0508] <Preparation of Composition 2 for Forming Particle-Containing Layer> Composition 2 for forming a particle-containing layer was obtained by the same method as the preparation method of Composition 1 for forming a particle-containing layer, except that the addition amount of the matting agent was changed to 3.6 parts by mass.

[0509] <Preparation of Composition 3 for Forming Particle-Containing Layer> The mixture obtained by mixing the components shown below was filtered using a 6-μm filter (F20, Marle Filter Systems Co., Ltd.) and then degassed by membrane using a 2x6 radial flow superformic (Polypore Co., Ltd.). By the above procedure, Composition 3 for forming a particle-containing layer was obtained.

[0510] · Acrylic polymer (AS-563A, Daicel Miraiz Co., Ltd., solid content: 27.5% by mass): 167 parts by mass · Nonionic surfactant (Nalacty CL95, Sanyo Chemical Industries, Ltd., solid content: 100% by mass): 0.7 parts by mass · Anionic surfactant (Lapizol A-90, NOF Corporation, water-diluted solution with a solid content concentration of 1% by mass): 55.7 parts by mass · Carnauba wax dispersion (Cerosol 524, Chukyo Yushi Co., Ltd., solid content: 30% by mass): 7 parts by mass · Carbodiimide compound (Carbodilite V-02-L2, Nisshinbo Chemical Inc., water-diluted with a solid content concentration of 10% by mass): 20.9 parts by mass · Matting agent (Snowtex XL, Nissan Chemical Industries, Ltd., solid content: 40% by mass, average particle diameter: 50 nm): 2.8 parts by mass · Matting agent (Aerosil OX50, Nippon Aerosil Co., Ltd., solid content: 10% by mass, water dispersion, median diameter: 0.2 μm): 3.5 parts by mass · Water: 743 parts by mass

[0511] <Preparation of Composition 4 for Forming Particle-Containing Layer> Composition 4 for forming a particle-containing layer was obtained in the same manner as the preparation method of Composition 1 for forming a particle-containing layer, except that the addition amount of the matting agent was 6.0 parts by mass.

[0512] <Manufacture of Temporary Support 1> Temporary support 1 was manufactured by the following method.

[0513] (Extrusion Molding) Pellets of polyethylene terephthalate (PET) manufactured using a citric acid chelate organic titanium complex described in Japanese Patent No. 5575671 as a polymerization catalyst were dried to reduce the moisture content of the pellets to 50 ppm or less. The dried pellets were charged into the hopper of a single-screw kneading extruder with a diameter of 30 mm and melted at 280°C. The melt was passed through a filter (pore size: 2 μm) and then extruded from the die onto a cooling roll at 25°C to obtain an unstretched film. In the above method, the melt was adhered to the cooling roll using the electrostatic printing method.

[0514] (Stretching and Coating) The cured unstretched film was successively biaxially stretched by the following method to form a particle-containing layer with a thickness of 40 nm on a polyethylene terephthalate film with a thickness of 16 μm.

[0515] (a) Longitudinal Stretching The unstretched film was passed between two pairs of nip rolls with different peripheral speeds and stretched in the longitudinal direction (transport direction). The conditions for longitudinal stretching are shown below. · Preheating temperature: 75°C · Stretching temperature: 100°C · Stretching ratio: 3.4 times · Stretching speed: 1,300% / second

[0516] (b) Coating Composition 1 for forming a particle-containing layer was coated on one side of the longitudinally stretched film using a bar coater so that the thickness after film formation was 40 nm.

[0517] (c) Lateral stretching The film coated with the composition 1 for forming the particle-containing layer was laterally stretched using a tenter under the following conditions. · Preheating temperature: 110 °C · Stretching temperature: 120 °C · Stretching ratio: 4.2 times · Stretching speed: 50% / second

[0518] (Heat setting and heat relaxation) The biaxially stretched film after longitudinal and lateral stretching was heat-set under the following conditions. · Heat setting temperature: 227 °C · Heat setting time: 6 seconds

[0519] After heat setting, the tenter width was reduced, and the biaxially stretched film was heat-relaxed under the following conditions. · Heat relaxation temperature: 190 °C · Heat relaxation rate: 4%

[0520] (Winding) After heat setting and heat relaxation, both ends of the film were trimmed, extrusion processing (narrowing) was performed at a width of 10 mm at the ends of the film, and then the film was wound at a tension of 40 kg / m. The width of the film was 1.5 m, and the winding length of the film was 6,300 m. The obtained film roll was used as the temporary support 1.

[0521] The temporary support 1 includes a polyethylene terephthalate film (base material) and a particle-containing layer in this order. The haze of the temporary support 1 was 0.2%. The haze was measured as the total haze using a haze meter (Nippon Denshoku Industries Co., Ltd., NDH2000). The heat shrinkage rate due to heating at 150°C for 30 minutes was 1.0% on the MD (Machine Direction, conveyance direction) side and 0.2% on the TD (Transverse Direction, direction perpendicular to the conveyance direction on the film surface) side. Measured from a cross-sectional TEM photograph, the thickness of the particle-containing layer was 40 nm. The average particle diameter of the particles contained in the particle-containing layer, measured by the above method using an HT-7700 type transmission electron microscope (TEM) manufactured by Hitachi High-Technologies Corporation, was 50 nm.

[0522] <Manufacture of Temporary Supports 2 to 11> According to the following table, temporary supports were obtained by the same method as the manufacturing method of the temporary support 1, except that the type of the composition for forming the particle-containing layer and the arrangement of the particle-containing layer were appropriately changed.

[0523]

Table 1

[0524] In the above table, the temporary support in which the number indicating the type of the composition for forming the particle-containing layer is described in the column of "Second Surface" includes the particle-containing layer arranged as the outermost layer on the second surface side of the temporary support. In the above table, the temporary support in which the number indicating the type of the composition for forming the particle-containing layer is described in the column of "First Surface" includes the particle-containing layer arranged as the outermost layer on the first surface side of the temporary support.

[0525] <Preparation of Photosensitive Resin Layer Forming Composition 1> A solvent and the following components were mixed to prepare the photosensitive resin layer forming composition 1.

[0526]

Table 2

[0527] <Preparation of Composition 2 for Forming Photosensitive Resin Layer> A solvent and the following components were mixed to prepare Composition 2 for forming a photosensitive resin layer.

[0528] [Table 3]

[0529] <Preparation of Composition 1 for Forming Thermoplastic Resin Layer> A solvent and the following components were mixed to prepare Composition 1 for forming a thermoplastic resin layer.

[0530] [Table 4]

[0531] The meanings of the abbreviations described in the above table are shown below. · A-2: Benzyl methacrylate / methacrylic acid / acrylic acid copolymer (75 mass% / 10 mass% / 15 mass%, weight average molecular weight: 30,000, Tg: 75 °C, acid value: 186 mgKOH / g) · B-1: Compound having the structure shown below (dye that develops color with acid)

[0532] [Chemical formula]

[0533] · C-1: Compound having the structure shown below (photoacid generator, the compound described in paragraph 0227 of JP-A 2013-47765, synthesized according to the method described in paragraph 0227.)

[0534] [Chemical formula]

[0535] · D-3: NK Ester A-DCP (tricyclodecane dimethanol diacrylate, Shin-Nakamura Chemical Co., Ltd.) · D-4: 8UX-015A (Multifunctional urethane acrylate compound, Taisei Fine Chemical Co., Ltd.) · D-5: Aronix TO-2349 (Multifunctional acrylate compound having a carboxy group, Toagosei Co., Ltd.) · E-1: Megafac F-552 (Fluorine-based surfactant, DIC Corporation) · F-1: Phenothiazine (Fuji Film Wako Pure Chemical Corporation) · F-2: CBT-1 (Carboxybenzotriazole, Johoku Chemical Industry Co., Ltd.)

[0536] <Preparation of Composition 1 for Forming Water-Soluble Resin Layer> The following components were mixed to prepare Composition 1 for forming a water-soluble resin layer. · Ion-exchanged water: 38.12 parts by mass · Methanol (Mitsubishi Gas Chemical Company, Inc.): 57.17 parts by mass · Kuraray Poval 4-88LA (Polyvinyl alcohol, Kuraray Co., Ltd.): 3.22 parts by mass · Polyvinylpyrrolidone K-30 (Nippon Shokubai Co., Ltd.): 1.49 parts by mass · Megafac F-444 (Fluorine-based surfactant, DIC Corporation): 0.0035 parts by mass

[0537] <Example 1> On the second surface of Temporary Support 1, Composition 1 for forming a photosensitive resin layer was applied using a slit nozzle. The applied Composition 1 for forming a photosensitive resin layer was dried at 100 °C for 120 seconds to form a photosensitive resin layer having a thickness of 5 μm. The photosensitive transfer material obtained by the above procedure includes a temporary support and a photosensitive resin layer in this order.

[0538] <Examples 2 to 14 and Comparative Example 1> According to the description in Table 5, a photosensitive transfer material was obtained by the same procedure as described in Example 1, except that the type of the temporary support and the thickness of the photosensitive resin layer were appropriately changed.

[0539] <Example 15> Using a slit nozzle, a thermoplastic resin layer-forming composition 1 was applied onto the second surface of the temporary support 1. The applied thermoplastic resin layer-forming composition 1 was dried at 100°C for 120 seconds to form a thermoplastic resin layer having a thickness of 2 µm.

[0540] Composition 1 for forming a water-soluble resin layer was applied onto the thermoplastic resin layer using a slit nozzle. The applied composition 1 for forming a water-soluble resin layer was dried at 120°C for 120 seconds to form a water-soluble resin layer having a thickness of 1 µm. The water-soluble resin layer was an intermediate layer.

[0541] Photosensitive resin layer-forming composition 2 was applied onto the water-soluble resin layer using a slit nozzle. The applied photosensitive resin layer-forming composition 2 was dried at 100°C for 120 seconds to form a photosensitive resin layer having a thickness of 2 µm.

[0542] The photosensitive transfer material obtained by the above procedure contains a temporary support, a thermoplastic resin layer, a water-soluble resin layer, and a photosensitive resin layer in this order.

[0543] <Temporary support L * Value> After peeling the temporary support from the photosensitive transfer material, the L of the first surface of the temporary support * value and L of the second surface * The L value was measured by the following method. Using a spectrophotometer (CM-700d, Konica Minolta, Inc.), a total of 10 L values were measured at 3 cm intervals along the width direction of the target surface. * The specific measurement conditions are as follows: L values at 10 points measured by the SCE method * The values were arithmetically averaged. The obtained value was used to calculate the L of the target surface using the SCE method. * The measurement results are shown in Table 5. ·Light source: D65 light source Mode: SCI+SCE mode Measuring diameter: 8mmφ

[0544] <Minimum resolution line width and linearity> A copper layer with a thickness of 200 nm was formed by sputtering on a polyethylene terephthalate (PET) film with a thickness of 100 μm to fabricate a PET substrate with a copper layer. The photosensitive transfer material and the PET substrate with a copper layer were laminated by a roll-to-roll method using a vacuum laminator (MCK Co., Ltd., roll temperature: 110 °C, linear pressure: 1.0 MPa, linear speed: 0.5 m / min). The obtained laminate includes at least a PET film, a copper layer, a photosensitive resin layer, and a temporary support in this order. The obtained laminate was pressure-defoamed for 0.5 hours under the conditions of 0.6 MPa and 60 °C using an autoclave device. Using an ultra-high pressure mercury lamp, the photosensitive resin layer was exposed through a line and space pattern mask (the duty ratio is 1:1, and the line width changes stepwise from 1 μm to 20 μm at intervals of 1 μm) without peeling the temporary support. After peeling the temporary support, it was developed. The development was carried out for 30 seconds by shower development using a 1.0 mass% aqueous sodium carbonate solution at 25 °C. By the above method, the exposure amount (hereinafter referred to as the "reference exposure amount") at which the line width of the resin pattern corresponding to the 20-μm line and space pattern of the mask becomes exactly 20 μm was determined. Next, a resin pattern was formed by the same method as above except that the photosensitive resin layer was exposed at the reference exposure amount. The resin pattern was observed using a scanning electron microscope (SEM). The minimum value of the line width of the resin pattern without peeling of the resin pattern and without residue in the space portion of the resin pattern was adopted as the minimum resolution line width. The measurement results are shown in the following table. The smaller the minimum resolution line width, the better the resolution.

[0545] Next, among the obtained resin patterns, a resin pattern with a line width of 10 μm was observed using a scanning electron microscope (SEM), and the maximum value - minimum value of the line width (hereinafter referred to as the "line width variation value") was measured in a range of 100 μm in length. Based on the line width variation value, the linearity of the resin pattern was evaluated according to the following criteria. The evaluation results are shown in Table 5. A: The line width variation value is less than 0.4 μm. B: The line width variation value is 0.4 μm or more and less than 0.7 μm. C: The line width variation value is 0.7 μm or more and less than 1.0 μm. D: The variation value of the line width is 1.0 μm or more and less than 1.5 μm. E: The variation value of the line width is 1.5 μm or more.

[0546] <Conveyability> A copper layer with a thickness of 200 nm was formed by sputtering on a polyethylene terephthalate film (PET film) with a thickness of 100 μm to produce a PET substrate with a copper layer. The photosensitive transfer material and the PET substrate with a copper layer were laminated using a roll-to-roll method with a vacuum laminator (MCK Co., Ltd., roll temperature: 120 °C, line pressure: 1.0 MPa, line speed: 0.5 m / min). The layer structure of the obtained laminate is PET film / copper layer / photosensitive resin layer / temporary support. The temporary support of the laminate was visually observed and evaluated for the occurrence of wrinkles according to the following criteria. The evaluation results are shown in Table 5. A: No wrinkles were confirmed at all. B: Visible strong wrinkles (e.g., wrinkles with a width of several tens of μm to several hundreds of μm) were confirmed.

[0547]

Table 5

[0548] Table 5 shows that the linearity of the resin patterns in Examples 1 to 15 is superior to that of the resin pattern in Comparative Example 1.

[0549] <Preparation of Composition for Forming Photosensitive Resin Layer> Compositions A-1 to A-10 for forming a photosensitive resin layer having the compositions shown in the following table were each prepared.

[0550]

Table 6

[0551]

Table 7

[0552] (Compound B) The structure of Compound B is shown below.

[0553] [Chemical formula]

[0554] (Compound C) The structure of Compound C is shown below.

[0555] [Chemical formula]

[0556] (Preparation of P-1 solution) As the P-1 solution, a 36.3 mass% solid content solution of polymer P-1 having the following structure (solvent: propylene glycol monomethyl ether acetate) was used. Polymer P-1 is an alkali-soluble resin. In polymer P-1, the numerical value at the lower right of each structural unit indicates the content ratio (mol%) of each structural unit. The P-1 solution was prepared by the polymerization step and addition step shown below.

[0557] - Polymerization step - Into a 2000 mL flask, propylene glycol monomethyl ether acetate (manufactured by Sanwa Chemical Industry Co., Ltd., trade name PGM-Ac) (60 g) and propylene glycol monomethyl ether (manufactured by Sanwa Chemical Industry Co., Ltd., trade name PGM) (240 g) were introduced. The resulting liquid was heated to 90 °C while stirring at a stirring speed of 250 rpm (round per minute; the same applies hereinafter). As the preparation of the dropping solution (1), methacrylic acid (107.1 g), methyl methacrylate (manufactured by Mitsubishi Gas Chemical Co., Inc., trade name MMA) (5.46 g), and cyclohexyl methacrylate (manufactured by Mitsubishi Gas Chemical Co., Inc., trade name CHMA) (231.42 g) were mixed and diluted with PGM-Ac (60 g) to obtain the dropping solution (1). As the preparation of the dropping solution (2), 9.637 g of dimethyl 2,2'-azobis(2-methylpropionate) (manufactured by Fujifilm Wako Pure Chemical Corporation, trade name V-601) was dissolved in 136.56 g of PGM-Ac to obtain the dropping solution (2). The dropping solution (1) and the dropping solution (2) were simultaneously dropped into the above-mentioned 2000 mL flask (specifically, a 2000 mL flask containing a liquid heated to 90°C) over 3 hours. Next, the container of the dropping solution (1) was washed with 12 g of PGM-Ac, and the washing solution was dropped into the above-mentioned 2000 mL flask. Next, the container of the dropping solution (2) was washed with 6 g of PGM-Ac, and the washing solution was dropped into the above-mentioned 2000 mL flask. During these droppings, the reaction solution in the above-mentioned 2000 mL flask was maintained at 90°C and stirred at a stirring speed of 250 rpm. Further, as a post-reaction, it was stirred at 90°C for 1 hour. To the reaction solution after the post-reaction, 2.401 g of V-601 was added as the first additional addition of the initiator. Further, the container of V-601 was washed with 6 g of PGM-Ac, and the washing solution was introduced into the reaction solution. Then, it was stirred at 90°C for 1 hour. Next, 2.401 g of V-601 was added to the reaction solution as the second additional addition of the initiator. Further, the container of V-601 was washed with 6 g of PGM-Ac, and the washing solution was introduced into the reaction solution. Then, it was stirred at 90°C for 1 hour. Next, 2.401 g of V-601 was added to the reaction solution as the third additional addition of the initiator. Further, the container of V-601 was washed with 6 g of PGM-Ac, and the washing solution was introduced into the reaction solution. Then, it was stirred at 90°C for 3 hours.

[0558] -Addition step- After stirring at 90°C for 3 hours, 178.66 g of PGM-Ac was introduced into the reaction solution. Next, 1.8 g of tetraethylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Corporation) and 0.8 g of hydroquinone monomethyl ether (manufactured by Fujifilm Wako Pure Chemical Corporation) were added to the reaction solution. Further, each container was washed with 6 g of PGM-Ac, and the washing solution was introduced into the reaction solution. Then, the temperature of the reaction solution was raised to 100°C. Next, glycidyl methacrylate (manufactured by NOF Corporation, trade name Blemmer G) (76.03 g) was added dropwise to the reaction solution over 1 hour. The container of Blemmer G was washed with PGM-Ac (6 g), and the washing solution was introduced into the reaction solution. Thereafter, as an addition reaction, stirring was carried out at 100 °C for 6 hours. Next, the reaction solution was cooled and filtered through a dust-removing mesh filter (100 mesh) to obtain a solution (1158 g) of polymer P-1 (solid content concentration: 36.3 mass%). The weight-average molecular weight of the obtained polymer P-1 was 27,000, the number-average molecular weight was 15,000, and the acid value was 95 mgKOH / g. The structure of polymer P-1 is shown below. The molar ratio of the repeating units in the formula was 51.5:2:26.5:20 in order from the leftmost repeating unit.

[0559] [Chemical formula]

[0560] (Preparation of P-2 solution) According to the following method, a 36.5 mass% solution of polymer P-2 in terms of solid content was prepared as the P-2 solution. Polymer P-2 is an alkali-soluble resin. 82.4 g of propylene glycol monomethyl ether was charged into a flask and heated to 90 °C under a nitrogen stream. A solution prepared by dissolving 38.4 g of styrene, 30.1 g of dicyclopentanyl methacrylate, and 34.0 g of methacrylic acid in 20 g of propylene glycol monomethyl ether, and a solution prepared by dissolving 5.4 g of polymerization initiator V-601 (manufactured by Fuji Film Wako Pure Chemical Corporation) in 43.6 g of propylene glycol monomethyl ether acetate were simultaneously added dropwise over 3 hours. After the completion of the dropwise addition, 0.75 g of V-601 was added three times at 1-hour intervals. Then, the reaction was continued for another 3 hours. Thereafter, it was diluted with 58.4 g of propylene glycol monomethyl ether acetate and 11.7 g of propylene glycol monomethyl ether. Under an air stream, the temperature of the reaction solution was raised to 100 °C, and 0.53 g of tetraethylammonium bromide and 0.26 g of p-methoxyphenol were added. 25.5 g of glycidyl methacrylate (Blemmer GH manufactured by NOF Corporation) was added dropwise thereto over 20 minutes. This was reacted at 100 °C for 7 hours to obtain a solution of polymer P-2. The solid content concentration of the obtained solution was 36.5 mass%. Regarding polymer P-2, the weight average molecular weight in terms of standard polystyrene in GPC was 17,000, the dispersity was 2.4, and the acid value was 95 mgKOH / g. The amount of residual monomer measured using gas chromatography was less than 0.1 mass% with respect to the solid content of polymer P-2 for any monomer. The structure of polymer P-2 is shown below. The molar ratio of the repeating units in the formula was 41.0:15.2:23.9:19.9 in order from the repeating unit on the left side.

[0561] [Chemical formula]

[0562] (Preparation of P-3 solution) According to the following method, a 36.2 mass% solution of polymer P-3 as a P-3 solution was prepared. Polymer P-3 is an alkali-soluble resin. 113.5 g of propylene glycol monomethyl ether was charged into a flask and heated to 90 °C under a nitrogen stream. A solution prepared by dissolving 172 g of styrene, 4.7 g of methyl methacrylate, and 112.1 g of methacrylic acid in 30 g of propylene glycol monomethyl ether, and a solution prepared by dissolving 27.6 g of polymerization initiator V-601 (manufactured by Fuji Film Wako Pure Chemical Corporation) in 57.7 g of propylene glycol monomethyl ether were simultaneously added dropwise over 3 hours. After the addition was completed, 2.5 g of V-601 was added three times at 1-hour intervals. Thereafter, the reacti...

Claims

1. A temporary support having a first surface and a second surface on the opposite side of the first surface, a photosensitive resin layer on the second surface of the temporary support, and The L value of the second surface of the temporary support measured by the SCE method is ＊ 0.6 or more and 1.5 or less, and the temporary support is a polyester film composed of two or more layers, and the surface layer having at least the second surface does not contain particles and has a phase separation structure, a photosensitive transfer material.

2. The photosensitive transfer material according to claim 1, wherein the surface layer on the first surface side of the temporary support does not contain particles.

3. The L value of the first surface of the temporary support measured by the SCE method is 2.0 or less. The photosensitive transfer material according to claim 1 or claim 2. ＊ Value is 2.0 or less. The photosensitive transfer material according to claim 1 or claim 2.

4. The photosensitive transfer material according to any one of claims 1 to 3, wherein the arithmetic mean roughness Ra of the first surface of the temporary support is 1 nm to 50 nm.

5. The photosensitive transfer material according to any one of claims 1 to 4, wherein the surface layer having the first surface has a phase separation structure.

6. The photosensitive transfer material according to any one of claims 1 to 5, wherein the surface layer contains a polyester resin having an alicyclic structure.

7. The photosensitive transfer material according to claim 6, wherein the alicyclic structure is a cyclohexane ring.

8. The photosensitive transfer material according to claim 6 or 7, wherein the surface layer contains a copolymerized polyethylene terephthalate having isophthalic acid as a copolymerization component.

9. A method for manufacturing a resin pattern using the photosensitive transfer material according to any one of claims 1 to 8, comprising the steps of preparing a substrate, bringing the photosensitive transfer material into contact with the substrate and disposing the photosensitive resin layer and the temporary support on the substrate in this order, pattern exposing the photosensitive resin layer, developing the exposed photosensitive resin layer to form a resin pattern, and a method for manufacturing a resin pattern.

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