Method for manufacturing transfer film and conductive pattern

Abstract

Provided are a transfer film and an application thereof, the transfer film comprising a temporary support, a transfer layer, and a protective film in this order, wherein the storage elastic modulus of the transfer layer at 25 °C on the protective film side is 1.0×106 Pa to 3.0×108 Pa.

Description

[Technical Field]

[0001] This disclosure relates to a method for manufacturing a transfer film and a conductive pattern. [Background technology]

[0002] Transfer films are widely used in various pattern formation methods, such as photolithography. Typically, a transfer film includes a transfer layer. For example, in a pattern formation method using a transfer film, the transfer layer is placed on an object (e.g., a substrate) by transfer. The transfer layer placed on the object can then form a pattern through processes such as exposure and development.

[0003] Patent Document 1 below discloses a transfer film comprising a support film and a photosensitive resin layer made of a specific photosensitive resin composition provided on the support film. Patent Document 1: Japanese Unexamined Patent Publication No. 2020-086238 [Overview of the project] [Problems that the invention aims to solve]

[0004] However, conventional pattern formation methods using transfer films may result in reduced resolution for the following reasons. Transferring the transfer layer to an object is performed, for example, by bonding the transfer film to the object. However, if the adhesion between the transfer layer and the object is poor, for example, the developer may penetrate the gap between the transfer layer and the object during development, which can reduce resolution. Furthermore, if the transfer film includes both a transfer layer and a protective film, a portion of the transfer layer may adhere to the surface of the removed protective film during the process of peeling the protective film from the transfer film. In other words, a portion of the transfer layer may be removed along with the protective film. When a portion of the transfer layer is removed along with the protective film, the original properties of the transfer layer are not expressed, which can result in reduced resolution, for example.

[0005] One embodiment of the present disclosure aims to provide a transfer film having excellent resolution. Another embodiment of the present disclosure aims to provide a method for manufacturing a conductor pattern using a transfer film having excellent resolution. [Means for solving the problem]

[0006] This disclosure includes the following aspects: <1> The device comprises a temporary support, a transfer layer, and a protective film in this order, wherein the storage modulus of the transfer layer on the protective film side at 25°C is 1.0 × 10⁻⁶ 6 Pa~3.0×10 8 A transfer film with Pa. <2> The storage modulus of the transfer layer on the temporary support side at 25°C is 1.0 × 10⁻⁶ 6 It is Pa or higher. <1> The transfer film described above. <3> The surface roughness Ra of the transfer layer facing the temporary support is 0.1 nm to 15 nm. <1> or <2> The transfer film described above. <4> The surface roughness Ra of the temporary support facing the transfer layer is 0.1 nm to 15 nm. <1> ~ <3> A transfer film as described in one of the following. <5> The above transfer layer is a photosensitive layer. <1> ~ <4> A transfer film as described in one of the following. <6> The above transfer layer includes an intermediate layer and a photosensitive layer. <1> ~ <4> A transfer film as described in one of the following. <7> The above-mentioned intermediate layer contains an alkali-soluble resin and a polymerizable compound, and the ratio of the mass of the polymerizable compound to the mass of the alkali-soluble resin in the intermediate layer is 0.5 or more. <6> The transfer film described above. <8> The thickness of the above intermediate layer is 10 μm or less. <6> or <7> The transfer film described above. <9> The above intermediate layer includes a thermoplastic resin layer and a water-soluble resin layer. <6> ~ <8> A transfer film as described in one of the following. <10> The transfer film according to any one of <5> to <9>, wherein the photosensitive layer contains an alkali-soluble resin and a polymerizable compound, and the ratio of the mass of the polymerizable compound to the mass of the alkali-soluble resin in the photosensitive layer is 0.6 or more. <11> The transfer film according to any one of <5> to <10>, wherein the thickness of the photosensitive layer is 10 μm or less. <12> Peeling the protective film of the transfer film according to any one of <1> to <11>, laminating the transfer film and a substrate including a metal layer, and arranging the transfer layer and the temporary support on the metal layer of the substrate in this order; exposing the transfer layer; developing the transfer layer to form a resist pattern; etching or plating the metal layer not covered by the resist pattern; and peeling the resist pattern, in this order, a method for manufacturing a conductor pattern. <13> Peeling the protective film of the transfer film according to any one of <1> to <11>, laminating the transfer film and a substrate including a metal layer, and arranging the transfer layer and the temporary support on the metal layer of the substrate in this order; peeling the temporary support; exposing the transfer layer; developing the transfer layer to form a resist pattern; etching or plating the metal layer not covered by the resist pattern; and peeling the resist pattern, in this order, a method for manufacturing a conductor pattern. <14> The method for manufacturing a conductor pattern according to <13>, wherein the peeling strength of the temporary support in the peeling of the temporary support is 0.3 mN / mm to 2.0 mN / mm.

Advantages of the Invention

[0007] According to one embodiment of the present disclosure, a transfer film having excellent resolution is provided. According to another embodiment of the present disclosure, a method for manufacturing a conductor pattern using a transfer film having excellent resolution is provided.

Brief Description of the Drawings

[0008] [Figure 1] This is a schematic diagram showing an example of the configuration of a transfer film in one embodiment. [Figure 2] This is a schematic plan view showing pattern A. [Figure 3] This is a schematic plan view showing Pattern B. [Modes for carrying out the invention]

[0009] The contents of this disclosure are described below. While the explanation will be given with reference to the attached drawings, reference numerals may be omitted. In this disclosure, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. In this disclosure, "(meth)acrylic" refers to both acrylic and methacrylic, or either of them; "(meth)acrylate" refers to both acrylate and methacrylate, or either of them; and "(meth)acryloyl" refers to both acryloyl and methacryloyl, or either of them. In this disclosure, the amount of each component in a composition means the total amount of multiple substances corresponding to each component present in the composition, unless otherwise specified. In this disclosure, the term "process" includes not only independent processes but also any process that cannot be clearly distinguished from other processes, as long as its intended purpose is achieved. In the notation of groups (atomic groups) in this disclosure, notations that do not specify substitution or unsubstituted include both those with and without substituents. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups. In this disclosure, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Generally, the light used for exposure includes the emission spectrum of mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet (EUV) light, X-rays, electron beams, and other active light rays (active energy rays). In this disclosure, chemical structural formulas may also be described as simplified structural formulas in which hydrogen atoms are omitted. In this disclosure, "mass%" and "weight%" are synonymous, and "parts by mass" and "parts by weight" are synonymous. In this disclosure, a combination of two or more preferred embodiments is a more preferred embodiment. In this disclosure, "transparent" means that the average transmittance of visible light with wavelengths of 400 nm to 700 nm is 80% or more, and preferably 90% or more. In this disclosure, the average transmittance of visible light is a value measured using a spectrophotometer, which can be measured using, for example, a Hitachi U-3310 spectrophotometer manufactured by Hitachi, Ltd. In this disclosure, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are molecular weights obtained by detecting the solvent THF (tetrahydrofuran) using a differential refractometer with a gel permeation chromatography (GPC) analyzer using TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all product names of Tosoh Corporation) columns, and then converting them using polystyrene as a standard substance. In this disclosure, unless otherwise specified, the content of metal elements is measured using an inductively coupled plasma (ICP) spectrometer. In this disclosure, unless otherwise specified, the refractive index is the value measured using an ellipsometer at a wavelength of 550 nm. In this disclosure, unless otherwise specified, the hue values ​​are those measured using a colorimeter (CR-221, manufactured by Minolta, Inc.). In this disclosure, "alkali soluble" means that the solubility in 100 g of a 1% by mass aqueous solution of sodium carbonate at a liquid temperature of 22°C is 0.1 g or more. In this disclosure, "water-soluble" means that the solubility in 100g of water at a pH of 7.0 at a liquid temperature of 22°C is 0.1g or more. Therefore, for example, a water-soluble resin refers to a resin that satisfies the above-mentioned solubility conditions. In this disclosure, "solids" means all components excluding the solvent. In this disclosure, the thickness of each layer of the transfer film is measured by observing a cross-section perpendicular to the main surface of the transfer film using a scanning electron microscope (SEM), measuring the thickness of each layer at five or more arbitrary points based on the obtained observation image, and calculating the average value.

[0010] <Transfer film> A transfer film according to one embodiment of the present disclosure comprises, in this order, a temporary support, a transfer layer, and a protective film, wherein the storage modulus of the transfer layer on the protective film side at 25°C is 1.0 × 10 6 Pa~3.0×10 8 The storage modulus of the protective film side of the transfer layer is Pa. In this disclosure, the "storage modulus of the protective film side of the transfer layer" is defined by the storage modulus of the layer closest to the protective film in the transfer layer. For example, if the transfer layer has a multilayer structure, the storage modulus of the layer closest to the protective film among the multiple layers included in the transfer layer is called the "storage modulus of the protective film side of the transfer layer," and if the transfer layer has a single layer structure, the storage modulus of a single transfer layer is called the "storage modulus of the protective film side of the transfer layer." The storage modulus of the protective film side of the transfer layer at 25°C is 1.0 × 10⁻⁶. 6 When the storage modulus of the transfer layer on the protective film side of the transfer layer at 25°C is 3.0 × 10⁻⁶. 8 When the Pa value is less than or equal to Pa, the adhesion between the transfer layer and the object (e.g., a substrate) is improved during the transfer of the transfer layer to the object, and the resolution is also improved. Therefore, according to one embodiment of the present disclosure, a transfer film having excellent resolution is provided.

[0011] Each layer in the transfer film may have a single-layer or multi-layer structure. Examples of transfer layers include a photosensitive layer and an intermediate layer. Examples of intermediate layers include a thermoplastic resin layer and a water-soluble resin layer. Examples of the configuration of a transfer film are shown below. However, the configuration of the transfer film is not limited to the following examples. In each of the following configurations, the photosensitive layer is preferably a negative-type photosensitive layer. It is also preferable that the photosensitive layer be a colored resin layer.

[0012] (1) "Temporary support / photosensitive layer / protective film" (2) "Temporary support / intermediate layer / photosensitive layer / protective film" (3) "Temporary support / thermoplastic resin layer / water-soluble resin layer / photosensitive layer / protective film"

[0013] The structure of the transfer film will be described with reference to Figure 1. Figure 1 is a schematic diagram showing the structure of a transfer film according to a certain embodiment. The transfer film 100 shown in Figure 1 includes a temporary support 10, an intermediate layer 20, a photosensitive layer 30, and a protective film 40 in this order.

[0014] From the viewpoint of suppressing bubble generation in the lamination process described later, the maximum width of the waviness of the transfer film is preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 60 μm or less. The maximum width of the waviness of the transfer film is preferably 0 μm or more, more preferably 0.1 μm or more, and even more preferably 1 μm or more. The maximum width of the waviness of the transfer film is measured by the following procedure. First, the transfer film is cut perpendicular to the main surface to a size of 20 cm in length and 20 cm in width to prepare a test sample. If the transfer film includes a protective film, the protective film is peeled off. Next, the test sample is placed on a smooth, horizontal stage with the surface of the temporary support facing the stage. After placement, a 3D surface image is obtained by scanning the surface of the test sample in a 10 cm square area in the center of the test sample with a laser microscope (for example, VK-9700SP manufactured by Keyence Corporation), and the minimum concave height is subtracted from the maximum convex height observed in the obtained 3D surface image. The above procedure is performed on 10 test samples, and the arithmetic mean is defined as the "maximum width of the transfer film's waviness."

[0015] (Components of the transfer film: temporary support) A transfer film according to one embodiment of the present disclosure includes a temporary support, which is a peelable support that supports the transfer layer.

[0016] The surface roughness Ra of the temporary support facing the transfer layer is preferably 0.1 nm to 15 nm, more preferably 0.1 nm to 10 nm, even more preferably 0.1 nm to 6 nm, and particularly preferably 0.1 nm to 2 nm. Specifically, "the surface of the temporary support facing the transfer layer" refers to the surface of the temporary support that faces the transfer layer. When the surface roughness Ra of the temporary support facing the transfer layer is large, the peelability of the temporary support is improved, and for example, adhesion of the transfer layer to the surface of the peeled temporary support is suppressed. When the surface roughness Ra of the temporary support facing the transfer layer is small, the increase in the surface roughness Ra of the transfer layer caused by the temporary support is suppressed. In addition, when the surface roughness Ra of the temporary support facing the transfer layer is small, light scattering is suppressed during exposure of the transfer layer through the temporary support. As a result, resolution is improved.

[0017] The surface roughness Ra of the temporary support facing the transfer layer is the arithmetic mean roughness Ra measured by the following method: A 3D optical profiler (New View7300, Zygo) is used to obtain the surface profile of the target surface. The "Microscope Application" of "MetroPro ver8.3.2" is used as the measurement and analysis software. Next, the "Surface Map" screen is displayed using the above software, and histogram data is obtained on the "Surface Map" screen. The arithmetic mean roughness Ra of the target surface is calculated from the obtained histogram data. If the target surface is covered by other layers, the arithmetic mean roughness Ra of the target surface is measured after exposing the target surface by peeling off the other layers.

[0018] The temporary support may be a single-layer or multi-layer structure. The temporary support is preferably a film, and more preferably a resin film. The temporary support is preferably a film that is flexible and does not undergo significant deformation, shrinkage, or elongation under pressure, or under pressure and heat.

[0019] Examples of the film include polyethylene terephthalate (PET) film (e.g., biaxially stretched polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film. As the temporary support, a polyethylene terephthalate film is preferred. The film used as the temporary support preferably has no deformation such as wrinkles and no scratches.

[0020] From the viewpoint of being able to perform pattern exposure through the temporary support, it is preferable that the transparency of the temporary support is higher. The transmittance of the temporary support at 365 nm is preferably 60% or more, and more preferably 70% or more.

[0021] From the viewpoints of pattern formation property during pattern exposure through the temporary support and transparency of the temporary support, it is preferable that the haze of the temporary support is smaller. Specifically, the haze of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less.

[0022] From the viewpoints of pattern formation property during pattern exposure through the temporary support and transparency of the temporary support, it is preferable that the number of coarse particles, foreign matters, and defects contained in the temporary support is smaller. The number of particles, foreign matters, and defects with a diameter of 1 μm or more in the temporary support is preferably 50 pieces / 10 mm 2 or less, more preferably 10 pieces / 10 mm 2 or less, even more preferably 3 pieces / 10 mm 2 or less, and particularly preferably 0 pieces / 10 mm 2 .

[0023] The thickness of the temporary support is not particularly limited, but is preferably 5 μm to 200 μm, more preferably 10 μm to 150 μm from the viewpoints of ease of handling and versatility, and even more preferably 10 μm to 50 μm.

[0024] Examples of temporary supports include a biaxially oriented polyethylene terephthalate film with a thickness of 16 μm, a biaxially oriented polyethylene terephthalate film with a thickness of 12 μm, and a biaxially oriented polyethylene terephthalate film with a thickness of 9 μm.

[0025] Preferred embodiments of the temporary support are described, for example, in paragraphs 0017-0018 of Japanese Patent Publication No. 2014-85643, paragraphs 0019-0026 of Japanese Patent Publication No. 2016-27363, paragraphs 0041-0057 of International Publication No. 2012 / 081680, paragraphs 0029-0040 of International Publication No. 2018 / 179370, and paragraphs 0012-0032 of Japanese Patent Publication No. 2019-101405, the contents of which are incorporated herein by reference.

[0026] From the viewpoint of providing handling properties, a layer containing fine particles (also called a "lubricant layer" or "particle-containing layer") may be provided on the surface of the temporary support. The lubricant layer may be provided on one side of the temporary support or on both sides. The diameter of the particles contained in the lubricant layer is preferably 0.05 μm to 0.8 μm. The thickness of the lubricant layer is preferably 0.05 μm to 1.0 μm.

[0027] (Components of the transfer film: Transfer layer) A transfer film according to one embodiment of the present disclosure includes a transfer layer. The storage modulus of the protective film side of the transfer layer at 25°C is 1.0 × 10⁻⁶ 6 Pa~3.0×10 8 The storage modulus of the protective film side of the transfer layer at 25°C is 1.0 × 10⁻⁶. 6 When the storage modulus of the transfer layer on the protective film side of the transfer layer at 25°C is 3.0 × 10⁻⁶. 8 When the storage modulus is below Pa, the adhesion between the transfer layer and the object (e.g., a substrate) improves during the transfer of the transfer layer to the object, and the resolution also improves. From the viewpoint of resolution, the storage modulus of the protective film side of the transfer layer at 25°C is 1.0 × 10⁻⁶. 6 Pa~2.0×10 8It is preferably Pa, 1.0 × 10 7 Pa~1.0×10 8 It is more preferable that it be Pa.

[0028] The storage modulus of the temporary support side of the transfer layer at 25°C is 1.0 × 10⁻⁶ 6 It is preferable that it is Pa or higher. In this disclosure, the "storage modulus on the temporary support side of the transfer layer" is defined by the storage modulus of the layer closest to the temporary support in the transfer layer. For example, if the transfer layer has a multilayer structure, the storage modulus of the layer closest to the temporary support among the multiple layers included in the transfer layer is called the "storage modulus on the temporary support side of the transfer layer," and if the transfer layer has a single layer structure, the storage modulus of a single transfer layer is called the "storage modulus on the temporary support side of the transfer layer." The storage modulus on the temporary support side of the transfer layer at 25°C is 1.0 × 10⁻⁶. 6 When the storage modulus of the transfer layer on the surface of the peeled temporary support is greater than Pa, adhesion of the transfer layer to the surface of the temporary support is suppressed, and the decrease in resolution is also suppressed. When the storage modulus of the transfer layer on the temporary support side at 25°C is small, the resolution is improved, for example, in an exposure method in which the transfer layer and the photomask are in contact. From the viewpoint of resolution, the storage modulus of the transfer layer on the temporary support side at 25°C is 1.0 × 10⁻⁶. 6 Pa~3.0×10 8 It is preferably Pa, 1.0 × 10 6 Pa~2.0×10 8 It is more preferable that it be Pa, 1.0 × 10 7 Pa~1.0×10 8 It is even more preferable that it be Pa.

[0029] In this disclosure, the storage modulus is measured using a viscoelasticity measuring device (DHR-2 rheometer manufactured by T.A. Instruments), a 20 mmφ parallel plate, and a Peltier plate (Gap: approximately 0.5 mm) under the conditions of a temperature of 20°C to 125°C, a heating rate of 5°C / min, a frequency of 1 Hz, and a strain of 0.5%. Specifically, before measurement, the sample is melted on the Peltier plate at 80°C to 95°C, cooled to 20°C at a cooling rate of 5°C / min, and then measured in constant gap mode. The storage modulus value at 25°C is adopted.

[0030] The method for adjusting the storage modulus of the transfer layer is not limited. Factors that affect the storage modulus of the transfer layer include, for example, the composition of the transfer layer. The storage modulus of the transfer layer can be adjusted, for example, by the type of alkali-soluble resin, the type of polymerizable compound, the ratio of the mass of the polymerizable compound to the mass of the alkali-soluble resin, and the type of additive.

[0031] From the viewpoint of resolution, the surface roughness Ra of the transfer layer facing the temporary support is preferably 0.1 nm to 15 nm, more preferably 0.1 nm to 10 nm, even more preferably 0.1 nm to 6 nm, and particularly preferably 0.1 nm to 2 nm. Specifically, "the surface of the transfer layer facing the temporary support" refers to the surface of the transfer layer that faces the temporary support. The surface roughness Ra of the transfer layer facing the temporary support is measured by a method similar to the method for measuring the surface roughness Ra of the temporary support facing the transfer layer described in the "Temporary Support" section above.

[0032] The transfer layer may have a single-layer structure or a multi-layer structure. Preferably, the transfer layer includes a photosensitive layer. The transfer layer may also be a photosensitive layer. The transfer layer may further include layers other than the photosensitive layer. For example, the transfer layer may include an intermediate layer and a photosensitive layer. The intermediate layer improves the lamination properties of the transfer film. With the intermediate layer, for example, the conformability to the substrate during bonding of the transfer film to the substrate is improved, the inclusion of air bubbles between the substrate and the transfer film is suppressed, and the adhesion between the substrate and the transfer film is improved. Preferably, the intermediate layer is placed between the temporary support and the photosensitive layer. That is, the transfer film preferably includes a temporary support, an intermediate layer, a photosensitive layer, and a protective film in this order. Examples of intermediate layers include a thermoplastic resin layer and a water-soluble resin layer. The specific embodiments of each layer constituting the transfer layer will be described below.

[0033] (Component of the transfer layer: photosensitive layer) The photosensitive layer can form a pattern by exposure and development after being transferred onto a substrate, for example. The photosensitive layer may be a negative-type photosensitive layer or a positive-type photosensitive layer. It is preferable that the photosensitive layer is a negative-type photosensitive layer. When the photosensitive layer is a negative-type photosensitive layer, the formed pattern corresponds to the cured layer. When the photosensitive layer is a negative-type photosensitive layer, it is preferable that the negative-type photosensitive layer contains a resin, a polymerizable compound, and a polymerization initiator. Furthermore, when the photosensitive layer is a negative-type photosensitive layer, it is also preferable that the resin contains an alkali-soluble resin as part or all of it. In other words, in one embodiment, it is preferable that the photosensitive layer contains a resin including an alkali-soluble resin, a polymerizable compound, and a polymerization initiator. It is preferable that the photosensitive layer contains 10% to 90% by mass of alkali-soluble resin, 5% to 70% by mass of ethylenically unsaturated compound, and 0.01% to 20% by mass of photopolymerization initiator, based on the total mass of the photosensitive layer.

[0034] (Photosensitive layer component: Alkali-soluble resin) The photosensitive layer preferably contains an alkali-soluble resin. Suitable alkali-soluble resins include, for example, known alkali-soluble resins used in etching resists. Furthermore, the alkali-soluble resin is preferably a binder polymer. The alkali-soluble resin is preferably an alkali-soluble resin having acid groups. Polymer A, described later, is preferred as the alkali-soluble resin.

[0035] The photosensitive layer preferably contains polymer A as an alkali-soluble resin. To improve resolution by suppressing swelling of the photosensitive layer due to the developer, the acid value of polymer A is preferably 220 mgKOH / g or less, more preferably less than 200 mgKOH / g, and even more preferably less than 190 mgKOH / g. There is no particular lower limit to the acid value of polymer A. To improve developability, the acid value of polymer A is preferably 60 mgKOH / g or more, more preferably 120 mgKOH / g or more, even more preferably 150 mgKOH / g or more, and particularly preferably 170 mgKOH / g or more. The acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of sample, and in this disclosure, the unit is expressed as mgKOH / g. The acid value can be calculated, for example, from the average content of acid groups in the compound. The acid value of polymer A can be adjusted by the type of constituent units that make up polymer A and the content of constituent units containing acid groups.

[0036] The weight-average molecular weight of polymer A is preferably 5,000 to 500,000. A weight-average molecular weight of 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, even more preferably 60,000 or less, and particularly preferably 50,000 or less. On the other hand, a weight-average molecular weight of 5,000 or more is preferable from the viewpoint of controlling the properties of developed aggregates and the properties of the unexposed film, such as edge fusing and cut-tip properties in the photosensitive layer. The weight-average molecular weight of polymer A is more preferably 10,000 or more, even more preferably 20,000 or more, and particularly preferably 30,000 or more. Edge fusing refers to the degree to which the photosensitive layer tends to protrude from the edge of the roll when the transfer film is wound into a roll. Cut-tip properties refer to the degree to which chips tend to fly off when the unexposed film is cut with a cutter. If this chip adheres to the upper surface of the photosensitive layer, it will be transferred to the mask during subsequent exposure processes, causing defective products. The degree of dispersion of polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0. In this disclosure, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​measured using gel permeation chromatography. Furthermore, the degree of dispersion is the ratio of the weight-average molecular weight to the number-average molecular weight (weight-average molecular weight / number-average molecular weight).

[0037] From the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position shifts during exposure, polymer A preferably has aromatic hydrocarbon groups, and more preferably has constituent units having aromatic hydrocarbon groups. Examples of aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The content of constituent units having aromatic hydrocarbon groups in polymer A is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, particularly preferably 45% by mass or more, and most preferably 50% by mass or more, based on the total mass of polymer A. There is no particular upper limit, but it is preferably 95% by mass or less, more preferably 85% by mass or less. When multiple types of polymer A are contained, the content of constituent units having aromatic hydrocarbon groups is determined as the weight average.

[0038] Examples of monomers that form structural units having aromatic hydrocarbon groups include monomers having aralkyl groups, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.). Among these, monomers having aralkyl groups or styrene are preferred. In one embodiment, when the monomer forming structural units having aromatic hydrocarbon groups in polymer A is styrene, the content of styrene-derived structural units is preferably 20% to 50% by mass, more preferably 25% to 45% by mass, even more preferably 30% to 40% by mass, and particularly preferably 30% to 35% by mass, based on the total mass of polymer A.

[0039] Examples of aralkyl groups include substituted or unsubstituted phenylalkyl groups, with substituted or unsubstituted benzyl groups being preferred.

[0040] Examples of monomers having phenylalkyl groups other than substituted or unsubstituted benzyl groups include phenylethyl (meth)acrylate.

[0041] Examples of monomers having substituted or unsubstituted benzyl groups include (meth)acrylates having substituted or unsubstituted benzyl groups (e.g., benzyl (meth)acrylate, chlorobenzyl (meth)acrylate, etc.) and vinyl monomers having benzyl groups (e.g., vinylbenzyl chloride, vinylbenzyl alcohol, etc.). Among these, benzyl (meth)acrylate is preferred. In one embodiment, when the monomer forming the constituent unit having an aromatic hydrocarbon group in polymer A is benzyl (meth)acrylate, the content of the constituent unit derived from benzyl (meth)acrylate is preferably 50% to 95% by mass, more preferably 60% to 90% by mass, even more preferably 70% to 90% by mass, and particularly preferably 75% to 90% by mass, based on the total mass of polymer A.

[0042] Polymer A having a constituent unit having an aromatic hydrocarbon group is preferably obtained by polymerizing a monomer having an aromatic hydrocarbon group with at least one of the first monomers described later and / or at least one of the second monomers described later.

[0043] Polymer A, which does not have a constituent unit having an aromatic hydrocarbon group, is preferably obtained by polymerizing at least one of the first monomers described later, and more preferably by copolymerizing at least one of the first monomers with at least one of the second monomers described later.

[0044] The first monomer is a monomer having a carboxyl group in its 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.

[0045] The content of the constituent units derived from the first monomer in polymer A is preferably 5% to 50% by mass, more preferably 10% to 40% by mass, and even more preferably 15% to 30% by mass, based on the total mass of polymer A.

[0046] The content of the constituent units derived from the first monomer is preferably 10% to 50% by mass, based on the total mass of polymer A. A content of 10% by mass or more is preferable from the viewpoint of exhibiting good developability and controlling edge fusing, more preferably 15% by mass or more, and even more preferably 20% by mass or more. A content of 50% by mass or less is preferable from the viewpoint of high resolution and tail shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern, and in these viewpoints, 35% by mass or less is more preferable, 30% by mass or less is even more preferable, and 27% by mass or less is particularly preferable.

[0047] The second monomer is non-acidic and has at least one ethylenically unsaturated group in its molecule. Examples of the second monomer include (meth)acrylates such as 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 alcohols such as 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.

[0048] The content of the constituent units derived from the second monomer in polymer A is preferably 5% to 60% by mass, more preferably 15% to 50% by mass, and even more preferably 20% to 45% by mass, based on the total mass of polymer A.

[0049] Furthermore, it is preferable that polymer A contains at least one structural unit selected from the group consisting of structural units having an aralkyl group and structural units derived from styrene, from the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position shifts during exposure. As polymer A, for example, copolymers containing methacrylic acid, benzyl methacrylate and styrene, copolymers containing methacrylic acid, methyl methacrylate and benzyl methacrylate and styrene, etc., are preferred.

[0050] In one embodiment, polymer A is preferably a polymer containing 25% to 40% by mass of constituent units having aromatic hydrocarbon groups, 20% to 35% by mass of constituent units derived from the first monomer, and 30% to 45% by mass of constituent units derived from the second monomer. In another embodiment, polymer A is preferably a polymer containing 70% to 90% by mass of constituent units having aromatic hydrocarbon groups and 10% to 25% by mass of constituent units derived from the first monomer.

[0051] Polymer A may have a branched structure and / or an alicyclic structure in its side chains. A branched structure or an alicyclic structure can be introduced into the side chains of polymer A by using a monomer containing a group having a branched structure in its side chains, or a monomer containing a group having an alicyclic structure in its side chains. The alicyclic structure may be monocyclic or polycyclic.

[0052] Specific examples of monomers containing a group having a branched structure in its side chain include i-propyl (meth)acrylate, i-butyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, i-amyl (meth)acrylate, t-amyl (meth)acrylate, isoamyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and t-octyl (meth)acrylate. Among these, i-propyl (meth)acrylate, i-butyl (meth)acrylate, or t-butyl methacrylate are preferred, and i-propyl methacrylate or t-butyl methacrylate are more preferred.

[0053] Specific examples of monomers containing a group with an alicyclic structure in its side chain include monomers having a monocyclic aliphatic hydrocarbon group and monomers having a polycyclic aliphatic hydrocarbon group. Also, (meth)acrylates having an alicyclic hydrocarbon group with 5 to 20 carbon atoms are examples. More specific examples include (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 Examples include C-1-adamantyl, octahydro-4,7-menthanoinden-5-yl (meth)acrylate, octahydro-4,7-menthanoinden-1-ylmethyl (meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl (meth)acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fentyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, and cyclohexyl (meth)acrylate.

[0054] Among these (meth)acrylic acid esters, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fentyl (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecane (meth)acrylate are preferred, and cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate are more preferred.

[0055] The photosensitive layer may contain polymer A alone or two or more types. When two or more types are included, it is preferable to use a mixture of two types of polymer A having aromatic hydrocarbon groups, or to use a mixture of polymer A having aromatic hydrocarbon groups and polymer A not having aromatic hydrocarbon groups. In the latter case, the content of polymer A having aromatic hydrocarbon groups is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of polymer A.

[0056] The synthesis of polymer A is preferably carried out by adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to a solution obtained by diluting one or more monomers described above with a solvent such as acetone, methyl ethyl ketone, or isopropanol, and then heating and stirring. In some cases, the synthesis may be carried out by adding a portion of the mixture dropwise to the reaction solution. After the reaction is complete, the solvent may be further added to adjust the concentration to the desired level. In addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may also be used as synthesis methods.

[0057] The glass transition temperature (Tg) of polymer A is preferably 30°C or higher and 135°C or lower. By using polymer A having a Tg of 135°C or lower in the photosensitive layer, line width thickening and deterioration of resolution when the focal position shifts during exposure can be suppressed. From this viewpoint, the Tg of polymer A is more preferably 130°C or lower, even more preferably 120°C or lower, and particularly preferably 110°C or lower. Furthermore, using polymer A having a Tg of 30°C or higher is preferable from the viewpoint of improving edge fusing resistance. From this viewpoint, the Tg of polymer A is more preferably 40°C or higher, even more preferably 50°C or higher, particularly preferably 60°C or higher, and most preferably 70°C or higher.

[0058] Alkali-soluble resins may be used individually or in mixtures of two or more types. The ratio of alkali-soluble resin to the total mass of the photosensitive layer is preferably 10% to 90% by mass, more preferably 30% to 70% by mass, and even more preferably 40% to 60% by mass. A ratio of alkali-soluble resin to the photosensitive layer of 90% by mass or less is preferable from the viewpoint of controlling the development time. On the other hand, a ratio of alkali-soluble resin to the photosensitive layer of 10% by mass or more is preferable from the viewpoint of improving edge fusing resistance.

[0059] The photosensitive layer may contain resins other than alkali-soluble resins. Examples of resins other than alkali-soluble resins include any resin whose solubility in 100 g of a 1% aqueous solution of sodium carbonate at a liquid temperature of 22°C is less than 0.1 g. Examples include acrylic resins, styrene-acrylic copolymers (provided the styrene content is 40% by mass or less), polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0060] (Composition of the photosensitive layer: polymerizable compounds) When the photosensitive layer is a negative-type photosensitive layer, it is preferable that the negative-type photosensitive layer contains a polymerizable compound having polymerizable groups. In this disclosure, "polymerizable compound" means a compound that polymerizes upon the action of a polymerization initiator and is different from the alkali-soluble resin described above. The molecular weight of the polymerizable compound is preferably 1,500 or less. The molecular weight of the polymerizable compound is preferably 150 or more.

[0061] The type of polymerizable group is not limited as long as it is a group that participates in the polymerization reaction. Examples of polymerizable groups include groups having ethylenically unsaturated groups such as vinyl groups, acryloyl groups, methacryloyl groups, styryl groups, and maleimide groups. Examples of polymerizable groups include groups having cationic polymerizable groups such as epoxy groups and oxetane groups. Groups having ethylenically unsaturated groups are preferred as polymerizable groups, and acryloyl groups or methacryloyl groups are more preferred.

[0062] The polymerizable compound preferably contains polymerizable compounds having two or more polymerizable groups. More preferably, the polymerizable compound contains polymerizable compounds having two or more polymerizable groups and polymerizable compounds having three or more polymerizable groups.

[0063] As polymerizable compounds, compounds having one or more ethylenically unsaturated groups (i.e., ethylenically unsaturated compounds) are preferred in terms of having superior photosensitivity of the negative-type photosensitive layer, and compounds having two or more ethylenically unsaturated groups in one molecule (i.e., polyfunctional ethylenically unsaturated compounds) are more preferred. Furthermore, in terms of superior resolution and peelability, the number of ethylenically unsaturated groups in one molecule of the ethylenically unsaturated compound is preferably six or less, more preferably three or less, and even more preferably two or less.

[0064] In order to achieve a better balance between the photosensitivity, resolution, and peelability of the negative-type photosensitive layer, the photosensitive layer preferably contains a compound having two or three ethylenically unsaturated groups in one molecule (i.e., a difunctional or trifunctional ethylenically unsaturated compound), and more preferably contains a compound having two ethylenically unsaturated groups in one molecule (i.e., a difunctional ethylenically unsaturated compound). From the viewpoint of excellent peelability, the content of the difunctional ethylenically unsaturated compound relative to the total mass of the polymerizable compound is preferably 20% by mass or more, more preferably more than 40% by mass, and even more preferably 55% by mass or more, relative to the total mass of the negative-type photosensitive layer. There is no particular upper limit, and it may be 100% by mass. That is, all polymerizable compounds may be difunctional ethylenically unsaturated compounds. Furthermore, as the ethylenically unsaturated compound, a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group is preferred.

[0065] The photosensitive layer preferably contains an ethylenically unsaturated compound B1 having an aromatic ring and two ethylenically unsaturated groups. The ethylenically unsaturated compound B1 is a difunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule, among the ethylenically unsaturated compounds described above.

[0066] In the photosensitive layer, the mass ratio of the ethylenically unsaturated compound B1 content to the ethylenically unsaturated compound content is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 55% by mass or more, and particularly preferably 60% by mass or more, from the viewpoint of superior resolution. There is no particular upper limit, but from the viewpoint of peelability, it is preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, and particularly preferably 85% by mass or less.

[0067] Examples of aromatic rings in ethylenically unsaturated compound B1 include aromatic hydrocarbon rings such as benzene rings, naphthalene rings, and anthracene rings; aromatic heterocycles such as thiophene rings, furan rings, pyrrole rings, imidazole rings, triazole rings, and pyridine rings; and fused rings thereof. Aromatic hydrocarbon rings are preferred, and benzene rings are more preferred. The above aromatic rings may have substituents. Ethyleneally unsaturated compound B1 may have only one aromatic ring, or it may have two or more aromatic rings.

[0068] Ethylene-unsaturated compound B1 is preferably a bisphenol structure because it improves resolution by suppressing swelling of the photosensitive layer due to the developer. Examples of bisphenol structures 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), with the bisphenol A structure being preferred.

[0069] Examples of ethylenically unsaturated compounds B1 having a bisphenol structure include compounds having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. The two polymerizable groups may be directly bonded to both ends of the bisphenol structure or bonded via one or more alkylene oxy groups. The alkylene oxy groups added to both ends of the bisphenol structure are preferably ethylene oxy groups or propylene oxy groups, with ethylene oxy groups being more preferred. The number of alkylene oxy groups added to the bisphenol structure is not particularly limited, but 4 to 16 per molecule is preferred, and 6 to 14 is more preferred. Ethyleneally unsaturated compounds B1 having a bisphenol structure are described in paragraphs 0072 to 0080 of Japanese Patent Application Publication No. 2016-224162, and the contents described in this publication are incorporated herein by reference.

[0070] As the ethylenically unsaturated compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferred, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferred. Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin Nakamura Chemical Co., Ltd.), and 2,2-bis(4-(methacryloxydodecaethoxy) Examples include trapoxy(phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and ethoxylated(10)bisphenol A diacrylate (NK ester A-BPE-10, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).

[0071] From the viewpoint of line width change during exposure time, line width change at development temperature, and sensitivity, it is preferable that the ethylenically unsaturated compound B1 includes a compound represented by the following formula (Bis).

[0072] [ka]

[0073] In formula (Bis), R1 and R2 each independently represent a hydrogen atom or a methyl group, A is C2H4, B is C3H6, n1 and n3 each independently are integers from 1 to 39, and n1+n3 is an integer from 2 to 40, and n2 and n4 each independently are integers from 0 to 29, and n2+n4 is an integer from 0 to 30, and the arrangement of the repeating units -(AO)- and -(BO)- may be random or in blocks. In the case of blocks, either -(AO)- or -(BO)- may be on the bisphenol structure side. In one embodiment, n1+n2+n3+n4 is preferably an integer from 2 to 20, more preferably from 2 to 16, and even more preferably from 4 to 12. Also, n2+n4 is preferably an integer from 0 to 10, more preferably from 0 to 4, even more preferably from 0 to 2, and particularly preferably 0.

[0074] Ethylene-unsaturated compound B1 may be used alone or in combination of two or more types. The content of ethylenically unsaturated compound B1 in the photosensitive layer is preferably 10% by mass or more, and more preferably 20% by mass or more, relative to the total mass of the photosensitive layer, from the viewpoint of superior resolution. There is no particular upper limit, but from the viewpoint of transferability and edge fusion (the phenomenon in which components in the photosensitive layer seep out from the edges of the transfer film), it is preferably 70% by mass or less, and more preferably 60% by mass or less.

[0075] The photosensitive layer may contain ethylenically unsaturated compounds other than the ethylenically unsaturated compound B1 described above. The ethylenically unsaturated compounds other than ethylenically unsaturated compound B1 are not particularly limited and can be appropriately selected from known compounds. Examples include compounds having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compounds), difunctional ethylenically unsaturated compounds without aromatic rings, and trifunctional or more ethylenically unsaturated compounds.

[0076] Examples of monofunctional ethylenically unsaturated compounds 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.

[0077] Examples of bifunctional ethylenically unsaturated compounds that do not have an aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate.

[0078] Examples of alkylene glycol di(meth)acrylates include tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), tricyclodecanedimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate.

[0079] Examples of polyalkylene glycol di(meth)acrylates include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate.

[0080] Examples of urethane di(meth)acrylates include propylene oxide-modified urethane di(meth)acrylates and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates. Examples of commercially available urethane di(meth)acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).

[0081] Examples of ethylenically unsaturated compounds with three or more functions include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide modified products thereof. Here, "(tri / tetra / penta / hexa)(meth)acrylate" is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate. In one embodiment, the photosensitive layer preferably contains the ethylenically unsaturated compound B1 described above and a trifunctional or higher ethylenically unsaturated compound, and more preferably contains the ethylenically unsaturated compound B1 described above and two or more trifunctional or higher ethylenically unsaturated compounds. In this case, the mass ratio of the ethylenically unsaturated compound B1 to the trifunctional or higher ethylenically unsaturated compounds is preferably (total mass of ethylenically unsaturated compound B1):(total mass of trifunctional or higher ethylenically unsaturated compounds) = 1:1 to 5:1, more preferably 1.2:1 to 4:1, and even more preferably 1.5:1 to 3:1. Also in one embodiment, the photosensitive layer preferably contains the ethylenically unsaturated compound B1 described above and two or more trifunctional ethylenically unsaturated compounds.

[0082] Examples of alkylene oxide modified products of ethylenically unsaturated compounds with three or more functions include caprolactone-modified (meth)acrylate compounds (such as KAYARAD® DPCA-20 manufactured by Nippon Kayaku Co., Ltd. and A-9300-1CL manufactured by Shin Nakamura Chemical Industry Co., Ltd.), alkylene oxide-modified (meth)acrylate compounds (such as KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin Nakamura Chemical Industry Co., Ltd., and EBECRYL® 135 manufactured by Daicel Ornex), ethoxylated glycerin triacrylate (such as A-GLY-9E manufactured by Shin Nakamura Chemical Industry Co., Ltd.), Aronics® TO-2349 (manufactured by Toagosei Co., Ltd.), Aronics M-520 (manufactured by Toagosei Co., Ltd.), and Aronics M-510 (manufactured by Toagosei Co., Ltd.).

[0083] Furthermore, as an ethylenically unsaturated compound other than ethylenically unsaturated compound B1, an ethylenically unsaturated compound having an acid group as described in paragraphs 0025 to 0030 of Japanese Patent Application Publication No. 2004-239942 may be used.

[0084] From the viewpoint of resolution and linearity, the ratio Mm / Mb of the ethylenically unsaturated compound content in the photosensitive layer to the alkali-soluble resin content Mb is preferably 1.0 or less, more preferably 0.9 or less, and particularly preferably 0.5 to 0.9. Furthermore, from the viewpoint of curability and resolution, the ethylenically unsaturated compound in the photosensitive layer preferably contains a (meth)acrylic compound, and more preferably contains a (meth)acrylate compound. Moreover, from the viewpoint of curability, resolution and linearity, the ethylenically unsaturated compound in the photosensitive layer preferably contains a (meth)acrylic compound, and the content of the acrylic compound relative to the total mass of the (meth)acrylic compound contained in the photosensitive layer is preferably 60% by mass or less.

[0085] The molecular weight (or weight-average molecular weight (Mw) if there is a distribution) of the ethylenically unsaturated compound containing ethylenically unsaturated compound B1 is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.

[0086] Polymerizable compounds preferably contain an oxyethylene chain. The oxyethylene chain is a substructure represented by -CH2-CH2-O-. Examples of polymerizable compounds containing an oxyethylene chain include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin Nakamura Chemical Co., Ltd.), and 2,2-bis(4-(methacryloxydodecaethoxytetrapropoxy)phenyl Examples include 2,2-(4-(methacryloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 2,2-(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and ethoxylated (10)bisphenol A diacrylate (NK ester A-BPE-10, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).

[0087] The polymerizable compound may be used alone or in combination of two or more. The content of the polymerizable compound in the photosensitive layer is preferably 10% to 70% by mass, more preferably 20% to 60% by mass, and even more preferably 20% to 50% by mass, based on the total mass of the photosensitive layer.

[0088] When the photosensitive layer contains an alkali-soluble resin and a polymerizable compound, the ratio of the mass of the polymerizable compound to the mass of the alkali-soluble resin in the photosensitive layer is preferably 0.6 or higher, more preferably 0.7 to 1.1, and particularly preferably 0.8 to 1.0. The ratio of the mass of the polymerizable compound to the mass of the alkali-soluble resin in the photosensitive layer affects the storage modulus of the photosensitive layer. For example, if the ratio of the mass of the polymerizable compound to the mass of the alkali-soluble resin in the photosensitive layer is large, the storage modulus of the photosensitive layer will be small. When the storage modulus of the photosensitive layer is small, the adhesion between the transfer layer and the object (e.g., a substrate) during transfer of the transfer layer to the object is improved, and the resolution is also improved. On the other hand, if the ratio of the mass of the polymerizable compound to the mass of the alkali-soluble resin in the photosensitive layer is small, the storage modulus of the photosensitive layer will be large. When the storage modulus of the photosensitive layer is large, the adhesion of the transfer layer to the surface of the peeled temporary support or protective film is suppressed, and the decrease in resolution is also suppressed.

[0089] (Components of the photosensitive layer: polymerization initiator) When the photosensitive layer is a negative-type photosensitive layer, it is preferable that the negative-type photosensitive layer contains a polymerization initiator. The polymerization initiator is selected according to the type of polymerization reaction, and examples include thermal polymerization initiators and photopolymerization initiators. Other examples of polymerization initiators include radical polymerization initiators and cationic polymerization initiators.

[0090] The negative photosensitive layer preferably contains a photopolymerization initiator. The photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound upon exposure to active light such as ultraviolet light, visible light, and X-rays. The photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used. Examples of photopolymerization initiators include photoradical polymerization initiators and photocationic polymerization initiators, with photoradical polymerization initiators being preferred.

[0091] Examples of photo-radical polymerization initiators include photopolymerization initiators having an oxime ester structure, photopolymerization initiators having an α-aminoalkylphenone structure, photopolymerization initiators having an α-hydroxyalkylphenone structure, photopolymerization initiators having an acylphosphine oxide structure, and photopolymerization initiators having an N-phenylglycine structure.

[0092] Furthermore, the negative photosensitive layer preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and their derivatives as a photoradical polymerization initiator, from the viewpoint of photosensitivity, visibility of exposed and unexposed areas, and resolution. 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 derivatives of the 2,4,5-triarylimidazole dimer include 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.

[0093] As photoradical polymerization initiators, for example, polymerization initiators described in paragraphs 0031 to 0042 of Japanese Patent Publication No. 2011-95716 and paragraphs 0064 to 0081 of Japanese Patent Publication No. 2015-14783 may be used.

[0094] Examples of photoradical polymerization initiators include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (trade name: manufactured by Midori Chemical Co., Ltd.), benzophenone, TAZ-111 (trade name: manufactured by Midori Chemical Co., Ltd.), Irgacure OXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad 651 and 369 (trade name: manufactured by IGM Resins BV), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0095] Examples of commercially available photoradical polymerization initiators include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyl oxime) (trade name: IRGACURE® OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyl oxime) (trade name: IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins BV), and 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907 (manufactured by IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (product name: Omnirad 127, manufactured by IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (product name: Omnirad 369, manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropan-1-one (product name: Omnirad 1173, manufactured by IGM Resins BV), 1-hydroxycyclohexylphenyl ketone (product name: Omnirad 184, manufactured by IGM Resins BV), 2,2-dimethoxy-1,2-diphenylethane-1-one (product name: Omnirad 651, manufactured by IGM Resins (Manufactured by BV), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (Trade name: Omnirad TPO H, manufactured by IGM Resins BV), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Trade name: Omnirad 819, manufactured by IGM Resins BV)(Manufactured by DKSH Japan Co., Ltd.), oxime ester-based photopolymerization initiator (product name: Lunar 6, manufactured by DKSH Japan Co., Ltd.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (product name: B-CIM, manufactured by Hampford), 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (product name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyl oxime) (product name: TR-PBG-305, manufactured by Tokyo Chemical Industry Co., Ltd.) Examples include 1,2-propanedione,3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazole-3-yl]-,2-(O-acetyloxime) (trade name: TR-PBG-326, manufactured by Changzhou Strong Electronic 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, manufactured by Changzhou Strong Electronic Materials Co., Ltd.).

[0096] A photocationic polymerization initiator (photoacid generator) is a compound that generates acid upon receiving active light. While compounds that are sensitive to active light with a wavelength of 300 nm or higher, preferably 300-450 nm, and generate acid are preferred as photocationic polymerization initiators, their chemical structure is not limited. Furthermore, photocationic polymerization initiators that are not directly sensitive to active light with a wavelength of 300 nm or higher can also be preferably used in combination with a sensitizer, provided they become sensitive to active light with a wavelength of 300 nm or higher and generate acid. As the photocationic polymerization initiator, a photocationic polymerization initiator that generates an acid with a pKa of 4 or less is preferred, a photocationic polymerization initiator that generates an acid with a pKa of 3 or less is more preferred, and a photocationic polymerization initiator that generates an acid with a pKa of 2 or less is particularly preferred. There is no specific lower limit for the pKa, but for example, -10.0 or higher is preferred.

[0097] Examples of photocationic polymerization initiators include ionic photocationic polymerization initiators and nonionic photocationic polymerization initiators. Examples of ionic photocationic polymerization initiators include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts. As an ionic photocationic polymerization initiator, an ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of Japanese Patent Application Publication No. 2014-85643 may be used.

[0098] Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triazines, diazomethane compounds, imidosulfonate compounds, and oximesulfonate compounds. For trichloromethyl-s-triazines, diazomethane compounds, and imidosulfonate compounds, compounds described in paragraphs 0083 to 0088 of Japanese Patent Publication No. 2011-221494 may be used. For oximesulfonate compounds, compounds described in paragraphs 0084 to 0088 of International Publication No. 2018 / 179640 may be used.

[0099] The photosensitive layer may contain one type of photopolymerization initiator alone, or two or more types. The amount of photopolymerization initiator in the photosensitive layer is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, based on the total mass of the photosensitive layer. There is no particular upper limit, but is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the photosensitive layer.

[0100] (Photosensitive layer components: dyes) The photosensitive layer preferably contains a dye, from the viewpoint of visibility of exposed and unexposed areas, pattern visibility after development, and resolution. It is more preferable that the dye contains a dye (also simply called "dye N") whose maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development is 450 nm or higher, and whose maximum absorption wavelength changes with the presence of an acid, base, or radical. Although the detailed mechanism is unknown, the presence of dye N improves adhesion with adjacent layers (e.g., temporary support and intermediate layer) and results in superior resolution.

[0101] In this disclosure, the phrase "the maximum absorption wavelength of a dye changes due to an acid, base, or radical" may mean any of the following: a dye in a colored state becomes decolorized due to an acid, base, or radical; a dye in a decolorized state becomes colored due to an acid, base, or radical; or a dye in a colored state changes to a colored state of another hue. Specifically, dye N may be a compound that changes from a decolorized state to a colored state upon exposure, or a compound that changes from a colored state to a decolorized state upon exposure. In this case, the dye may change its colored or decolorized state due to the generation and action of an acid, base, or radical within the photosensitive layer upon exposure, or it may be a dye that changes its colored or decolorized state due to a change in the state within the photosensitive layer (e.g., pH) due to an acid, base, or radical. Furthermore, the dye may change its colored or decolorized state upon direct stimulation by an acid, base, or radical without exposure.

[0102] In particular, from the viewpoint of visibility and resolution of the exposed and unexposed areas, the dye N is preferably a dye whose maximum absorption wavelength changes with acid or radicals, and more preferably a dye whose maximum absorption wavelength changes with radicals. From the viewpoint of visibility and resolution of the exposed and unexposed areas, the photosensitive layer preferably contains both a dye N whose maximum absorption wavelength changes due to radicals, and a photoradical polymerization initiator. Furthermore, from the viewpoint of visibility between the exposed and unexposed areas, it is preferable that the dye N is a dye that develops color in response to an acid, base, or radical.

[0103] An example of the color development mechanism of dye N in this disclosure is a configuration in which a photoradical polymerization initiator, a photocationic polymerization initiator (i.e., a photoacid generator), or a photobase generator is added to the photosensitive layer, and after exposure, a radical-reactive dye, an acid-reactive dye, or a base-reactive dye (e.g., a leuco dye) develops color due to radicals, acids, or bases generated from the photoradical polymerization initiator, photocationic polymerization initiator, or photobase generator.

[0104] From the viewpoint of visibility of the exposed and unexposed areas, the maximum absorption wavelength of dye N in the wavelength range of 400 nm to 780 nm during color development is preferably 550 nm or higher, more preferably 550 nm to 700 nm, and even more preferably 550 nm to 650 nm. Furthermore, dye N may have only one maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development, or it may have two or more. If dye N has two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm during color development, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths should be 450 nm or higher.

[0105] The maximum absorption wavelength of dye N is obtained by measuring the transmission spectrum of a solution containing dye N (at a temperature of 25°C) in the range of 400 nm to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) in an atmospheric environment, and detecting the wavelength at which the light intensity is minimum (i.e., the maximum absorption wavelength).

[0106] Examples of dyes that develop or decolorize upon exposure include leuco compounds. Examples of dyes that decolorize upon exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes. From the viewpoint of visibility between the exposed and unexposed areas, leuco compounds are preferred as dye N.

[0107] Examples of leuco compounds include leuco compounds having a triarylmethane skeleton (i.e., triarylmethane dyes), leuco compounds having a spiropyran skeleton (i.e., spiropyran dyes), leuco compounds having a fluorane skeleton (i.e., fluorane dyes), leuco compounds having a diarylmethane skeleton (i.e., diarylmethane dyes), leuco compounds having a rhodamine lactam skeleton (i.e., rhodamine lactam dyes), leuco compounds having an indolylphthalide skeleton (i.e., indolylphthalide dyes), and leuco compounds having a leucoauramine skeleton (i.e., leucoauramine dyes). Among these, triarylmethane dyes or fluorane dyes are preferred, and leuco compounds having a triphenylmethane skeleton (i.e., triphenylmethane dyes) or fluorane dyes are more preferred.

[0108] As a leuco compound, it is preferable to have a lactone ring, sultine ring, or sultone ring from the viewpoint of visibility between the exposed and unexposed areas. This allows the lactone ring, sultine ring, or sultone ring of the leuco compound to react with radicals generated from a photoradical polymerization initiator or acids generated from a photocationic polymerization initiator, thereby changing the leuco compound to a closed state and decolorizing it, or changing the leuco compound to an open state and developing color. As a leuco compound, it is preferable to have a lactone ring, sultine ring, or sultone ring, and the lactone ring, sultine ring, or sultone ring opens and develops color in response to radicals or acids, and more preferably a lactone ring, and the lactone ring opens and develops color in response to radicals or acids.

[0109] Examples of dye N include the following dyes and leuco compounds. Specific examples of dyes among dye N include Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuchsine, Methyl Violet 2B, Quinaldine Red, Rose Bengal, Methanyl Yellow, Thymol Sulfophthalein, Xylenol Blue, Methyl Orange, Paramethyl Red, Congofred, Benzopurine 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Parafuchsine, Victoria Pure Blue-Naphthalene Sulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Co., Ltd.), Oil Pink #312 (manufactured by Orient Chemical Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Co., Ltd.), Oil Scarlet #308 (manufactured by Orient Chemical Co., Ltd.) Examples include: Oil Red OG (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Industry Co., Ltd.), Oil Green #502 (manufactured by Orient Chemical Industry Co., Ltd.), Spiron Red BEH Special (manufactured by Hodogaya Chemical Industry Co., Ltd.), m-Cresol Purple, Cresol Red, Rhodamine B, Rhodamine 6G, Sulforhodamine B, Auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-pN,N-bis(hydroxyethyl)aminophenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0110] Specific examples of leuco compounds among the pigment N include p,p',p''-hexamethyltriaminotriphenylmethane (also called leucocrystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoylleucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(Np-tolyl-N-ethyl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluorane, 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, and 3-(N-cyclohexyl-N-methylamino)-6 -Methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-xylidinofluorane, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorane, 3-(N,N-diethylamino)-6-methoxy-7-aminofluorane, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluorane, 3-(N,N-diethylamino)-7-chlorofluorane, 3-(N,N-diethylamino) (Tylamino)-7-benzylaminofluorane, 3-(N,N-diethylamino)-7,8-benzofluorane, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluorane, 3-(N,N-dibutylamino)-6-methyl-7-xylidinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3,3-bis(1-ethyl-2-methylindole-3-yl)phthalide, 3,3-bis(1-n-butyl-2-methylindole-3-yl)phthalide Examples include cylindole-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-azaphthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)phthalide, and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthene-3-one.

[0111] From the viewpoint of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, 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. As dye N, leucocrystal violet, crystal violet lactone, brilliant green, or Victoria pure blue naphthalene sulfonate are preferred.

[0112] The dye may be used alone or in combination of two or more types. From the viewpoint of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, the dye content is preferably 0.1% by mass or more, more preferably 0.1% to 10% by mass, even more preferably 0.1% to 5% by mass, and particularly preferably 0.1% to 1% by mass, relative to the total mass of the photosensitive layer. Furthermore, from the viewpoint of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, the dye content of dye N is preferably 0.1% by mass or more, more preferably 0.1% to 10% by mass, even more preferably 0.1% to 5% by mass, and particularly preferably 0.1% to 1% by mass, relative to the total mass of the photosensitive layer.

[0113] The content of dye N refers to the amount of dye present when all of the dye N in the photosensitive layer is brought into a colored state. Below, we will explain the method for quantifying the content of dye N using a dye that develops color via radicals as an example. Two solutions are prepared by dissolving 0.001 g or 0.01 g of dye in 100 mL of methyl ethyl ketone. To each of the obtained solutions, the photoradical polymerization initiator Irgacure OXE01 (trade name, manufactured by BASF) is added, and radicals are generated by irradiating with 365 nm light, bringing all of the dye into a colored state. Then, under an atmospheric atmosphere, the absorbance of each solution at a liquid temperature of 25°C is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), and a calibration curve is created. Next, the absorbance of the solution in which all of the dye has developed color is measured in the same manner as above, except that 3 g of the photosensitive layer is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the photosensitive layer, the amount of dye contained in the photosensitive layer is calculated based on the calibration curve.

[0114] (Composition of the photosensitive layer: thermally crosslinkable compound) The photosensitive layer preferably contains a thermally crosslinkable compound from the viewpoint of the strength of the resulting cured film and the tackiness of the resulting uncured film. In this disclosure, thermally crosslinkable compounds having ethylenically unsaturated groups, as described later, will not be treated as ethylenically unsaturated compounds, but as thermally crosslinkable compounds. Examples of thermally crosslinkable compounds include methylol compounds and blocked isocyanate compounds. Among these, blocked isocyanate compounds are preferred from the viewpoint of the strength of the resulting cured film and the tackiness of the resulting uncured film. Since blocked isocyanate compounds react with hydroxyl groups and carboxyl groups, for example, if an alkali-soluble resin and / or an ethylenically unsaturated compound has at least one of a hydroxyl group and a carboxyl group, the hydrophilicity of the formed film tends to decrease, and the function of the film when the cured photosensitive layer is used as a protective film is enhanced. A blocked isocyanate compound refers to "a compound having a structure in which the isocyanate groups of isocyanate are protected (so-called masked) with a blocking agent."

[0115] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100°C to 160°C, and more preferably 130°C to 150°C. The dissociation temperature of the blocked isocyanate refers to "the temperature of the endothermic peak associated with the deprotection reaction of the blocked isocyanate, as measured by differential scanning calorimetry (DSC) analysis using a differential scanning calorimetry meter." As the differential scanning calorimetry meter, for example, a differential scanning calorimetry meter (model: DSC6200) manufactured by Seiko Instruments Inc. can be suitably used. However, the differential scanning calorimetry meter is not limited to this.

[0116] Examples of blocking agents with a dissociation temperature of 100°C to 160°C include active methylene compounds [malonic acid diesters (e.g., dimethyl malonate, diethyl malonate, di-n-butyl malonate, and di-2-ethylhexyl malonate)] and oxime compounds (e.g., formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime, which are compounds having a structure represented by -C(=N-OH)- in the molecule). Among these, blocking agents with a dissociation temperature of 100°C to 160°C are preferably those containing oxime compounds, for example, from the viewpoint of storage stability.

[0117] Blocked isocyanate compounds are preferably those having an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the film and enhancing adhesion to the transfer target. Blocked isocyanate compounds having an isocyanurate structure can be obtained, for example, by protecting hexamethylene diisocyanate by isocyanurating it. Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure obtained by using an oxime compound as a blocking agent are preferred from the viewpoint of making it easier to set the dissociation temperature within a favorable range and reducing development residue compared to compounds without an oxime structure.

[0118] Blocked isocyanate compounds may have polymerizable groups. There are no particular restrictions on the polymerizable groups, and known polymerizable groups can be used, with radical polymerizable groups being preferred. Examples of polymerizable groups include ethylenically unsaturated groups such as (meth)acryloxy groups, (meth)acrylamide groups, and styryl groups, as well as epoxy groups such as glycidyl groups. Among these, ethylenically unsaturated groups are preferred as polymerizable groups, (meth)acryloxy groups are more preferred, and acryloxy groups are even more preferred.

[0119] Commercially available blocked isocyanate compounds can be used. Examples of commercially available blocked isocyanate compounds include Karenz® AOI-BM, Karenz® MOI-BM, Karenz® MOI-BP, etc. (all manufactured by Showa Denko K.K.), and the block-type Duranate series (e.g., Duranate® TPA-B80E, Duranate® WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation). In addition, compounds with the following structures can also be used as blocked isocyanate compounds.

[0120] [ka]

[0121] The thermally crosslinkable compound may be used alone or in combination of two or more types. When the photosensitive layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1% to 50% by mass, and more preferably 5% to 30% by mass, relative to the total mass of the photosensitive layer.

[0122] (Composition of the photosensitive layer: Other components) The photosensitive layer may contain components other than those described above. Examples of other components include radical polymerization inhibitors, surfactants, sensitizers, and various additives. These other components may be used individually or in combination of two or more.

[0123] The photosensitive layer may contain a radical polymerization inhibitor. Examples of radical polymerization inhibitors include the thermal polymerization inhibitors described in paragraph 0018 of Japanese Patent No. 4502784. Among these, phenothiazine, phenoxazine, or 4-methoxyphenol are preferred. Other radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. In order not to impair the sensitivity of the photosensitive layer, it is preferable to use nitrosophenylhydroxyamine aluminum salt as the radical polymerization inhibitor.

[0124] The radical polymerization inhibitor may be used alone or in combination of two or more types. When the photosensitive layer contains a radical polymerization inhibitor, the content of the radical polymerization inhibitor is preferably 0.001% to 5.0% by mass, more preferably 0.01% to 3.0% by mass, and even more preferably 0.02% to 2.0% by mass, relative to the total mass of the photosensitive layer. Furthermore, the content of the radical polymerization inhibitor is preferably 0.005% to 5.0% by mass, more preferably 0.01% to 3.0% by mass, and even more preferably 0.01% to 1.0% by mass, relative to the total mass of the polymerizable compound.

[0125] The photosensitive layer preferably contains a surfactant. Examples of surfactants include those described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Unexamined Patent Publication No. 2009-237362. Furthermore, nonionic surfactants, fluorinated surfactants, or silicone surfactants are preferred as surfactants.

[0126] Examples of commercially available fluorine-based surfactants include Megafac (product name) 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-5 65, F-563, F-568, F-575, F-780, EXP.MFS-330, EXP.MFS-578, EXP.MFS-578-2, EXP.MFS-579, EXP.MFS-586, EXP.MF S-587, EXP.MFS-628, EXP.MFS-631, EXP.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, DS-21 (all manufactured by DIC Corporation), Florard (product name) FC430, FC431, FC171 (all manufactured by Sumitomo 3M Limited), Surflon (product name) S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC Inc.), PolyFox (product name) PF636, PF656, Examples include PF6320, PF6520, PF7002 (all manufactured by OMNOVA), Futergent (trade name) 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (all manufactured by Neos Co., Ltd.), and U-120E (Unichem Co., Ltd.). Furthermore, fluorinated surfactants that have a molecular structure with a functional group containing a fluorine atom, and in which the functional group containing the fluorine atom is cleaved and the fluorine atom volatilizes when heated, are also suitably used. Examples of such fluorinated surfactants include the Megafac (product name) DS series manufactured by DIC Corporation (Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafac (product name) DS-21.

[0127] Furthermore, as a fluorinated surfactant, it is also preferable to use 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. Block polymers can also be used as fluorinated surfactants. Fluorinated surfactants can also preferably be fluorinated polymer compounds containing a structural unit derived from a (meth)acrylate compound having a fluorine atom and a structural unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkylene oxy groups (preferably ethylene oxy groups, propylene oxy groups). As a fluorinated surfactant, fluorinated polymers having ethylenically unsaturated groups in their side chains can also be used. Examples include Megafac (trade name) RS-101, RS-102, RS-718K, RS-72-K (all manufactured by DIC Corporation). As a fluorinated surfactant, for example, a compound having a linear perfluoroalkyl group with 7 or more carbon atoms may be used. However, from the viewpoint of improving environmental suitability, it is preferable to use alternative materials such as perfluorooctanoic acid (PFOA) or perfluorooctanesulfonic acid (PFOS) as the fluorine-based surfactant.

[0128] Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters. Specific examples include Pluronic (trade name) L10, L31, L61, L62, 10R5, 17R2, 25R2 (all manufactured by BASF), Tetronic (trade name) 304, 701, 704, 901, 904, 150R1, and HYDROPALAT WE. Examples include 3323 (manufactured by BASF), Solspers (trade name) 20000 (manufactured by Lubrizol Nippon Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries Ltd.), Paionin (trade name) D-1105, D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), Orfin E1010, Surfinol 104, 400, 440 (manufactured by Nisshin Chemical Industry Co., Ltd.).

[0129] Examples of silicone-based surfactants include linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups are introduced into the side chains or terminals. Specific examples of silicone-based surfactants include EXP.S-309-2, EXP.S-315, EXP.S-503-2, EXP.S-505-2 (all manufactured by DIC Corporation), DOWSIL (product name) 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (all manufactured by Toray Dow Corning Co., Ltd.), as well as X-22-4952, X-22-4272, X-22-6 266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341 , KF-6001, KF-6002, KP-101, KP-103, KP-104, KP-105, KP-106, KP-109, KP-112, KP-120, KP-121, KP-124, K P-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, KP-652 (all manufactured by Shin-Etsu Chemical Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance) Examples include BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, and BYK323 (all manufactured by Bic Chemie).

[0130] The photosensitive layer may contain one surfactant alone or two or more surfactants. The surfactant content is preferably 0.001% to 10% by mass, and more preferably 0.01% to 3% by mass, relative to the total mass of the photosensitive layer.

[0131] The photosensitive layer may contain a sensitizer. The sensitizer is not particularly limited, and known sensitizers, dyes, and pigments can be used. Examples of sensitizers 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 (e.g., 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

[0132] The sensitizer may be used alone or in combination of two or more types. When the photosensitive layer contains a sensitizer, the amount of sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving sensitivity to the light source and improving the curing speed by balancing polymerization rate and chain transfer, 0.01% to 5% by mass and more preferably 0.05% to 1% by mass are preferred relative to the total mass of the photosensitive layer.

[0133] The photosensitive layer may contain known additives in addition to the above components, as needed. Examples of additives include plasticizers, heterocyclic compounds, benzotriazoles, carboxybenzotriazoles, pyridines (such as isonicotinamide), purine bases (such as adenine), and solvents. The photosensitive layer may contain each additive individually or in combination of two or more.

[0134] Examples of 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.

[0135] Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole. Commercially available carboxybenzotriazoles, such as CBT-1 (Johoku Chemical Industry Co., Ltd., trade name), can be used.

[0136] The total content of benzotriazoles and carboxybenzotriazoles is preferably 0.01% to 3% by mass, and more preferably 0.05% to 1% by mass, based on the total mass of the photosensitive layer. A content of 0.01% by mass or more is preferable from the viewpoint of providing storage stability to the photosensitive layer. On the other hand, a content of 3% by mass or less is preferable from the viewpoint of maintaining sensitivity and suppressing dye decolorization.

[0137] The photosensitive layer may contain at least one selected from the group consisting of plasticizers and heterocyclic compounds. Examples of plasticizers and heterocyclic compounds include those described in paragraphs 0097-0103 and 0111-0118 of International Publication No. 2018 / 179640.

[0138] The photosensitive layer may contain a solvent. When a photosensitive layer is formed using a photosensitive resin composition containing a solvent, the solvent may remain in the photosensitive layer.

[0139] Furthermore, the photosensitive layer may further contain known additives such as metal oxide particles, antioxidants, dispersants, acid builders, development accelerators, conductive fibers, thermoacid generators, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic precipitation inhibitors. Additives to be contained in the photosensitive layer are described in paragraphs 0165 to 0184 of Japanese Patent Application Publication No. 2014-85643, and the contents of this publication are incorporated herein by reference.

[0140] (Composition of the photosensitive layer: impurities, etc.) The photosensitive layer may contain a predetermined amount of impurities. Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and their ions. Among these, halide ions, sodium ions, and potassium ions are particularly prone to contamination as impurities, and therefore, their content is preferably as follows.

[0141] The impurity content in the photosensitive layer is preferably 80 ppm or less by mass, more preferably 10 ppm or less, and even more preferably 2 ppm or less. The impurity content can be 1 ppb or more by mass, and may also be 0.1 ppm or more.

[0142] Methods to keep impurities within the above range include selecting raw materials for the composition that have a low impurity content, preventing the inclusion of impurities during the production of the photosensitive layer, and removing them by washing. By such methods, the amount of impurities can be kept within the above range.

[0143] Impurities can be quantified using known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0144] The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive layer is preferably low. The content of these compounds relative to the total mass of the photosensitive layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less, based on mass. The lower limit can be 10 ppb or more, or 100 ppb or more, based on mass relative to the total mass of the photosensitive layer. The content of these compounds can be suppressed in the same way as the metal impurities mentioned above. Furthermore, they can be quantified by known measurement methods.

[0145] From the viewpoint of improving reliability and lamination, the water content in the photosensitive layer is preferably 0.01% to 1.0% by mass, and more preferably 0.05% to 0.5% by mass.

[0146] (Composition of the photosensitive layer: residual monomer) The photosensitive layer may contain residual monomers corresponding to each constituent unit of the alkali-soluble resin described above. From the viewpoint of patternability and reliability, the content of residual monomers is preferably 5,000 ppm by mass or less, more preferably 2,000 ppm by mass or less, and even more preferably 500 ppm by mass or less, relative to the total mass of the alkali-soluble resin. There is no particular lower limit, but it is preferably 1 ppm by mass or more, and more preferably 10 ppm by mass or more. From the viewpoint of patternability and reliability, the residual monomers of each constituent unit of the alkali-soluble resin are preferably 3,000 ppm by mass or less, more preferably 600 ppm by mass or less, and even more preferably 100 ppm by mass or less, relative to the total mass of the photosensitive layer. There is no particular lower limit, but it is preferably 0.1 ppm by mass or more, and more preferably 1 ppm by mass or more.

[0147] It is preferable that the amount of residual monomers when synthesizing alkali-soluble resins by polymer reactions be within the above range. For example, when synthesizing alkali-soluble resins by reacting glycidyl acrylate with a carboxylic acid side chain, it is preferable that the glycidyl acrylate content be within the above range. The amount of residual monomers can be measured by known methods such as liquid chromatography and gas chromatography.

[0148] (Physical properties of the photosensitive layer, etc.) From the viewpoint of developability and resolution, the thickness of the photosensitive layer is preferably 20 μm or less, more preferably 10 μm or less, even more preferably 8 μm or less, particularly preferably 5 μm or less, and most preferably 1 μm or more and 5 μm or less.

[0149] For superior adhesion, the transmittance of light at a wavelength of 365 nm in the photosensitive layer is preferably 10% or more, preferably 30% or more, and more preferably 50% or more. There is no particular upper limit, but 99.9% or less is preferred.

[0150] (Method for forming a photosensitive layer) The method for forming the photosensitive layer is not particularly limited as long as it is a method capable of forming a layer containing the above-mentioned components. For example, a method for forming the photosensitive layer includes preparing a photosensitive resin composition containing an alkali-soluble resin, an ethylenically unsaturated compound, a photopolymerization initiator, and a solvent, applying the photosensitive resin composition to a surface such as an intermediate layer, and drying the coating film of the photosensitive resin composition. Heat drying and reduced-pressure drying are preferred methods for drying the coating film of the photosensitive resin composition. In this disclosure, "drying" means removing at least a portion of the solvent contained in the composition. Examples of drying methods include natural drying, heat drying, and reduced-pressure drying. These methods can be applied individually or in combination. The drying temperature is preferably 80°C or higher, more preferably 90°C or higher. The upper limit is preferably 130°C or lower, more preferably 120°C or lower. Drying can also be performed by continuously changing the temperature. The drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. Furthermore, there is no particular upper limit, but it is preferable to keep it at 600 seconds or less, and more preferably at 300 seconds or less.

[0151] Examples of photosensitive resin compositions used for forming the photosensitive layer include compositions containing an alkali-soluble resin, an ethylenically unsaturated compound, a photopolymerization initiator, the above-mentioned optional components, and a solvent. It is preferable that the photosensitive resin composition contains a solvent to adjust the viscosity of the photosensitive resin composition and facilitate the formation of the photosensitive layer.

[0152] The solvent contained in the photosensitive resin composition is not particularly limited as long as it can dissolve or disperse the alkali-soluble resin, ethylenically unsaturated compound, photopolymerization initiator, and any of the above-mentioned optional components; known solvents can be used. Examples of solvents include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol and ethanol, etc.), ketone solvents (acetone and methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aprotic polar solvents (N,N-dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents, amide solvents, lactone solvents, and mixed solvents containing two or more of these. Preferably, the photosensitive resin composition contains at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. Among these, a mixed solvent comprising 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 is more preferred, and a mixed solvent comprising at least three types: 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 is even more preferred.

[0153] Examples of alkylene glycol ether solvents 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. Examples of alkylene glycol ether acetate solvents include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate. As solvents, solvents described in paragraphs 0092 to 0094 of International Publication No. 2018 / 179640 and solvents described in paragraph 0014 of Japanese Patent Application Publication No. 2018-177889 may be used, and these contents are incorporated herein.

[0154] The photosensitive resin composition may contain one solvent alone or two or more solvents. The solvent content when applying the photosensitive resin composition is preferably 50 to 1,900 parts by mass, and more preferably 100 to 900 parts by mass, per 100 parts by mass of the total solids in the photosensitive resin composition.

[0155] The method for preparing the photosensitive resin composition is not particularly limited. For example, one method involves preparing a solution in which each component is dissolved in the solvent, and then mixing the resulting solution in a predetermined ratio to prepare the photosensitive resin composition. It is preferable to filter the photosensitive resin composition using a filter with a pore size of 0.2 μm to 30 μm before forming the photosensitive layer.

[0156] The method of applying the photosensitive resin composition is not particularly limited and may be done by known methods. Examples of application methods include slit coating, spin coating, curtain coating, and inkjet coating. The photosensitive layer may also be formed by applying the photosensitive resin composition onto a protective film (described later) and drying it.

[0157] (Component of the transfer layer: intermediate layer) The intermediate layer preferably contains an alkali-soluble resin and a polymerizable compound. Examples of alkali-soluble resins include the alkali-soluble resin that is a component of the photosensitive layer described above and the alkali-soluble resin that is a component of the thermoplastic resin layer described later. Examples of polymerizable compounds include the polymerizable compound that is a component of the photosensitive layer described above.

[0158] When the intermediate layer contains an alkali-soluble resin and a polymerizable compound, the ratio of the mass of the polymerizable compound to the mass of the alkali-soluble resin in the intermediate layer is preferably 0.5 or more, more preferably 0.6 to 1.1, and particularly preferably 0.6 to 0.9. The ratio of the mass of the polymerizable compound to the mass of the alkali-soluble resin in the intermediate layer affects the storage modulus of the intermediate layer. For example, as the ratio of the mass of the polymerizable compound to the mass of the alkali-soluble resin in the intermediate layer increases, the storage modulus of the intermediate layer decreases. When the storage modulus of the intermediate layer decreases, the adhesion between the transfer layer and the object (e.g., a substrate) improves during the transfer of the transfer layer to the object, and the resolution also improves. On the other hand, as the ratio of the mass of the polymerizable compound to the mass of the alkali-soluble resin in the intermediate layer decreases, the storage modulus of the intermediate layer increases. When the storage modulus of the intermediate layer increases, adhesion of the transfer layer to the surface of the peeled temporary support or protective film is suppressed, and the decrease in resolution is also suppressed.

[0159] From the viewpoint of adhesion to adjacent layers, the thickness of the intermediate layer is preferably 1 μm or more, and more preferably 2 μm or more. From the viewpoint of developability and resolution, the thickness of the intermediate layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less.

[0160] The intermediate layer may have a single-layer structure or a multi-layer structure. Preferred intermediate layers include, for example, a thermoplastic resin layer and a water-soluble resin layer. The intermediate layer may include a thermoplastic resin layer, a water-soluble resin layer, or both a thermoplastic resin layer and a water-soluble resin layer. Preferably, the intermediate layer includes a thermoplastic resin layer and a water-soluble resin layer. When the intermediate layer includes a thermoplastic resin layer and a water-soluble resin layer, the transfer film preferably includes a temporary support, a thermoplastic resin layer, a water-soluble resin layer, a photosensitive layer, and a protective film in this order. Another example of an intermediate layer is an oxygen-blocking layer with oxygen-blocking function, as described as a "separation layer" in Japanese Patent Publication No. 5-72724. When the intermediate layer is an oxygen-blocking layer, the sensitivity during exposure is improved, the time load on the exposure machine is reduced, and productivity is improved.

[0161] (Intermediate layer component: thermoplastic resin layer) The thermoplastic resin layer improves, for example, the conformability of the transfer film to the substrate during lamination, suppresses the inclusion of air bubbles between the substrate and the transfer film, and improves the adhesion between the substrate and the transfer film.

[0162] (Components of the thermoplastic resin layer: alkali-soluble resin) The thermoplastic resin layer preferably contains an alkali-soluble resin as the thermoplastic resin. Examples of alkali-soluble resins 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.

[0163] As the alkali-soluble resin, acrylic resin is preferred from the viewpoint of developability and adhesion to adjacent layers. Here, acrylic resin means a resin having at least one constituent unit selected from the group consisting of constituent units derived from (meth)acrylic acid, constituent units derived from (meth)acrylic acid ester, and constituent units derived from (meth)acrylamide. As for the acrylic resin, it is preferable that the total content of constituent units derived from (meth)acrylic acid, constituent units derived from (meth)acrylic acid ester, and constituent units derived from (meth)acrylamide is 50% by mass or more of the total mass of the acrylic resin. In particular, it is preferable that the total content of constituent units derived from (meth)acrylic acid and constituent units derived from (meth)acrylic acid ester is 30% by mass to 100% by mass, and more preferably 50% by mass to 100% by mass, of the total mass of the acrylic resin.

[0164] Furthermore, the alkali-soluble resin is preferably a polymer having an acid group. Examples of acid groups include carboxyl groups, sulfol groups, phosphate groups, and phosphonic acid groups, with carboxyl groups being preferred. From the viewpoint of developability, alkali-soluble resins with an acid value of 60 mg KOH / g or higher are more preferred, and carboxyl group-containing acrylic resins with an acid value of 60 mg KOH / g or higher are even more preferred. There is no particular upper limit to the acid value of the alkali-soluble resin, but it is preferably 200 mg KOH / g or less, and more preferably 150 mg KOH / g or less.

[0165] The carboxyl group-containing acrylic resin with an acid value of 60 mgKOH / g or more is not particularly limited and can be appropriately selected from known resins. For example, examples include the alkali-soluble resin which is a carboxyl group-containing acrylic resin with an acid value of 60 mgKOH / g or more from the polymer described in paragraph 0025 of Japanese Patent Application Publication No. 2011-95716, the carboxyl group-containing acrylic resin with an acid value of 60 mgKOH / g or more from the polymer described in paragraphs 0033 to 0052 of Japanese Patent Application Publication No. 2010-237589, and the carboxyl group-containing acrylic resin with an acid value of 60 mgKOH / g or more from the alkali-soluble resin described in paragraphs 0053 to 0068 of Japanese Patent Application Publication No. 2016-224162. The copolymerization ratio of the constituent units having carboxyl groups in the above carboxyl group-containing acrylic resin is preferably 5% to 50% by mass, more preferably 10% to 40% by mass, and even more preferably 12% to 30% by mass, based on the total mass of the acrylic resin. As for the alkali-soluble resin, an acrylic resin having constituent units derived from (meth)acrylic acid is particularly preferred from the viewpoint of developability and adhesion to adjacent layers.

[0166] Alkali-soluble resins may have reactive groups. Reactive groups can be polymerizable groups, such as groups capable of addition polymerization, polycondensation, or polyaddition, and include ethylenically unsaturated groups; polycondensable groups such as hydroxyl groups and carboxyl groups; and polyaddition reactive groups such as epoxy groups and (blocked) isocyanate groups.

[0167] The weight-average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and even more preferably 20,000 to 50,000.

[0168] The thermoplastic resin layer may contain one alkali-soluble resin alone, or it may contain two or more alkali-soluble resins.

[0169] From the viewpoint of developability and adhesion to adjacent layers, the content of alkali-soluble resin is preferably 10% to 99% by mass, more preferably 20% to 90% by mass, even more preferably 40% to 80% by mass, and particularly preferably 50% to 70% by mass, relative to the total mass of the thermoplastic resin layer.

[0170] (Components of the thermoplastic resin layer: pigment) The thermoplastic resin layer preferably contains a dye (also simply called "dye B") whose maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development is 450 nm or higher, and whose maximum absorption wavelength changes with the presence of an acid, base, or radical. The preferred embodiment of dye B is the same as the preferred embodiment of dye N, except as described later.

[0171] From the viewpoint of visibility and resolution between the exposed and unexposed areas, dye B is preferably a dye whose maximum absorption wavelength changes with an acid or radical, and more preferably a dye whose maximum absorption wavelength changes with an acid. From the viewpoint of visibility and resolution between the exposed and unexposed areas, the thermoplastic resin layer preferably contains both a dye whose maximum absorption wavelength changes with an acid as dye B, and a compound that generates acid with light, as described later.

[0172] Pigment B may be used alone or in combination of two or more types.

[0173] From the viewpoint of visibility of the exposed and unexposed areas, the content of dye B is preferably 0.2% by mass or more, more preferably 0.2% to 6% by mass, even more preferably 0.2% to 5% by mass, and particularly preferably 0.25% to 3.0% by mass, relative to the total mass of the thermoplastic resin layer.

[0174] Here, the content of dye B refers to the amount of dye when all of the dye B contained in the thermoplastic resin layer is brought to a colored state. Below, the method for quantifying the content of dye B is explained using a dye that develops color via radicals as an example. Two solutions are prepared by dissolving 0.001 g or 0.01 g of dye in 100 mL of methyl ethyl ketone. To each of the obtained solutions, the photoradical polymerization initiator Irgacure OXE01 (trade name, manufactured by BASF) is added, and radicals are generated by irradiating with 365 nm light, bringing all of the dye to a colored state. Then, under an atmospheric atmosphere, the absorbance of each solution at a liquid temperature of 25°C is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), and a calibration curve is created. Next, the absorbance of the solution in which all of the dye has developed color is measured in the same manner as above, except that 0.1 g of thermoplastic resin layer is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of dye contained in the thermoplastic resin layer is calculated based on the calibration curve.

[0175] (Components of the thermoplastic resin layer: compounds that generate acids, bases, or radicals upon exposure to light) The thermoplastic resin layer may contain a compound (also simply referred to as "compound C") that generates an acid, base, or radical upon exposure to light. Compound C is preferably a compound that generates an acid, base, or radical upon exposure to active light such as ultraviolet and visible light. Known photoacid generators, photobase generators, and photoradical polymerization initiators (i.e., photoradical generators) can be used as compound C. Among these, photoacid generators are preferred.

[0176] From the viewpoint of resolution, the thermoplastic resin layer preferably contains a photoacid generator. Examples of photoacid generators include photocationic polymerization initiators that may be contained in the photosensitive layer described above, and the preferred embodiments are the same except for the points described later.

[0177] From the viewpoint of sensitivity and resolution, the photoacid generator preferably contains at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds, and from the viewpoint of sensitivity, resolution and adhesion, it is more preferable to contain an oxime sulfonate compound. In addition, a photoacid generator having the following structure is also preferred.

[0178] [ka]

[0179] The thermoplastic resin layer may contain a photoradical polymerization initiator. Examples of photoradical polymerization initiators include those that may be contained in the photosensitive layer described above, and the preferred embodiments are the same.

[0180] The thermoplastic resin layer may contain a photobase generator. The photobase generator is not particularly limited as long as it is a known photobase generator, for example, 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, {[(2,6-dinitrobenzyl)oxy]carbonyl}cyclohexylamine, bis{[(2,6-nitrobenzyl)oxy]carbonyl}hexane-1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) Examples include -1-benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt(III)tris(triphenylmethylborate), 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.

[0181] The thermoplastic resin layer may contain compound C alone or may contain two or more compounds.

[0182] From the viewpoint of visibility and resolution of the exposed and unexposed areas, the content of compound C is preferably 0.1% to 10% by mass, and more preferably 0.5% to 5% by mass, relative to the total mass of the thermoplastic resin layer.

[0183] (Components of the thermoplastic resin layer: plasticizer) From the viewpoint of resolution, adhesion to adjacent layers, and developability, it is preferable that the thermoplastic resin layer contains a plasticizer.

[0184] The plasticizer is preferably smaller in molecular weight (or weight-average molecular weight (Mw) if it is an oligomer or polymer) than the alkali-soluble resin. The molecular weight (weight-average molecular weight (Mw)) of the plasticizer is preferably between 200 and 2,000.

[0185] The plasticizer is not particularly limited as long as it is a compound that is compatible with alkali-soluble resins and exhibits plasticity. However, from the viewpoint of imparting plasticity, the plasticizer preferably has an alkylene oxy group in its molecule, and polyalkylene glycol compounds are more preferred. The alkylene oxy group contained in the plasticizer is more preferably a polyethylene oxy structure or a polypropylene oxy structure.

[0186] Furthermore, from the viewpoint of resolution and storage stability, it is preferable that the plasticizer contains a (meth)acrylate compound. From the viewpoint of compatibility, resolution, and adhesion to adjacent layers, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound. Examples of (meth)acrylate compounds used as plasticizers include the (meth)acrylate compounds described above as ethylenically unsaturated compounds contained in the photosensitive layer.

[0187] In transfer films, when a thermoplastic resin layer and a photosensitive layer are laminated in direct contact, it is preferable that both the thermoplastic resin layer and the photosensitive layer contain the same (meth)acrylate compound. This is because the inclusion of the same (meth)acrylate compound in both the thermoplastic resin layer and the photosensitive layer suppresses the diffusion of components between layers, thereby improving storage stability.

[0188] When a thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, it is preferable that the (meth)acrylate compound does not polymerize in the exposed area after exposure, from the viewpoint of adhesion with adjacent layers.

[0189] Furthermore, as a (meth)acrylate compound used as a plasticizer, a polyfunctional (meth)acrylate compound having two or more (meth)acryloyl groups in one molecule is preferred from the viewpoint of resolution, adhesion to adjacent layers, and developability.

[0190] Furthermore, as the (meth)acrylate compound used as a plasticizer, (meth)acrylate compounds having an acid group or urethane (meth)acrylate compounds are also preferred.

[0191] The thermoplastic resin layer may contain one type of plasticizer alone, or it may contain two or more types of plasticizers.

[0192] From the viewpoint of resolution, adhesion to adjacent layers, and developability, the plasticizer content is preferably 1% to 70% by mass, more preferably 10% to 60% by mass, and particularly preferably 20% to 50% by mass, relative to the total mass of the thermoplastic resin layer.

[0193] (Components of the thermoplastic resin layer: surfactant) From the viewpoint of uniform thickness, the thermoplastic resin layer preferably contains a surfactant. Examples of surfactants include those that may be contained in the photosensitive layer described above, and the preferred embodiments are the same.

[0194] The thermoplastic resin layer may contain one surfactant alone, or it may contain two or more surfactants.

[0195] The surfactant content is preferably 0.001% to 10% by mass, and more preferably 0.01% to 3% by mass, relative to the total mass of the thermoplastic resin layer.

[0196] (Components of the thermoplastic resin layer: sensitizer) The thermoplastic resin layer may contain a sensitizer. The sensitizer is not particularly limited and includes sensitizers that may be contained in the photosensitive layer as described above.

[0197] The thermoplastic resin layer may contain one type of sensitizer alone, or it may contain two or more types of sensitizers.

[0198] The sensitizer content can be appropriately selected depending on the purpose, but from the viewpoint of improving sensitivity to the light source and visibility of the exposed and unexposed areas, a range of 0.01% to 5% by mass, and more preferably 0.05% to 1% by mass, is preferred based on the total mass of the thermoplastic resin layer.

[0199] (Components of the thermoplastic resin layer: additives, etc.) The thermoplastic resin layer may contain known additives in addition to the above components, as needed. Furthermore, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese Patent Application Publication No. 2014-85643, and the contents described in this publication are incorporated herein by reference.

[0200] (Physical properties of thermoplastic resin layers, etc.) The thickness of the thermoplastic resin layer is not particularly limited, but from the viewpoint of adhesion to adjacent layers, it is preferably 1 μm or more, and more preferably 2 μm or more. There is no particular upper limit, but from the viewpoint of developability and resolution, it is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less.

[0201] (Method for forming a thermoplastic resin layer) The method for forming the thermoplastic resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components. For example, a method for forming the thermoplastic resin layer includes preparing a thermoplastic resin composition containing the above components and a solvent, applying the thermoplastic resin composition to the surface of a temporary support or the like, and drying the coating film of the thermoplastic resin composition. The thermoplastic resin composition preferably contains a solvent to adjust the viscosity of the thermoplastic resin composition and facilitate the formation of the thermoplastic resin layer.

[0202] The solvent contained in the thermoplastic resin composition is not particularly limited as long as it can dissolve or disperse the above-mentioned components contained in the thermoplastic resin layer. Examples of solvents contained in the thermoplastic resin composition include the solvents that may be contained in the photosensitive resin composition described above, and the preferred embodiments are the same.

[0203] The solvent contained in the thermoplastic resin composition may be a single type or two or more types. The solvent content when applying the thermoplastic resin composition is preferably 50 to 1,900 parts by mass, and more preferably 100 to 900 parts by mass, per 100 parts by mass of total solids in the thermoplastic resin composition.

[0204] The preparation of the thermoplastic resin composition and the formation of the thermoplastic resin layer may be carried out in accordance with the method for preparing the photosensitive resin composition and the method for forming the photosensitive layer described above. For example, after preparing a thermoplastic resin composition by first preparing a solution in which each component contained in the thermoplastic resin layer is dissolved in the above solvent, and then mixing the resulting solution in a predetermined ratio, The obtained thermoplastic resin composition is applied to the surface of a temporary support, and the coating film of the thermoplastic resin composition is dried to form a thermoplastic resin layer. Alternatively, after forming a photosensitive layer and an intermediate layer on the protective film described later, a thermoplastic resin layer may be formed on the surface of the intermediate layer.

[0205] (Components of the transfer layer: water-soluble resin layer) The water-soluble resin layer preferably contains a water-soluble resin. Examples of water-soluble resins include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and copolymers thereof. From the viewpoint of suppressing the mixing of components between multiple layers, the resin contained in the water-soluble resin layer is preferably different from both polymer A contained in the photosensitive layer and the thermoplastic resin (e.g., alkali-soluble resin) contained in the thermoplastic resin layer.

[0206] The water-soluble resin layer preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone, from the viewpoint of oxygen barrier properties and suppression of component mixing when applying multiple layers and during storage after application.

[0207] The water-soluble resin layer may contain one type of water-soluble resin alone, or it may contain two or more types of water-soluble resins.

[0208] The content of the water-soluble resin in the water-soluble resin layer is not particularly limited, but from the viewpoint of oxygen barrier properties and suppressing the mixing of components when applying multiple layers and during storage after application, it is preferably 50% to 100% by mass, more preferably 70% to 100% by mass, even more preferably 80% to 100% by mass, and particularly preferably 90% to 100% by mass, relative to the total mass of the water-soluble resin layer.

[0209] Furthermore, the water-soluble resin layer may contain additives such as surfactants as needed.

[0210] The thickness of the water-soluble resin layer is not particularly limited, but is preferably 0.1 μm to 5 μm, and more preferably 0.5 μm to 3 μm. If the thickness of the water-soluble resin layer is within the above range, it does not reduce oxygen barrier properties, it suppresses the mixing of components when applying multiple layers and during storage after application, and it suppresses an increase in the time required to remove the water-soluble resin layer during development.

[0211] The method for forming the water-soluble resin layer is not particularly limited. For example, one method involves preparing a water-soluble resin composition containing the above-mentioned resin and any additives, applying it to the surface of a thermoplastic resin layer or a photosensitive layer, and drying the coating of the water-soluble resin composition to form the water-soluble resin layer. Preferably, the water-soluble resin composition contains a solvent to adjust the viscosity of the water-soluble resin composition and facilitate the formation of the water-soluble resin layer.

[0212] The solvent contained in the water-soluble resin composition is not particularly limited as long as it can dissolve or disperse the resin, and 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 C1-C3 alcohols, acetone, ethylene glycol, and glycerin, with C1-C3 alcohols being preferred, and methanol or ethanol being more preferred.

[0213] (Components of transfer film: protective film) A transfer film according to one embodiment of the present disclosure includes a protective film. The materials constituting the protective film include resin films and paper, with resin films being preferred from the viewpoint of strength and flexibility. Examples of resin films include polyethylene films, polypropylene films, polyethylene terephthalate films, cellulose triacetate films, polystyrene films, and polycarbonate films. Among these, polyethylene films, polypropylene films, or polyethylene terephthalate films are preferred.

[0214] The thickness (layer thickness) of the protective film is not particularly limited, but is preferably 1 μm to 100 μm, more preferably 5 μm to 50 μm, even more preferably 5 μm to 40 μm, and particularly preferably 15 μm to 30 μm. Furthermore, the arithmetic mean roughness Ra value of the surface of the protective film that is in contact with the photosensitive layer (hereinafter 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 even more preferably 0.05 μm or less, from the viewpoint of superior resolution. This is thought to be because having the Ra value of the surface of the protective film within the above range improves the uniformity of the layer thickness of the photosensitive layer and the formed resin pattern. The lower limit of the Ra value of the surface of the protective film is not particularly limited, but is preferably 0.001 μm or more.

[0215] The Ra value of the protective film surface is measured using the following method. A 3D optical profiler (New View7300, Zygo) is used to measure the surface of the protective film under the following conditions to obtain the optical film surface profile. The measurement and analysis software used is the Microscope Application of MetroPro ver8.3.2. Next, the Surface Map screen is displayed in the above analysis software, and histogram data is obtained from the Surface Map screen. From the obtained histogram data, the arithmetic mean roughness is calculated to obtain the Ra value of the protective film surface. If the protective film is laminated to a transfer film, the protective film should be peeled from the transfer film, and the Ra value of the surface on the peeled side should be measured.

[0216] The introduction of the protective film onto the transfer film is carried out by known methods. For example, the protective film is placed on top of the transfer layer by lamination of the transfer layer and the protective film. Examples of equipment used for laminating the transfer layer and the protective film include known laminators such as vacuum laminators and auto-cut laminators. The laminator is preferably equipped with a heatable roller such as a rubber roller and capable of applying pressure and heating. In addition, in the manufacture of the transfer film, the transfer layer and the temporary support may be formed on top of the protective film in this order.

[0217] (Relationship between temporary support, photosensitive layer, and protective film) In a transfer film according to one embodiment of the present disclosure, it is preferable that the elongation at break of the cured film with a cured photosensitive layer at 120°C is 15% or more, the arithmetic mean roughness Ra of the photosensitive layer side surface of the temporary support is 50 nm or less, and the arithmetic mean roughness Ra of the photosensitive layer side surface of the protective film is 150 nm or less.

[0218] Furthermore, the transfer film relating to this 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 of the cured film with the photosensitive layer cured at 120°C, and Y represents the value (nm) of the arithmetic mean roughness Ra of the surface on the photosensitive layer side of the temporary support. X × Y is more preferably 750 or less.

[0219] It is preferable that the elongation at break of the cured film with a photosensitive layer cured at 120°C is more than twice as large as the elongation at break at 23°C. The elongation at break is measured by curing a 20 μm thick photosensitive layer with a pressure of 120 mJ / cm using an ultra-high pressure mercury lamp. 2 After exposure and curing, use a high-pressure mercury lamp at 400 mJ / cm². 2 The film is then subjected to further exposure and heated at 145°C for 30 minutes. The resulting cured film is then measured by a tensile test.

[0220] Furthermore, the transfer film relating to this disclosure preferably satisfies the following formula (R2). Y≦Z formula (R2) Here, in equation (R2) above, Y represents the arithmetic mean roughness Ra value (nm) of the photosensitive surface of the temporary support, and Z represents the arithmetic mean roughness Ra value (nm) of the photosensitive surface of the protective film.

[0221] (Transfer film manufacturing method) The method for manufacturing the transfer film according to this disclosure is not particularly limited, and known manufacturing methods, such as known methods for forming each layer, can be used. The method for manufacturing the transfer film according to this disclosure will be described below with reference to Figure 1. However, the transfer film according to this disclosure is not limited to having the configuration shown in Figure 1.

[0222] A method for manufacturing the transfer film 100 includes, for example, the steps of: applying an intermediate layer composition to the surface of a temporary support 10, drying the coating of the intermediate layer composition to form an intermediate layer 20; and applying a photosensitive resin composition containing an alkali-soluble resin and an ethylenically unsaturated compound to the surface of the intermediate layer 20, and drying the coating of the photosensitive resin composition to form a photosensitive layer 30. In the above manufacturing method, it is preferable to use an intermediate layer composition containing at least one selected from the group consisting of water and a water-miscible organic solvent, and further to use a photosensitive resin composition containing an alkali-soluble resin, an ethylenically unsaturated compound, and at least one selected from the group consisting of alkylene glycol ether solvent and alkylene glycol ether acetate solvent.

[0223] A transfer film 100 is manufactured by pressing a protective film 40 onto the photosensitive layer 30 of the laminate manufactured by the above manufacturing method. In the manufacturing method of the transfer film used in this disclosure, it is preferable to manufacture a transfer film 100 comprising a temporary support 10, an intermediate layer 20, a photosensitive layer 30, and a protective film 40 by including a step of providing the protective film 40 so as to contact the side of the photosensitive layer 30 opposite to the side on which the temporary support 10 is provided. After manufacturing the transfer film 100 by the above manufacturing method, the transfer film 100 may be wound up to produce and store a transfer film in roll form. The transfer film in roll form can be provided in its original form for the lamination process with the substrate using the roll-to-roll method described later.

[0224] A transfer film according to one embodiment of this disclosure can be suitably used in various applications requiring precise microfabrication by photolithography. After patterning the photosensitive layer, the photosensitive layer may be etched as a coating, or electroforming, mainly by electroplating, may be performed. The cured film obtained by patterning may be used as a permanent film, for example, as an interlayer insulating film, a wiring protective film, or a wiring protective film having an index matching layer. The transfer film according to one embodiment of this disclosure is preferably used for forming resist patterns. Furthermore, the transfer film according to one embodiment of this disclosure can be suitably used in applications such as forming various wiring in semiconductor packages, printed circuit boards, and sensor substrates, conductive films such as touch panels, electromagnetic shielding materials, and film heaters, liquid crystal sealing materials, and forming structures in the fields of micromachines and microelectronics.

[0225] Furthermore, in one embodiment of the present disclosure, a transfer film may also preferably be characterized in that the photosensitive layer is a colored resin layer containing a pigment. In addition to the above, the colored resin layer is suitable for applications such as forming colored pixels or black matrices in color filters used in liquid crystal display devices (LCDs) and solid-state image sensors (e.g., CCDs (charge-coupled devices) and CMOSs ​​(complementary metal oxide semiconductors)). Some liquid crystal display windows in recent electronic devices are fitted with a cover glass having a black frame-shaped light-shielding layer formed on the back edge of a transparent glass substrate or the like to protect the liquid crystal display window. A colored resin layer can be used to form such a light-shielding layer. The embodiments of the colored resin layer other than the pigment are the same as those described above.

[0226] The pigment used in the colored resin layer can be appropriately selected according to the desired hue, and can be chosen from black pigment, white pigment, or chromatic pigments other than black and white. Among these, black pigment is preferably selected when forming black patterns.

[0227] As the black pigment, any known black pigment (organic pigment or inorganic pigment, etc.) can be appropriately selected, as long as it does not impair the effects described herein. Among these, from the viewpoint of optical density, suitable black pigments include, for example, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, and graphite, with carbon black being particularly preferred. As for carbon black, from the viewpoint of surface resistance, carbon black in which at least a portion of the surface is coated with resin is preferred.

[0228] From the viewpoint of dispersion stability, the particle size of the black pigment is preferably 0.001 μm to 0.1 μm in number-average particle size, and more preferably 0.01 μm to 0.08 μm. Here, particle size refers to the diameter of a circle with the same area as the pigment particle, calculated from the area of ​​the pigment particle taken with an electron microscope. The number-average particle size is the average value obtained by calculating the above particle size for any 100 particles and averaging the obtained particle sizes of 100 particles.

[0229] As a pigment other than black pigment, for white pigments, the white pigments described in paragraphs 0015 and 0114 of Japanese Patent Publication No. 2005-007765 can be used. Specifically, among the white pigments, titanium dioxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate are preferred as inorganic pigments, titanium dioxide or zinc oxide are more preferred, and titanium dioxide is even more preferred. Among the inorganic pigments, rutile-type or anatase-type titanium dioxide is even more preferred, and rutile-type titanium dioxide is particularly preferred. Furthermore, the surface of the titanium dioxide may be treated with silica, alumina, titania, zirconia, or organic matter, and two or more treatments may be applied. This suppresses the catalytic activity of titanium dioxide and improves heat resistance and fading properties. From the viewpoint of reducing the thickness of the photosensitive layer after heating, at least one of alumina treatment and zirconia treatment is preferred as a surface treatment for the surface of titanium dioxide, and both alumina treatment and zirconia treatment are particularly preferred.

[0230] Furthermore, if the photosensitive layer is a colored resin layer, from the viewpoint of transferability, it is also preferable that the photosensitive layer further contains chromatic pigments other than black and white pigments. When chromatic pigments are included, the particle size of the chromatic pigment is preferably 0.1 μm or less, and more preferably 0.08 μm or less, in terms of superior dispersibility. Examples of chromatic pigments include Victoria Pure Blue BO (Color Index (CI) 42595), Auramin (CI41000), Fat Black HB (CI26150), Monolight Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11), Fastel Pink B Supra (CI Pigment Red 81), Monastral First Blue (CI Pigment Examples include CI Pigment Blue 15), Monolight First Black B (CI Pigment Black 1), Carbon, CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red 215, CI Pigment Green 7, CI Pigment Blue 15:1, CI Pigment Blue 15:4, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64, and CI Pigment Violet 23. Among these, CI Pigment Red 177 is preferred.

[0231] If the photosensitive layer contains a pigment, the pigment content is preferably more than 3% by mass and 40% by mass or less, more preferably more than 3% by mass and 35% by mass or less, even more preferably more than 5% by mass and 35% by mass or less, and particularly preferably 10% by mass or more and 35% by mass or less, based on the total mass of the photosensitive layer.

[0232] When the photosensitive layer contains pigments other than black pigment (white pigment and chromatic pigment), the content of pigments other than black pigment is preferably 30% by mass or less, more preferably 1% to 20% by mass, and even more preferably 3% to 15% by mass, relative to the black pigment.

[0233] Furthermore, when the photosensitive layer contains a black pigment and is formed from a photosensitive resin composition, it is preferable that the black pigment (preferably carbon black) is introduced into the photosensitive resin composition in the form of a pigment dispersion. The dispersion may be prepared by pre-mixing the black pigment and a pigment dispersant to obtain a mixture, adding it to an organic solvent (or vehicle), and dispersing it in a disperser. The pigment dispersant can be selected according to the pigment and solvent, and for example, commercially available dispersants can be used. The vehicle refers to the medium portion that disperses the pigment in the case of a pigment dispersion, and is liquid in form, containing a binder component that holds the black pigment in a dispersed state and a solvent component (preferably an organic solvent) that dissolves and dilutes the binder component.

[0234] There are no particular restrictions on the disperser, and examples of known dispersers include kneaders, roll mills, attritors, super mills, dissolvers, homomixers, and sand mills. Furthermore, fine grinding may be performed using frictional force through mechanical grinding. For information on dispersers and fine grinding, refer to the "Dictionary of Pigments" (by Kunizo Asakura, 1st edition, Asakura Shoten, 2000, pp. 438, 310).

[0235] <Method for manufacturing conductor patterns> A method for manufacturing a conductor pattern according to one embodiment of the present disclosure includes, in this order: peeling off a protective film from a transfer film according to one embodiment of the present disclosure (hereinafter sometimes referred to as the "protective film peeling step"), bonding the transfer film to a substrate including a metal layer and arranging the transfer layer and the temporary support on the metal layer of the substrate in this order (hereinafter sometimes referred to as the "bonding step"), exposing the transfer layer (hereinafter sometimes referred to as the "exposure step"), developing the transfer layer to form a resist pattern (hereinafter sometimes referred to as the "resist pattern formation step"), etching or plating the metal layer not covered by the resist pattern (hereinafter sometimes referred to as the "etching or plating step"), and peeling off the resist pattern (hereinafter sometimes referred to as the "resist pattern peeling step"). The method for manufacturing a conductor pattern described above may also include peeling off a temporary support between the bonding step and the exposure step (hereinafter sometimes referred to as the "temporary support peeling step"). The method for manufacturing a conductor pattern described above may also include a temporary support peeling step before the exposure step.

[0236] A method for manufacturing a conductor pattern according to another embodiment of the present disclosure includes, in this order: peeling off a protective film from a transfer film according to one embodiment of the present disclosure (i.e., a "protective film peeling step"), bonding the transfer film to a substrate including a metal layer and arranging the transfer layer and the temporary support on the metal layer of the substrate in this order (i.e., a "bonding step"), peeling off the temporary support (i.e., a "temporary support peeling step"), exposing the transfer layer (i.e., an "exposure step"), developing the transfer layer to form a resist pattern (i.e., a "resist pattern formation step"), etching or plating the metal layer not covered by the resist pattern (i.e., an "etching or plating step"), and peeling off the resist pattern (i.e., a "resist pattern peeling step").

[0237] The following describes specific aspects of the steps according to each of the embodiments described above. The transfer film used in the method for manufacturing the conductor pattern is as previously described. Therefore, a detailed explanation of the transfer film will be omitted in the following description.

[0238] (Protective film removal process) In the protective film peeling step, the protective film of the transfer film is peeled off. A known method can be used for peeling off the protective film. In the protective film peeling step, for example, a mechanism similar to the cover film peeling mechanism described in paragraphs 0161 to 0162 of Japanese Patent Application Publication No. 2010-072589 can be used.

[0239] The peel strength of the protective film is preferably 0.3 mN / mm to 2.0 mN / mm, more preferably 0.3 mN / mm to 1.5 mN / mm, and particularly preferably 0.5 mN / mm to 1.0 mN / mm. A higher peel strength of the protective film prevents unintentional peeling and improves handling. A lower peel strength makes it less likely for the transfer layer to adhere to the surface of the peeled protective film. The peel strength of the protective film is measured by the following method: After attaching tape (PRINTACK manufactured by Nitto Denko Corporation) to the surface of the protective film of the transfer film, a sample is prepared by cutting it to a size of 70 mm x 10 mm. The temporary support of the sample is fixed on the sample stage. Using a tensile and compression testing machine (SV-55 manufactured by Imada Seisakusho Co., Ltd.), the tape is pulled at 5.5 mm / second in a 180-degree direction to peel off the protective film, and the peel strength of the protective film is measured. Furthermore, the matters concerning the peel strength of the protective film described above apply not only to the protective film of the transfer film used in the method of manufacturing the conductor pattern according to this disclosure, but also to the protective film described in the section "Components of the transfer film: Protective film" above.

[0240] (Bonding process) In the bonding process, a transfer film and a substrate including a metal layer are bonded together, and a transfer layer and a temporary support are arranged in this order on the metal layer of the substrate. The bonding of the transfer film and the substrate preferably includes pressing the transfer film and the substrate together.

[0241] The method of pressing the transfer film and the substrate is not particularly limited, and known transfer methods and laminating methods can be used. The bonding of the transfer film and the substrate is preferably performed by overlapping the transfer film and the substrate and applying pressure and heat using means such as a roll. For bonding, known laminators such as laminators, vacuum laminators, and autolaminators that can enhance productivity can be used. The laminating temperature is not particularly limited, but for example, it is preferably 70°C to 130°C.

[0242] The method for manufacturing a conductor pattern including the bonding process is preferably performed by a roll-to-roll method. Hereinafter, the roll-to-roll method will be described. The roll-to-roll method means using a substrate that can be wound up and unwound as the substrate, and before any process included in the method for manufacturing a conductor pattern, a process of unwinding the substrate or a structure including the substrate (also referred to as the "unwinding process"), and after any process, a process of winding up the substrate or a structure including the substrate (also referred to as the "winding-up process"), and performing at least any process (preferably all processes, or all processes other than the heating process) while transporting the substrate or a structure including the substrate. The unwinding method in the unwinding process and the winding method in the winding-up process are not particularly limited, and known methods can be used in the manufacturing method to which the roll-to-roll method is applied.

[0243] Examples of the substrate include a resin substrate, a glass substrate, and a semiconductor substrate. Preferred embodiments of the substrate include, for example, those described in paragraph 0140 of WO 2018 / 155193, the content of which is incorporated herein. Preferred materials for the resin substrate are cycloolefin polymer and polyimide. The thickness of the resin substrate is preferably 5 μm to 200 μm, more preferably 10 μm to 100 μm.

[0244] The substrate includes a metal layer. The substrate may include two or more metal layers. Examples of the metal included in the metal layer include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au. The metal layer preferably includes at least one selected from the group consisting of copper and silver, and more preferably includes copper or silver.

[0245] The substrate may include a layer other than the metal layer. Examples of the layer other than the metal layer include a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer. Examples of the conductive metal oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO2. In the present disclosure, "conductive" means that the volume resistivity is less than 1×10 6 Ωcm. The volume resistivity of the conductive metal oxide is preferably less than 1×10 4 Ωcm.

[0246] The substrate may include at least one of transparent electrodes and routing wires. Such a substrate can be suitably used as a substrate for a touch panel. The transparent electrodes can function suitably as electrodes for a touch panel. The transparent electrodes are preferably composed of metal oxide films such as ITO (indium tin oxide) and IZO (indium zinc oxide), as well as metal meshes and metal nanowires. Examples of metal nanowires include silver and copper. Among these, silver conductive materials such as silver mesh and silver nanowires are preferred. Metal is preferred as the material for the routing wires. Examples of metals used as the material for the routing wires include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, as well as alloys composed of two or more of these metal elements. Copper, molybdenum, aluminum, or titanium are preferred as the material for the routing wires, with copper being particularly preferred.

[0247] (Temporary support removal process) In the temporary support peeling step, the temporary support is peeled off. Specifically, the temporary support of the laminate obtained by the bonding step is peeled off. By peeling off the temporary support, the transfer layer is usually exposed. Known methods can be used for peeling off the temporary support. In the temporary support peeling step, for example, a mechanism similar to the cover film peeling mechanism described in paragraphs 0161 to 0162 of Japanese Patent Application Publication No. 2010-072589 can be used.

[0248] The peel strength of the temporary support during peeling is preferably 0.3 mN / mm to 2.5 mN / mm, more preferably 0.3 mN / mm to 1.5 mN / mm, and particularly preferably 0.5 mN / mm to 1.0 mN / mm. A higher peel strength of the temporary support prevents unintentional peeling and improves handling. A lower peel strength makes it less likely for the transfer layer to adhere to the surface of the peeled temporary support. Also, since the protective film is peeled off before the temporary support, it is preferable to make the peel strength of the temporary support higher than the peel strength of the protective film. The peel strength of the temporary support is measured by the following method: The protective film is peeled off from the transfer film, and a laminate is obtained by bonding the transfer film and the substrate (specifically a copper substrate) under the conditions of a laminate roll temperature of 100°C, a linear pressure of 0.6 MPa, and a linear speed (laminate speed) of 4.0 m / min. After applying tape (NITTO PRINTACK) to the surface of the temporary support of the laminate obtained by the bonding process described above, the sample is prepared by cutting it to 70 mm x 10 mm. The sample substrate is fixed on the sample stand. Using a tensile and compression testing machine (Imada Seisakusho Co., Ltd. SV-55), the tape is pulled at 5.5 mm / second in a 180-degree direction to peel off the temporary support and measure the peel strength of the temporary support. The above-mentioned matters concerning the peel strength of the temporary support may also be applied to the temporary support described in the "Components of Transfer Film: Temporary Support" section above. When the above-mentioned matters concerning the peel strength of the temporary support are applied to the temporary support described in the "Components of Transfer Film: Temporary Support" section above, the laminate used for measuring the peel strength of the temporary support is obtained by peeling the protective film from the transfer film and bonding the transfer film and substrate under the conditions of a laminating roll temperature of 100°C, a linear pressure of 0.6 MPa, and a linear speed (laminating speed) of 4.0 m / min.

[0249] (Exposure process) In the exposure process, the transfer layer is exposed. In the exposure process, it is preferable to perform pattern exposure on the transfer layer. "Pattern exposure" refers to exposure in a patterned manner, that is, exposure in a manner in which exposed areas and unexposed areas exist. The positional relationship between the exposed and unexposed areas in pattern exposure is not particularly limited and can be adjusted as appropriate. Exposure may be performed along the direction from the substrate toward the transfer layer, or along the direction from the transfer layer toward the substrate.

[0250] The detailed arrangement and specific size of the pattern in pattern exposure are not particularly limited. For example, to improve the display quality of a display device (e.g., a touch panel) equipped with an input device having circuit wiring, and to reduce the area occupied by the output wiring, it is preferable that at least a portion of the pattern (preferably the electrode pattern and / or output wiring portion of the touch panel) includes fine lines with a width of 20 μm or less, and more preferably fine lines with a width of 10 μm or less.

[0251] The light source used for exposure can be appropriately selected and used as long as it emits light of a wavelength (e.g., 365 nm or 405 nm) that can expose the transfer layer (especially the photosensitive layer). Specifically, examples include ultra-high pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes). The exposure dose is 5 mJ / cm². 2 ~200 mJ / cm 2 Preferably, 10 mJ / cm 2 ~100mJ / cm 2 This is more preferable. Preferred embodiments of the light source, exposure amount, and exposure method used for exposure are, for example, described in paragraphs 0146-0147 of International Publication No. 2018 / 155193, which are incorporated herein by reference.

[0252] The exposure process may be performed after or before the temporary support is removed. If the temporary support is removed before exposure, the mask may be exposed in contact with the transfer layer (especially the photosensitive layer) or exposed in close proximity without contact. If exposure is performed without removing the temporary support, the mask may be exposed in contact with the temporary support or exposed in close proximity without contact. To prevent mask contamination due to contact between the transfer layer (especially the photosensitive layer) and the mask, and to avoid the influence of foreign matter adhering to the mask on exposure, it is preferable to perform pattern exposure without removing the temporary support. The exposure method can be appropriately selected from the following: in the case of contact exposure, the contact exposure method; and in the case of non-contact exposure, the proximity exposure method, the lens system or mirror system projection exposure method, or the direct exposure method using an exposure laser, etc. In the case of lens system or mirror system projection exposure, an exposure machine with an appropriate numerical aperture (NA) of the lens can be used according to the required resolution and depth of field. In the direct exposure method, drawing may be performed on the transfer layer (especially the photosensitive layer), or reduction projection exposure may be performed on the transfer layer (especially the photosensitive layer) via a lens. Furthermore, exposure may be performed not only in the atmosphere, but also under reduced pressure or vacuum, and exposure may also be performed with a liquid such as water interposed between the light source and the transfer layer (especially the photosensitive layer).

[0253] (Resist pattern formation process) In the resist pattern formation process, the transfer layer is developed to form a resist pattern. Development can be performed using a developer solution.

[0254] As the developer, known developers such as the developer described in Japanese Patent Publication No. 5-72724 can be used. Preferably, the developer is an alkaline aqueous solution containing a compound with a pKa of 7 to 13 at a concentration of 0.05 mol / L to 5 mol / L. The developer may also contain a water-soluble organic solvent and / or a surfactant. Examples of alkaline compounds that may be included in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide). The developer described in paragraph 0194 of International Publication No. 2015 / 093271 is also preferred as a developer.

[0255] A preferred developing method is, for example, the developing method described in paragraph 0195 of International Publication No. 2015 / 093271.

[0256] The development method is not particularly limited and may include paddle development, shower development, shower and spin development, and dip development. Shower development is a development process in which the exposed or unexposed areas are removed by spraying the developer solution onto the photosensitive layer after exposure. After development, it is preferable to spray a cleaning agent onto the film with a shower and remove the development residue by scrubbing with a brush. The temperature of the developer solution is not particularly limited, but 20°C to 40°C is preferred.

[0257] (Etching or plating process) In the etching or plating process, etching or plating is performed on the metal layer not covered by the resist pattern. Etching the metal layer not covered by the resist pattern removes the uncovered metal layer, forming a conductive pattern. Plating the metal layer not covered by the resist pattern forms a conductive pattern on top of the uncovered metal layer. The latter method is sometimes referred to as the semi-additive method. In some embodiments, etching is preferred on the metal layer not covered by the resist pattern. In some embodiments, plating is preferred on the metal layer not covered by the resist pattern.

[0258] As etching methods, known methods can be applied, for example, the methods described in paragraphs 0209 to 0210 of Japanese Patent Publication No. 2017-120435, the methods described in paragraphs 0048 to 0054 of Japanese Patent Publication No. 2010-152155, wet etching methods involving immersion in an etching solution, and dry etching methods such as plasma etching.

[0259] For wet etching, the etching solution used should be appropriately selected as either acidic or alkaline depending on the material to be etched. Examples of acidic etching solutions include aqueous solutions of a single acidic component selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, as well as aqueous solutions of an acidic component and a salt selected from ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component may be a combination of multiple acidic components. Examples of alkaline etching solutions include aqueous solutions of a single alkaline component selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (such as tetramethylammonium hydroxide), as well as aqueous solutions of an alkaline component and a salt (such as potassium permanganate). The alkaline component may be a combination of multiple alkaline components.

[0260] Known methods can be applied for plating, such as electroplating and electroless plating. Electroplating is preferred, and electroplated copper is more preferred.

[0261] Examples of components of the plating solution used in electroplating include water-soluble copper salts. As the water-soluble copper salt, any water-soluble copper salt commonly used as a component of plating solutions can be used. Preferably, the water-soluble copper salt is at least one selected from the group consisting of inorganic copper salts, copper alkanesulfonates, copper alkanolsulfonates, and organic copper acids. Examples of inorganic copper salts include copper sulfate, copper oxide, copper chloride, and copper carbonate. Examples of copper alkanesulfonates include copper methanesulfonate and copper propanesulfonate. Examples of copper alkanolsulfonates include copper isethionate and copper propanolsulfonate. Examples of organic copper acids include copper acetate, copper citrate, and copper tartrate.

[0262] The plating solution may contain sulfuric acid. By including sulfuric acid in the plating solution, the pH and sulfate ion concentration of the plating solution can be adjusted.

[0263] The electroplating method and conditions are not limited. For example, a conductive pattern can be formed on a conductive pattern by supplying a transparent substrate after the developing process to a plating tank to which a plating solution has been added. In electroplating, a conductive pattern can be formed, for example, by controlling the current density and the transport speed of the transparent substrate.

[0264] The temperature of the plating solution used in electroplating is preferably 70°C or lower, and more preferably 10°C to 40°C. The current density in electroplating is 0.1 A / dm². 2 ~100A / dm 2 Preferably, 0.5 A / dm 2 ~20A / dm 2It is more preferable that it is. By increasing the current density, the productivity of the conductor pattern can be improved. By decreasing the current density, the uniformity of the thickness of the conductor pattern can be improved.

[0265] (Resist pattern stripping process) In the resist pattern stripping process, the resist pattern is stripped. The method for stripping the resist pattern is not particularly limited, and examples include a method of removing it by chemical treatment, and a method of removing it using a remover is preferable. As a method for stripping the resist pattern, there is a method of immersing a substrate having the resist pattern in a stirred remover having a liquid temperature preferably of 30°C to 80°C, more preferably 50°C to 80°C, for 1 minute to 30 minutes.

[0266] Examples of the remover include a remover in which an inorganic alkali component or an organic alkali component is dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof. Examples of the inorganic alkali component include sodium hydroxide and potassium hydroxide. Examples of the organic alkali component include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds. Also, the remover may be used and removed by a known method such as a spray method, a shower method, or a paddle method.

[0267] (Post-exposure process and post-bake process) The method for manufacturing a conductor pattern according to an embodiment may include a process of exposing (post-exposure process) and / or a process of heating (post-bake process) the resist pattern obtained by the resist pattern forming process. When the method for manufacturing a conductor pattern includes both the post-exposure process and the post-bake process, it is preferable to perform the post-bake after the post-exposure.

[0268] The exposure amount of the post-exposure is preferably 100 mJ / cm 2 ~5,000 mJ / cm 2 and more preferably 200 mJ / cm 2 ~3,000 mJ / cm 2This is preferable.

[0269] The post-bake temperature is preferably 80°C to 250°C, and more preferably 90°C to 160°C.

[0270] The post-bake time is preferably 1 to 180 minutes, and more preferably 10 to 60 minutes.

[0271] (Other processes) Examples of steps applicable to the method for manufacturing a conductor pattern include the steps described in paragraphs 0035 to 0051 of Japanese Patent Publication No. 2006-23696. Examples of steps applicable to the method for manufacturing a conductor pattern include, but are not limited to, the steps for reducing the visible light reflectance described in paragraph 0172 of International Publication No. 2019 / 022089 and the step for forming a new conductive layer on an insulating film described in paragraph 0172 of International Publication No. 2019 / 022089.

[0272] A method for manufacturing a conductor pattern according to one embodiment may include a step of performing a treatment to reduce the visible light reflectance of some or all of the multiple metal layers having a substrate. An example of a treatment to reduce the visible light reflectance is oxidation treatment. If the substrate has a metal layer containing copper, the visible light reflectance of the metal layer can be reduced by oxidizing the copper to copper oxide and blackening the metal layer. Treatments to reduce the visible light reflectance are described in paragraphs 0017 to 0025 of Japanese Patent Application Publication No. 2014-150118 and paragraphs 0041, 0042, 0048 and 0058 of Japanese Patent Application Publication No. 2013-206315, and the contents described in these publications are incorporated herein by reference.

[0273] A method for manufacturing a conductor pattern according to one embodiment may also preferably include the steps of forming an insulating film on the surface of the conductor pattern and 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. The step of forming the insulating film is not particularly limited and includes known methods for forming permanent films. Alternatively, an insulating photosensitive material may be used to form an insulating film with a desired pattern by photolithography. The step of forming a new conductive layer on the insulating film is not particularly limited and, for example, a conductive photosensitive material may be used to form a new conductive layer with a desired pattern by photolithography.

[0274] In the method for manufacturing the conductor pattern, it is preferable to use a substrate having multiple metal layers on both surfaces of the substrate, and to sequentially or simultaneously form circuits on the metal layers formed on both surfaces of the substrate. With such a configuration, it is possible to form a touch panel circuit wiring in which a first conductor pattern is formed on one surface of the substrate and a second conductor pattern is formed on the other surface. It is also preferable to form such a touch panel circuit wiring from both sides of the substrate using a roll-to-roll method.

[0275] (Applications of conductor patterns) The conductor pattern can be applied to various devices. An example of a device equipped with a conductor pattern manufactured by the above manufacturing method is an input device, preferably a touch panel, and more preferably a capacitive touch panel. Furthermore, the above input device can be applied to display devices such as organic EL displays and liquid crystal displays.

[0276] <Manufacturing method for touch panels> A method for manufacturing a touch panel according to one embodiment of the present disclosure includes, in this order: peeling off a protective film from a transfer film according to one embodiment of the present disclosure (i.e., a "protective film peeling step"), bonding the transfer film to a substrate including a metal layer, and arranging the transfer layer and temporary support on the metal layer of the substrate in this order (i.e., a "bonding step"), exposing the transfer layer (i.e., an "exposure step"), developing the transfer layer to form a resist pattern (i.e., a "resist pattern formation step"), etching or plating the metal layer not covered by the resist pattern (i.e., an "etching or plating step"), and peeling off the resist pattern (i.e., a "resist pattern peeling step"). The above method for manufacturing a touch panel may also include peeling off a temporary support between the bonding step and the exposure step (i.e., a "temporary support peeling step"). The above method for manufacturing a touch panel may also include a temporary support peeling step before the exposure step.

[0277] A method for manufacturing a touch panel according to another embodiment of the present disclosure includes, in this order: peeling off a protective film from a transfer film according to one embodiment of the present disclosure (i.e., a "protective film peeling step"), bonding the transfer film to a substrate including a metal layer, and arranging the transfer layer and temporary support on the metal layer of the substrate in this order (i.e., a "bonding step"), peeling off the temporary support (i.e., a "temporary support peeling step"), exposing the transfer layer (i.e., an "exposure step"), developing the transfer layer to form a resist pattern (i.e., a "resist pattern formation step"), etching or plating the metal layer not covered by the resist pattern (i.e., an "etching or plating step"), and peeling off the resist pattern (i.e., a "resist pattern peeling step").

[0278] The specific details of each step and the sequence in which each step is performed in the method for manufacturing a touch panel are as described in the sections on "Method for Manufacturing a Laminate" and "Method for Manufacturing Circuit Wiring" above, and the preferred embodiments are also as described. Aside from forming the wiring for the touch panel using the method described above, the method for manufacturing a touch panel can be based on known methods for manufacturing touch panels. Furthermore, the method for manufacturing a touch panel may include any other steps (other steps) not described above.

[0279] Figures 2 and 3 show examples of mask patterns used in the manufacture of touch panels. In pattern A shown in Figure 2 and pattern B shown in Figure 3, GR is the non-image area (light-shielding area), EX is the image area (exposure area), and DL is a hypothetical alignment frame. In the manufacturing method of a touch panel, for example, by exposing the photosensitive layer through a mask having pattern A shown in Figure 2, a touch panel can be manufactured in which circuit wiring having pattern A corresponding to EX is formed. Specifically, it can be manufactured by the method described in Figure 1 of International Publication No. 2016 / 190405. In an example of a manufactured touch panel, the central part of the exposure area EX (the patterned part where the lines are connected) is the part where transparent electrodes (electrodes for the touch panel) are formed, and the peripheral part of the exposure area EX (the part with thin lines) is the part where wiring for the peripheral extraction area is formed.

[0280] The above method for manufacturing a touch panel produces a touch panel having at least wiring for the touch panel. Preferably, the touch panel has a transparent substrate, electrodes, and an insulating layer or protective layer. Known methods for detection in a touch panel include resistive, capacitive, ultrasonic, electromagnetic induction, and optical methods. Among these, the capacitive method is preferred.

[0281] Examples of touch panel types include the so-called in-cell type (for example, those described in Figures 5, 6, 7, and 8 of Japanese Patent Publication No. 2012-517051), the so-called on-cell type (for example, those described in Figure 19 of Japanese Patent Application Publication No. 2013-168125, and those described in Figures 1 and 5 of Japanese Patent Application Publication No. 2012-89102), OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (for example, those described in Figure 2 of Japanese Patent Application Publication No. 2013-54727), various out-cell types (so-called GG, G1·G2, GFF, GF2, GF1, and G1F, etc.), and other configurations (for example, those described in Figure 6 of Japanese Patent Application Publication No. 2013-164871). Examples of touch panels include those described in paragraph 0229 of Japanese Patent Application Publication No. 2017-120435. [Examples]

[0282] The embodiments of the present invention will be described in more detail below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate without departing from the spirit of the embodiments of the present invention. Therefore, the scope of the embodiments of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass. In the following examples, the weight-average molecular weight of the resin is the weight-average molecular weight obtained in polystyrene equivalent by gel permeation chromatography (GPC). The theoretical acid value was used.

[0283] <Provisional support 1> Temporary support 1 was prepared by the following method.

[0284] (Particle-containing layer-forming composition 1) The components were mixed according to the formulation shown below to obtain particle-containing layer-forming composition 1. After preparing particle-containing layer-forming composition 1, it was filtered through a 6 μm filter (F20, manufactured by MAHLE FILM Systems, Inc.), and then degassed using a 2x6 radial flow superphobic filter (manufactured by Polypore, Inc.).

[0285] • Acrylic polymer (AS-563A, manufactured by Daicel Finechem Co., Ltd., solids content 27.5% by mass) 167 parts Nonionic surfactant (Naroacty CL95, manufactured by Sanyo Chemical Industries, Ltd., solid content 100% by mass) 0.7 parts • Anionic surfactant (Rapizol A-90, manufactured by NOF Corporation, diluted with water to 1% solids by mass) 114.4 parts Carnauba wax dispersion (Celosol 524, manufactured by Chukyo Oils Co., Ltd., solids content 30% by mass) 7 parts • Carbodiimide compound (Carbodilite V-02-L2, manufactured by Nisshinbo Chemical Co., Ltd., diluted with water to 10% solids by mass) 20.9 parts • Matting agent (Snowtex XL, manufactured by Nissan Chemical Corporation, solid content 40% by mass, average particle size 50 nm): 2.8 parts ·Wednesday: 690.2 copies

[0286] (Extrusion molding) Pellets of polyethylene terephthalate, polymerized using a citric acid chelate organotitanium complex as described in Japanese Patent Publication No. 5575671, were dried to a moisture content of 50 ppm or less. These pellets were then placed in the hopper of a 30 mm diameter single-screw kneading extruder, melted at 280°C, and extruded. The molten material 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. The extruded melt was then brought into close contact with the cooling roll using an electrostatic application method.

[0287] (Stretching and application) The solidified, unstretched film was subjected to sequential biaxial stretching using the following method to obtain a temporary support containing a 16 μm thick polyester film and a 40 nm thick particle-containing layer.

[0288] (a) Longitudinal extension An unstretched film was passed between two pairs of nip rolls with different peripheral speeds and stretched in the longitudinal direction (conveying direction). The preheating temperature was 75°C, the stretching temperature was 90°C, the stretching ratio was 3.4 times, and the stretching speed was 1300% / second.

[0289] (b) Application Particle-containing layer-forming composition 1 was applied to one side of a longitudinally stretched film using a bar coater to a thickness of 40 nm after film formation.

[0290] (c) Lateral stretching The film, which had undergone the longitudinal stretching and coating described above, was then stretched transversely using a tenter under the following conditions. Preheating temperature: 110℃ Stretching temperature: 120℃ Stretching ratio: 4.2x Stretching speed: 50% / sec

[0291] (Thermal fixation and thermal relaxation) The biaxially oriented film, after longitudinal and transverse stretching, was heat-fixed under the following conditions. Heat fixing temperature: 227℃ Heat setting time: 6 seconds

[0292] After heat setting, the tenter width was reduced and heat relaxation was performed under the following conditions. Thermal relaxation temperature: 190℃ Thermal relaxation rate: 4%

[0293] (winding up) After heat setting and heat relaxation, both ends were trimmed, the ends were extruded (knurled) to a width of 10 mm, and then wound up under a tension of 40 kg / m. The width was 1.5 m and the length was 6300 m. The obtained film roll was used as temporary support 1. The haze of temporary support 1 was 0.2. The haze was measured as total optical haze using a haze meter (NDH2000, manufactured by Nippon Denshoku Industries Ltd.). The thermal shrinkage rate after heating at 150°C for 30 minutes was 1.0% on the MD (machine direction) side and 0.2% on the TD (transverse direction) side. The film thickness of the particle-containing layer was measured from a cross-sectional TEM image and was 40 nm. The average particle diameter of the particles contained in the particle-containing layer was measured using the above method with a Hitachi High-Technologies Corporation HT-7700 transmission electron microscope (TEM) and was 50 nm.

[0294] <Water-soluble resin composition> The following components were mixed to obtain a water-soluble resin composition to be used as material 1 for the water-soluble resin layer. • Ion-exchanged water: 38.12 parts Methanol (manufactured by Mitsubishi Gas Chemical Company, Inc.): 57.17 parts • Kuraray Poval 4-88LA (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.): 3.22 parts • Polyvinylpyrrolidone K-30 (manufactured by Nippon Shokubai Co., Ltd.): 1.49 parts • Megafac F-444 (fluorinated surfactant, manufactured by DIC Corporation): 0.0035 units

[0295] <Photosensitive resin composition> A mixed solvent containing methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd., 60 parts) and propylene glycol monomethyl ether acetate (manufactured by Showa Denko K.K., 40 parts) was prepared. Each component listed in Table 1 was mixed with the mixed solvent to prepare the photosensitive resin compositions shown as materials 1-4 and 5A-5E in Table 1. The amount of mixed solvent added was adjusted so that the solid content concentration of the photosensitive composition was 13% by mass.

[0296] [Table 1]

[0297] <Thermoplastic resin composition> The components listed in Table 2 were mixed to obtain a thermoplastic resin composition to be used as a material for a thermoplastic resin layer.

[0298] [Table 2]

[0299] The meanings of the abbreviations listed in Table 2 are as follows. A-2: Benzyl methacrylate / methacrylic acid / acrylic acid copolymer (75% by mass / 10% by mass / 15% by mass, weight-average molecular weight: 30,000, Tg: 75℃, acid value: 186 mgKOH / g) • B-1: Compounds with the structure shown below (pigments that develop color when exposed to acid)

[0300] [ka]

[0301] • C-1: Compound having the structure shown below (photoacid generator, compound described in paragraph 0227 of Japanese Patent Publication No. 2013-47765, synthesized according to the method described in paragraph 0227).

[0302] [ka]

[0303] • D-3: NK Ester A-DCP (Tricyclodecane dimethanol diacrylate, Shin-Nakamura Chemical Co., Ltd.) • D-4: 8UX-015A (Polyfunctional urethane acrylate compound, Taisei Fine Chemical Co., Ltd.) • D-5: Aronics TO-2349 (a polyfunctional acrylate compound containing a carboxyl group, Toagosei Co., Ltd.) • E-1: Megafuck F552 (DIC Corporation) F-1: Phenothiazine (Fujifilm Wako Pure Chemical Corporation) F-2: CBT-1 (Johoku Chemical Industry Co., Ltd.) • MEK: Methyl ethyl ketone • PGME: Propylene glycol monomethyl ether • PGMEA: Propylene glycol monomethyl ether acetate

[0304] <Transfer film> As described in Table 3, a thermoplastic resin layer, a water-soluble resin layer, and a photosensitive layer were formed on a temporary support in the following order, as needed. The thermoplastic resin was formed by coating and drying a thermoplastic resin composition. The water-soluble resin layer was formed by coating and drying a water-soluble resin composition. The photosensitive layer was formed by coating and drying a photosensitive resin composition. A protective film was placed on the photosensitive layer as described in Table 3 to obtain a transfer film.

[0305] <Copper substrate> A copper layer with a thickness of 200 nm was formed on a polyethylene terephthalate film by sputtering to obtain a copper substrate. The obtained copper substrate will be used for the following evaluations.

[0306] <Storage modulus> The storage modulus of the thermoplastic resin layer and the photosensitive layer were measured using a viscoelasticity measuring device (DHR-2 rheometer manufactured by T.A. Instruments), a 20 mmφ parallel plate, and a Peltier plate (Gap: approximately 0.5 mm) under the conditions of a temperature of 20°C to 125°C, a heating rate of 5°C / min, a frequency of 1 Hz, and a strain of 0.5%. Specifically, before measurement, the sample was melted on the Peltier plate at 80°C to 95°C, cooled to 20°C at a cooling rate of 5°C / min, and then measured in constant gap mode. The storage modulus value at 25°C was adopted. The measurement results are shown in Table 3.

[0307] <Roughness Ra> The surface roughness Ra of the temporary support facing the transfer layer and the surface roughness Ra of the transfer layer facing the temporary support were measured using the following method. The protective film was peeled off the transfer film, and the transfer film was attached to a copper substrate under the conditions of a laminating roll temperature of 100°C, a linear pressure of 0.6 MPa, and a linear velocity (laminating speed) of 4.0 m / min. A 3D optical profiler (New View7300, Zygo) was used to obtain the surface profile of the target surface. The "Microscope Application" of "MetroPro ver8.3.2" was used as the measurement and analysis software. The "Surface Map" screen was displayed using the above software, and histogram data was obtained on the "Surface Map" screen. From the obtained histogram data, the arithmetic mean roughness Ra of the target surface was calculated. The measurement results are shown in Table 3.

[0308] <Peel strength of protective film> The peel strength of the protective film was measured using the following method. After attaching tape (PRINTACK, manufactured by Nitto Denko Corporation) to the surface of the protective film of the transfer film, a sample was prepared by cutting it to a size of 70 mm x 10 mm. The temporary support of the sample was fixed on the sample stand. Using a tensile and compression testing machine (SV-55, manufactured by Imada Seisakusho Co., Ltd.), the tape was pulled at 5.5 mm / second in a 180-degree direction to peel the protective film from the sample, and the peel strength of the protective film was measured. The measurement results are shown in Table 3.

[0309] <Peel strength of the temporary support> The peel strength of the temporary support was measured using the following method. The protective film was peeled off the transfer film, and the transfer film was attached to the copper substrate under the conditions of a laminating roll temperature of 100°C, a linear pressure of 0.6 MPa, and a linear speed (laminating speed) of 4.0 m / min. After attaching tape (NITTO PRINTACK) to the surface of the temporary support, a sample was prepared by cutting it to 70 mm x 10 mm. The copper substrate of the sample was fixed on the sample stand. Using a tensile and compression testing machine (Imada Seisakusho Co., Ltd. SV-55), the tape was pulled at 5.5 mm / second in a 180-degree direction to peel the temporary support from the sample, and the peel strength of the temporary support was measured. The measurement results are shown in Table 3.

[0310] <Resolution> The protective film was peeled off the transfer film, and the transfer film was attached to a copper substrate under the conditions of a laminating roll temperature of 100°C, a linear pressure of 0.6 MPa, and a linear speed (laminating speed) of 4.0 m / min. The temporary support was peeled off from the resulting laminate, and the transfer layer placed on the copper substrate was brought into contact with a photomask having a line-and-space pattern, and the transfer layer was exposed using an ultra-high pressure mercury lamp. The exposed transfer layer was subjected to shower development for 40 seconds using a 1.0 mass% sodium carbonate aqueous solution at 28°C. The above series of procedures was performed by changing the line-and-space ratio (i.e., L / S) of the photomask in the range of 5 / 5 to 8 / 8, and the resolution was evaluated according to the following criteria. The evaluation results are shown in Table 3. A: Under conditions of L / S=5 / 5 to L / S=6 / 6, the resin patterns can be resolved without any residue. Under the conditions B:L / S=7 / 7 to L / S=8 / 8, the image can be resolved without any residue between patterns. The image cannot be resolved under the condition C:L / S=8 / 8.

[0311] <Laminating properties> The protective film was peeled off the transfer film, and the transfer film was attached to a copper substrate under the conditions of a laminating roll temperature of 100°C, a linear pressure of 0.6 MPa, and a linear speed (laminating speed) of 4.0 m / min. The resulting laminate was observed using an optical microscope. The number of bubbles between the transfer film and the copper substrate in a region with a width and length of 1 mm was counted. Based on the number of bubbles observed, the lamination properties were evaluated according to the following criteria. The evaluation results are shown in Table 3. A:0 pieces B: 1 or more but less than 10 C: 10 or more

[0312] <Poor peeling> The protective film was peeled off the transfer film, and the presence or absence of transfer layer deposits on the surface of the protective film was visually checked. Next, the transfer film was attached to a copper substrate under the conditions of a laminating roll temperature of 100°C, a linear pressure of 0.6 MPa, and a linear speed (laminating speed) of 4.0 m / min. The temporary support was peeled off from the resulting laminate, and the presence or absence of transfer layer deposits on the surface of the temporary support was visually checked. In a plan view, the area of ​​transfer layer deposits observed in a 100 mm wide and 100 mm long region on the surface of the protective film was determined, and the area of ​​transfer layer deposits observed in a 100 mm wide and 100 mm long region on the surface of the temporary support was determined. The area of ​​the observed region (i.e., 20,000 mm²) 2 The ratio of the area of ​​the transfer layer to the total area was determined, and the peeling defects were evaluated according to the following criteria. The evaluation results are shown in Table 3. A: 0% B: Greater than 0% and less than 0.1% C: 0.1% or more

[0313] [Table 3]

[0314] The "16KS40" listed in Table 3 refers to Lumirror 16KS40 manufactured by Toray Industries, Inc. "16FB40" listed in Table 3 refers to Lumirror 16FB40 manufactured by Toray Industries, Inc. In Table 3, "FG201" refers to Alpha-Fan FG-201 manufactured by Oji F-Tech Co., Ltd. The "M / B" listed in Table 3 refers to the mass ratio of the polymerizable compound to the alkali-soluble resin. The "10^5" listed in Table 3 is 10 5 It means... The "10^6" listed in Table 3 is 10 6 It means... The "10^7" listed in Table 3 is 10 7 It means... The "10^8" listed in Table 3 is 10 8 It means... In Table 3, the "Surface Roughness Ra" listed in the "Temporary Support" column refers to the surface roughness Ra of the temporary support facing the transfer layer. In Table 3, the "Surface Roughness Ra" listed in the "Transfer Layer" column refers to the surface roughness Ra of the transfer layer facing the temporary support.

[0315] In the examples shown in Table 3, the storage modulus of the protective film side of the transfer layer at 25°C is 1.0 × 10⁻⁶ 6 Pa~3.0×10 8 It is within the range of Pa. Table 3 shows that the resolution of the example is superior to that of the comparative example.

[0316] (Explanation of symbols) 10: Temporary support 20: Middle Class 30: Photosensitive layer 40: Protective film 100: Transfer film GR: Light-shielding area (non-image area) EX: Exposure area (image area) DL: Alignment frame

[0317] The disclosure of Japanese Patent Application No. 2021-030223, filed on 26 February 2021, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference.

Claims

1. It includes a temporary support, a transfer layer, and a protective film in this order. The storage modulus of the protective film side of the transfer layer at 25°C is 1.0 × 10⁻⁶ ６ Pa ~ 3.0 x 10 ８ Pa is, The storage modulus of the transfer layer on the temporary support side at 25°C is 1.0 × 10⁶ Pa or more. Transfer film.

2. The transfer film according to claim 1, wherein the surface roughness Ra of the transfer layer facing the temporary support is 0.1 nm to 15 nm.

3. The transfer film according to claim 1 or claim 2, wherein the surface roughness Ra of the temporary support facing the transfer layer is 0.1 nm to 15 nm.

4. The transfer film according to any one of claims 1 to 3, wherein the transfer layer is a photosensitive layer.

5. The transfer film according to any one of claims 1 to 4, wherein the transfer layer includes an intermediate layer and a photosensitive layer.

6. The transfer film according to claim 5, wherein the intermediate layer comprises an alkali-soluble resin and a polymerizable compound, and the ratio of the mass of the polymerizable compound to the mass of the alkali-soluble resin in the intermediate layer is 0.5 or more.

7. The transfer film according to claim 5 or claim 6, wherein the thickness of the intermediate layer is 10 μm or less.

8. The transfer film according to any one of claims 5 to 7, wherein the intermediate layer comprises a thermoplastic resin layer and a water-soluble resin layer.

9. The transfer film according to any one of claims 4 to 8, wherein the photosensitive layer comprises an alkali-soluble resin and a polymerizable compound, and the ratio of the mass of the polymerizable compound to the mass of the alkali-soluble resin in the photosensitive layer is 0.6 or more.

10. The transfer film according to any one of claims 4 to 9, wherein the thickness of the photosensitive layer is 10 μm or less.

11. A transfer film comprising a temporary support, a transfer layer, and a protective film in this order, wherein the storage modulus of the transfer layer on the protective film side at 25°C is 1.0 × 10⁶ Pa to 3.0 × 10⁸ Pa, and the protective film of the transfer film is peeled off. The transfer film and the substrate containing the metal layer are bonded together, and the transfer layer and the temporary support are arranged in this order on the metal layer of the substrate. Exposing the aforementioned transfer layer, Develop the aforementioned transfer layer to form a resist pattern, Etching or plating the metal layer that is not covered by the resist pattern, The process includes, in this order, peeling off the resist pattern, A method for manufacturing a conductor pattern.

12. A transfer film comprising a temporary support, a transfer layer, and a protective film in this order, wherein the storage modulus of the transfer layer on the protective film side at 25°C is 1.0 × 10⁶ Pa to 3.0 × 10⁸ Pa, and the protective film of the transfer film is peeled off. The transfer film and the substrate containing the metal layer are bonded together, and the transfer layer and the temporary support are arranged in this order on the metal layer of the substrate. The temporary support is to be removed, Exposing the aforementioned transfer layer, Develop the aforementioned transfer layer to form a resist pattern, Etching or plating the metal layer that is not covered by the resist pattern, The process includes, in this order, peeling off the resist pattern, A method for manufacturing a conductor pattern.

13. The method for manufacturing a conductor pattern according to claim 12, wherein the peel strength of the temporary support during the peeling of the temporary support is 0.3 mN / mm to 2.0 mN / mm.

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