Photosensitive transfer material, resin pattern manufacturing method, circuit wiring manufacturing method, touch panel manufacturing method, and polyethylene terephthalate film

Abstract

Provided are a photosensitive transfer material capable of producing a resin pattern with reduced defects, a method for producing a resin pattern using the photosensitive transfer material, a method for producing circuit wiring, and a method for producing a touch panel, and a polyethylene terephthalate film. The present invention provides a temporary support and a photosensitive resin layer disposed on the temporary support, and the number of foreign particles having a major axis of 3 μm or more contained in the temporary support is 0.5 / mm 2 The following are photosensitive transfer materials and their applications.

Description

[Technical Field]

[0001] The present disclosure relates to a photosensitive transfer material, a method for manufacturing a resin pattern, a method for manufacturing circuit wiring, a method for manufacturing a touch panel, and a polyethylene terephthalate film. [Background technology]

[0002] In display devices (organic electroluminescence (EL) display devices, liquid crystal display devices, etc.) equipped with a touch panel such as a capacitance-type input device, an electrode pattern corresponding to the sensor of the visible area, a conductive layer pattern such as wiring for the peripheral wiring portion and the extraction wiring portion, etc. is provided inside the touch panel.

[0003] Generally, the formation of a patterned layer requires only a small number of steps to obtain the desired pattern shape, and therefore a widely adopted method involves providing a layer of a photosensitive resin composition (photosensitive layer) on a substrate using a photosensitive transfer material, exposing the photosensitive layer through a mask having the desired pattern, and then developing it.

[0004] JP 2012-123394 A describes a photosensitive resin composition for a photosensitive film, which comprises a support film and a layer of a photosensitive resin composition formed on the support film, the haze of the support film being 0.01 to 2.0%, and the total number of particles with a diameter of 5 μm or more and aggregates with a diameter of 5 μm or more contained in the support film being 5 / mm 2 The document below describes a photosensitive element in which a layer made of a photosensitive resin composition contains a binder polymer, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator, and the layer made of the photosensitive resin composition has a thickness of 3 to 30 μm. Summary of the Invention [Problem to be solved by the invention]

[0005] According to one embodiment of the present invention, there is provided a photosensitive transfer material capable of producing a resin pattern with reduced defects. According to another embodiment of the present invention, there are provided a method for producing a resin pattern using the photosensitive transfer material, a method for producing circuit wiring, a method for producing a touch panel, and a polyethylene terephthalate film. [Means for solving the problem]

[0006] The present disclosure includes the following aspects. <1> The temporary support has a photosensitive resin layer disposed on the temporary support, and the number of foreign particles having a major diameter of 3 μm or more contained in the temporary support is 0.5 / mm 2 A photosensitive transfer material, which is: <2> The number of foreign particles with a major axis of 3 μm or more, which contain at least one element selected from the group consisting of F, Mg, Si, Ca, Ti, Fe, and Sb, contained in the temporary support is 0.5 particles / mm 2 Below is the <1> The photosensitive transfer material according to claim 1. <3> Among the foreign particles contained in the temporary support that have a major diameter of 3 μm or more, those with a maximum diameter of 1580 cm -1 and 1360 cm -1 The number of foreign particles at which two peaks are observed is 0.5 pieces / mm 2 Below is the <1> The photosensitive transfer material according to claim 1. <4> Among the foreign particles contained in the temporary support with a major axis of 3 μm or more, the number of foreign particles whose brightness is 10% or more lower than the brightness of the surrounding normal area is 0.5 particles / mm 2 Below is the <1> The photosensitive transfer material according to claim 1. <5> The temporary support is a single layer containing a resin, and the photosensitive resin layer is disposed directly on the temporary support. <1> ~ <4> 10. The photosensitive transfer material according to any one of the above items. <6> The thickness of the photosensitive resin layer is 10 μm or less. <1> ~ <5> Listed in one of the following Photosensitive transfer material. <7> <1> ~ <6> a step of laminating a surface of the photosensitive resin layer in the photosensitive transfer material described in any one of the above that is not facing the temporary support to a substrate; a step of patternwise exposing the photosensitive resin layer in the photosensitive transfer material after the laminating step; and a step of developing the photosensitive resin layer after the patternwise exposing step to form a resin pattern. <8> <1> ~ <6> a step of laminating a surface of the photosensitive resin layer in the photosensitive transfer material described in any one of the above that does not face the temporary support to a substrate; a step of pattern-exposing the photosensitive resin layer in the photosensitive transfer material after the laminating step; a step of developing the photosensitive resin layer after the pattern-exposing step to form a resin pattern; and a step of etching the substrate in an area where the resin pattern is not arranged. <9> <1> ~ <6> a step of laminating a surface of the photosensitive resin layer in the photosensitive transfer material according to any one of the above items, the surface not facing the temporary support, to a substrate; A method for manufacturing a touch panel, comprising: a step of pattern-exposing a photosensitive resin layer in a photosensitive transfer material after a bonding step; a step of developing the photosensitive resin layer after the pattern-exposing step to form a resin pattern; and a step of etching a substrate in an area where the resin pattern is not arranged. <10> The number of foreign particles with a major diameter of 3 μm or more is 0.5 / mm 2 Polyethylene terephthalate film: <11> The number of foreign particles with a major axis of 3 μm or more containing at least one element selected from the group consisting of F, Mg, Si, Ca, Ti, Fe, and Sb is 0.5 particles / mm 2 Below is the <10> The polyethylene terephthalate film according to claim 1. <12> Among foreign particles with a major diameter of 3 μm or more, those with a diameter of 1580 cm -1 and 1360 cm -1 The number of foreign particles at which two peaks are observed is 0.5 particles / mm 2 Below is the <10> The polyethylene terephthalate film according to claim 1. <13> Among foreign bodies with a major diameter of 3 μm or more, the number of foreign bodies whose brightness is 10% or more lower than the brightness of the surrounding normal area is 0.5 / mm 2 Below is the <10> The polyethylene terephthalate film according to claim 1. [Effects of the Invention]

[0007] According to one embodiment of the present invention, a photosensitive transfer material capable of producing a resin pattern with reduced defects can be provided. Also, according to another embodiment of the present invention, a method for producing a resin pattern using the photosensitive transfer material, a method for producing circuit wiring, a method for producing a touch panel, and a polyethylene terephthalate film can be provided. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a schematic diagram showing an example of the configuration of the photosensitive transfer material of the first embodiment. [Figure 2] FIG. 2 is a schematic diagram showing an example of the configuration of the photosensitive transfer material of the second embodiment. [Figure 3] FIG. 3 is a schematic plan view showing pattern A. [Figure 4] FIG. 4 is a schematic plan view showing pattern B. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present disclosure will be described below with reference to the accompanying drawings, in which reference numerals may be omitted.

[0010] In the description of groups (atomic groups) in this specification, when a notation does not specify whether the group is substituted or unsubstituted, it encompasses both unsubstituted and substituted groups. For example, the notation "alkyl group" encompasses not only alkyl groups without a substituent (unsubstituted alkyl groups) but also alkyl groups with a substituent (substituted alkyl groups). In this specification, "(meth)acrylic acid" refers to both acrylic acid and methacrylic acid or "(Meth)acrylate" represents either or both of acrylate and methacrylate, and "(meth)acryloyl" represents either or both of acryloyl and methacryloyl. In addition, chemical structural formulas in this specification may be written as simplified structural formulas in which hydrogen atoms are omitted.

[0011] In this specification, when a component contains multiple substances, the amount (content, etc.) of each component means the total amount (total content, etc.) of those multiple substances, unless otherwise specified. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In this specification, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.

[0012] In this specification, the term "process" does not only refer to an independent process, but also includes any process that achieves a desired purpose even if it cannot be clearly distinguished from other processes. In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. In addition, light used for exposure generally includes the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV (Extreme ultraviolet lithography) light), and actinic rays (activating electrons) such as X-rays. Examples include:

[0013] In this specification, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) are the same as those of TSKgel GMHxL, TSKgel G4000HxL, TSKgel Using a gel permeation chromatography (GPC) analyzer with a G2000HxL column (both are product names manufactured by Tosoh Corporation), The molecular weight is determined by detecting the compound in a THF (tetrahydrofuran) solvent using a differential refractometer and converting it using polystyrene as a standard substance. As used herein, a combination of two or more preferred embodiments is a more preferred embodiment. In this specification, unless otherwise specified, the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm. In this specification, the "solid content" of a composition refers to the components that form a layer produced using the composition, and when the composition contains a solvent (organic solvent, water, etc.), it refers to all components excluding the solvent. Furthermore, liquid components that form the layer are also considered to be solid content. In this specification, the thickness of each layer of the photosensitive transfer material is measured by observing a cross section of the photosensitive transfer material in a direction perpendicular to the main surface using a scanning electron microscope (SEM), measuring the thickness of each layer at any five or more points based on the obtained observation image, and calculating the average value.

[0014] [Photosensitive transfer material] The photosensitive transfer material according to the present disclosure includes a temporary support and a photosensitive resin layer disposed on the temporary support, and the number of foreign particles having a major axis of 3 μm or more contained in the temporary support is 0.5 particles / mm 2 The following is the result.

[0015] The present inventors have found that foreign matter contained in a temporary support used in a photosensitive transfer material impedes exposure and causes defects in a resin pattern. In particular, foreign matter with a major axis of 3 μm or more tends to easily cause defects. The photosensitive transfer material according to the present disclosure has a temporary support containing foreign matter with a major axis of 3 μm or more, and the number of foreign matter particles contained in the temporary support is 0.5 particles / mm 2 Therefore, a resin pattern with reduced defects can be produced.

[0016] The photosensitive transfer material according to the present disclosure will be described in detail below.

[0017] The photosensitive transfer material according to the present disclosure has a temporary support and a photosensitive resin layer. In the photosensitive transfer material, the temporary support and the photosensitive resin layer may be laminated directly without any other layer therebetween, or the temporary support and the photosensitive resin layer may be laminated via another layer. Also, another layer may be laminated on the surface of the photosensitive resin layer opposite to the surface facing the temporary support. Examples of layers other than the temporary support and the photosensitive resin layer include a thermoplastic resin layer, an intermediate layer, a refractive index adjusting layer, and a cover film. Each layer may be a single layer or a multi-layer consisting of two or more layers.

[0018] An example of an embodiment of the photosensitive transfer material according to the present disclosure is shown below, but the present disclosure is not limited thereto. (1) "Temporary support / photosensitive resin layer / refractive index adjusting layer / cover film" (2) "Temporary support / photosensitive resin layer / cover film" (3) "Temporary support / intermediate layer / photosensitive resin layer / cover film" (4) "Temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin layer / cover film" In each of the above configurations, the photosensitive resin layer is preferably a negative photosensitive resin layer. It is also preferable that the photosensitive resin layer is a colored resin layer. The photosensitive transfer material according to the present disclosure may be used as a photosensitive transfer material for a wiring protective film, or as a photosensitive transfer material for an etching resist, as described below. When the photosensitive transfer material is used as a wiring protective film, the photosensitive transfer material preferably has the structure (1) or (2) described above. Furthermore, when the photosensitive transfer material is used as an etching resist, the photosensitive transfer material preferably has the configurations (2) to (4) described above.

[0019] In the photosensitive transfer material, when the photosensitive resin layer further has other layers on the side opposite the temporary support side, the total thickness of the other layers arranged on the side opposite the temporary support side of the photosensitive resin layer is preferably 0.1% to 30% of the thickness of the photosensitive resin layer, and more preferably 0.1% to 20%.

[0020] From the viewpoint of preventing the generation of bubbles during the lamination step described below, the maximum waviness width of the photosensitive transfer material is preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 60 μm or less. The lower limit of the maximum waviness width of the photosensitive transfer material is 0 μm or more, preferably 0.1 μm or more, and more preferably 1 μm or more. The maximum waviness width of the photosensitive transfer material is a value measured by the following procedure. First, a photosensitive transfer material is cut perpendicular to the main surface to a size of 20 cm x 20 cm to prepare a test sample. If the photosensitive transfer material has a cover film, the cover film is peeled off. Next, the test sample is placed on a flat, horizontal stage with the surface of the temporary support facing the stage. After the sample is placed, a 10 cm square area in the center of the test sample is scanned with a laser microscope (e.g., Keyence VK-9700SP) to obtain a three-dimensional surface image. The minimum concave height is subtracted from the maximum convex height observed in the obtained three-dimensional surface image. This procedure is performed on 10 test samples, and the arithmetic average value is taken as the "maximum waviness width of the photosensitive transfer material."

[0021] The photosensitive transfer material according to the present disclosure will be described below by way of specific examples of embodiments. The photosensitive transfer material of the first embodiment described below has a configuration suitable for use as a photosensitive transfer material for etching resists, and the photosensitive transfer material of the second embodiment described below has a configuration suitable for use as a photosensitive transfer material for wiring protective films.

[0022] Photosensitive Transfer Material of First Embodiment The photosensitive transfer material of the first embodiment will be described below by taking an example. The photosensitive transfer material 20 shown in FIG. 1 has a temporary support 11, a transfer layer 12 including a thermoplastic resin layer 13, an intermediate layer 15, and a photosensitive resin layer 17, and a cover film 19, in this order. Although the photosensitive transfer material 20 shown in FIG. 1 has a cover film 19 arranged thereon, the cover film 19 does not necessarily have to be arranged. Furthermore, the photosensitive transfer material 20 shown in FIG. 1 has a configuration in which the thermoplastic resin layer 13 and the intermediate layer 15 are arranged, but the thermoplastic resin layer 13 and the intermediate layer 15 do not necessarily have to be arranged. Each element constituting the photosensitive transfer material of the first embodiment will be described below.

[0023] [Temporary support] The photosensitive transfer material according to the present disclosure includes a temporary support. The temporary support is a peelable support that supports the photosensitive resin layer or the laminate containing the photosensitive resin layer.

[0024] The temporary support preferably has optical transparency from the viewpoint of enabling exposure of the photosensitive resin layer through the temporary support when the photosensitive resin layer is subjected to patternwise exposure. In this specification, "having optical transparency" means that the transmittance of light of the wavelength used for patternwise exposure is 50% or more.

[0025] From the viewpoint of improving the exposure sensitivity of the photosensitive resin layer, the temporary support preferably has a transmittance of 60% or more, more preferably 70% or more, for light of the wavelength used for pattern exposure (preferably a wavelength of 365 nm).

[0026] The transmittance of a layer included in a photosensitive transfer material is the ratio of the intensity of light that passes through the layer and is emitted to the intensity of light that is incident when light is incident in a direction perpendicular to the main surface of the layer (i.e., in the thickness direction). The transmittance is measured using an "MCPD Series" product manufactured by Otsuka Electronics Co., Ltd.

[0027] The temporary support may be a single layer or a laminate of two or more layers. Examples of the temporary support include a support consisting of only a substrate, a laminate comprising a substrate and a particle-containing layer disposed on one side of the substrate, and a laminate comprising a substrate and particle-containing layers disposed on both sides of the substrate. Among these, from the viewpoint of obtaining a resin pattern with reduced defects, it is preferable that the temporary support consists of only a substrate.

[0028] Examples of the substrate constituting the temporary support include glass, resin, and paper. From the viewpoints of strength, flexibility, and light transmittance, the substrate constituting the temporary support is preferably a resin. The resin is preferably in the form of a sheet or film.

[0029] Examples of the resin film include a polyethylene terephthalate (PET) film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Of these, the resin film is preferably a PET film, and more preferably a biaxially stretched PET film.

[0030] When a particle-containing layer is disposed on one or both surfaces of the substrate, the particle-containing layer may be one layer or two or more layers.

[0031] The particle-containing layer is formed, for example, by applying a composition for the particle-containing layer onto a substrate and drying it. The particle-containing layer is also formed by co-extrusion when forming a resin film. It is also possible to use a binder polymer. The composition for the particle-containing layer preferably contains a binder polymer and particles. The type of binder polymer is not particularly limited and can be appropriately selected depending on the purpose, for example. Examples of binder polymers include acrylic resins, urethane resins, olefin resins, styrene-butadiene resins, ester resins, vinyl chloride resins, and vinylidene chloride resins. When the particle-containing layer is disposed by a co-extrusion method, it is preferable to use PET as the binder polymer.

[0032] The particle-containing layer may contain one type of binder polymer and one type of particles, or two or more types of binder polymer and particles.

[0033] The particles contained in the particle-containing layer are not particularly limited and can be appropriately selected depending on the purpose. The content of particles in the particle-containing layer can be appropriately adjusted by the amount of particles added to the composition for the particle-containing layer. In this specification, the particles contained in the particle-containing layer are referred to as "added particles."

[0034] The additive particles are to be distinguished from impurities unexpectedly mixed in during the manufacturing process of the temporary support and particles formed during the manufacturing process of the temporary support. The additive particles are preferably particles that do not melt at 200°C.

[0035] Whether or not the temporary support contains additive particles can be determined, for example, by the following method: Additive particles usually have uniform shape and distribution, and therefore can be determined by observation with an optical microscope.

[0036] Examples of the additive particles include inorganic particles and organic particles.

[0037] Examples of inorganic particles include particles of inorganic oxides such as silicon oxide (silica), titanium oxide (titania), zirconium oxide (zirconia), magnesium oxide (magnesia), and aluminum oxide (alumina).

[0038] Examples of organic particles include particles of polymers such as acrylic resin, polyester, polyurethane, polycarbonate, polyolefin, and polystyrene.

[0039] When the temporary support has a particle-containing layer, the additive particles contained in the particle-containing layer are preferably inorganic oxide particles.

[0040] The average particle size of the added particles is not particularly limited, but is, for example, 0.1 μm to 10 μm. The average particle size is measured by cutting a 100 nm thick slice with an ultramicrotome and using a transmission electron microscope (TEM).

[0041] In the photosensitive transfer material according to the present disclosure, the number of foreign particles having a major diameter of 3 μm or more contained in the temporary support is 0.5 particles / mm 2 0.2 pieces / mm or less 2 It is preferable that the number of particles is 0.1 or less per mm. 2 More preferably, it is 0.05 pieces / mm or less. 2 It is even more preferable that:

[0042] In this specification, the term "foreign matter" refers to a substance having an area in which a difference in polarization from the surrounding area can be observed when the temporary support is observed under a polarizing microscope. Examples of foreign matter include carbonized resin formed during the production of the substrate and catalysts used in the production of the substrate. In addition, when the particle-containing layer described above is provided, the added particles contained in the particle-containing layer are also considered to be foreign matter if a difference in polarization can be observed under a polarizing microscope.

[0043] If the temporary support contains foreign matter, it may interfere with exposure and cause defects in the resin pattern. Furthermore, if, after forming a resin pattern, the substrate in the area where the resin pattern is not arranged is etched to obtain a wiring pattern, defects may also occur in the wiring pattern. In particular, if the temporary support contains foreign matter with a major diameter of 3 μm or more, defects are likely to occur in the resin pattern. In the photosensitive transfer material according to the present disclosure, the number of foreign matter with a major diameter of 3 μm or more contained in the temporary support is 0.5 / mm 2 or less, defects in the resin pattern can be reduced.

[0044] In the photosensitive transfer material according to the present disclosure, the number of foreign particles having a major axis of 3 μm or more and containing at least one element selected from the group consisting of F, Mg, Si, Ca, Ti, Fe, and Sb contained in the temporary support is 0.5 particles / mm 2It is preferable that the number of particles is 0.2 or less per mm. 2 It is more preferable that the number is 0.1 or less per mm. 2 More preferably, it is 0.05 pieces / mm or less. 2 It is particularly preferred that:

[0045] The present inventors have found that when the base material constituting the temporary support is a resin film (preferably a polyethylene terephthalate film), foreign matter contained in the temporary support and containing at least one element selected from the group consisting of F, Mg, Si, Ca, Ti, Fe, and Sb tends to be colored black. Black-colored foreign matter can hinder exposure and is highly likely to cause wiring defects such as disconnections and pinholes. Therefore, when the number of foreign matter with a major diameter of 3 μm or more contained in the temporary support and containing at least one element selected from the group consisting of F, Mg, Si, Ca, Ti, Fe, and Sb is less than 0.5 / mm 2 If it is less than this, defects in the resin pattern are further reduced.

[0046] In the photosensitive transfer material according to the present disclosure, foreign matter contained in the temporary support having a major axis of 3 μm or more is detected by laser Raman spectroscopy at 1580 cm -1 and 1360 cm -1 The two peaks of The number of foreign particles observed is 0.5 / mm 2 It is preferable that the number of particles is 0.2 or less per mm. 2 It is more preferable that the number is 0.1 or less per mm. 2 More preferably, it is 0.05 pieces / mm or less. 2 It is particularly preferred that:

[0047] When the base material constituting the temporary support is a resin film (preferably a polyethylene terephthalate film), the inventors analyzed black-colored foreign matter contained in the temporary support and found that the black-colored foreign matter was detected at 1580 cm by laser Raman spectroscopy. -1 and 1360 cm -1 Two of them It was found that a peak of 1580 cm was observed in laser Raman spectroscopy. -1 The peak at 1360 cm in laser Raman spectroscopy is due to the graphite structure and is also called the G band. -1 The peak is derived from the diamond structure and is also called the D band.

[0048] When the base material constituting the temporary support is a resin film (preferably a polyethylene terephthalate film), if a compound containing at least one element selected from the group consisting of F, Mg, Si, Ca, Ti, Fe, and Sb is mixed in during the production of the temporary support, it is estimated that the resin present around the mixed compound is carbonized to form a carbide. It is thought that this carbide becomes a foreign substance in the temporary support. Of the foreign substances contained in the temporary support that have a major diameter of 3 μm or more, those with a diameter of 1580 cm or more measured by laser Raman spectroscopy are -1 and 1360 cm -1 Two peaks The number of foreign particles observed is 0.5 / mm 2 If it is less than this, defects in the resin pattern are further reduced.

[0049] In the photosensitive transfer material according to the present disclosure, the number of foreign particles having a major axis of 3 μm or more contained in the temporary support, whose brightness is 10% or more lower than the brightness of the surrounding normal area, is 0.5 particles / mm 2 Here, brightness refers to the brightness in an image obtained by observation in transmission mode using an optical microscope, and means the V value of the HSV color system. If the brightness is 10% or more lower than the brightness of the surrounding normal area, it means that the area is colored black. Black-colored foreign matter can cause exposure problems, such as breaks and pinholes. Therefore, among the foreign particles contained in the temporary support that are 3 μm or larger in major diameter, the number of foreign particles whose brightness is 10% or more lower than the brightness of the surrounding normal area is 0.5 particles / mm 2 If it is less than this, defects in the resin pattern are further reduced.

[0050] The number of foreign matters on the temporary support and the major diameter of the foreign matters are measured, for example, by the following method.

[0051] First, the temporary support is observed with a polarizing microscope (a simple polarizing microscope made by inserting a "U-POT" filter and a "U-AN360" filter into a "BX60" product, a 10x objective lens, manufactured by Olympus Corporation), and the portion where polarization is disturbed is identified as a foreign substance. Furthermore, the major diameter of the foreign substance is measured with an optical microscope (product name "BX60"; a 100x objective lens, manufactured by Olympus Corporation) and an observation area of ​​250 mm is identified. 2 The number of foreign matter particles with a major axis of 3 μm or more contained in the foreign matter is counted. If the foreign matter contains voids, the major axis is measured including the voids. The major axis refers to the length of the longest part of the area that makes up the foreign matter. The brightness of the foreign matter and the normal area around the foreign matter is measured using the V value displayed in the HSV color system in an image obtained by observing the image using an optical microscope in transmission mode. When displaying an image in the HSV color system, image editing software such as GIMP can be used.

[0052] The number of foreign particles with a major axis of 3 μm or more contained in the temporary support and containing at least one element selected from the group consisting of F, Mg, Si, Ca, Ti, Fe, and Sb is measured, for example, by the following method.

[0053] First, the temporary support is observed with a polarizing microscope (product name "BX60" with a "U-POT" filter and a "U-AN360" filter inserted to form a simple polarizing microscope, 10x objective lens, manufactured by Olympus Corporation), and any areas where polarization is disturbed are identified as foreign matter. Furthermore, the major diameter of the foreign matter is measured with an optical microscope (product name "BX60" with a 100x objective lens, manufactured by Olympus Corporation), and foreign matter with a major diameter of 3 μm or more is identified. Observation area: 250 mm 2 The foreign matter contained in the sample, which has a major axis of 3 μm or more, is cut using a microtome, and elemental analysis is performed by the SEM-EDX method using a SEM-EDX device (product name "JSM-7200F", manufactured by JEOL Ltd.). The detected foreign matter is compared with a normal area around the foreign matter, and the number of foreign matter in which at least one element selected from the group consisting of F, Mg, Si, Ca, Ti, Fe, and Sb is counted. Note that the normal area around the foreign matter is an area in which no polarization disturbance occurs when observed with the polarizing microscope.

[0054] In addition, among the foreign matters contained in the temporary support, those with a 1580 cm -1 and 1360 cm -1 The number of foreign particles at which two peaks are observed can be determined, for example, by the following method. It is measured in.

[0055] First, the temporary support is observed with a polarizing microscope (product name "BX60" with a "U-POT" filter and a "U-AN360" filter inserted to form a simple polarizing microscope, 10x objective lens, manufactured by Olympus Corporation), and any areas where polarization is disturbed are identified as foreign matter. Furthermore, the major diameter of the foreign matter is measured with an optical microscope (product name "BX60" with a 100x objective lens, manufactured by Olympus Corporation), and foreign matter with a major diameter of 3 μm or more is identified. Observation area: 250 mm 2 Foreign matter with a major axis of 3 μm or more contained in the sample is cut with a microtome and analyzed by laser Raman spectroscopy using a SEM-EDX device (product name "JSM-7200F" manufactured by JEOL Ltd.). Analysis is performed using an objective lens with a numerical aperture (NA) of 0.90 and a magnification of 100x, and an excitation wavelength of 785 nm. The difference spectrum between the foreign matter and the normal area around the foreign matter is taken, and the peak intensity at 1580 cm is measured. -1 and 1360 cm -1 The number of foreign particles for which the two peaks are observed is counted.

[0056] In the photosensitive transfer material according to the present disclosure, it is preferable that the temporary support does not substantially contain added particles from the viewpoint of obtaining a resin pattern with reduced defects. It is preferably substantially free of additive particles.

[0057] In the photosensitive transfer material according to the present disclosure, the temporary support preferably does not include the particle-containing layer. The temporary support is preferably a single layer containing a resin, and the photosensitive resin layer is preferably disposed directly on the temporary support. Whether the temporary support is a single layer containing a resin can be determined by cutting the temporary support in the thickness direction and examining the cross section.

[0058] The thickness of the temporary support is not particularly limited, and may be appropriately selected depending on the material from the viewpoints of the strength as a support, the flexibility required for bonding to the circuit wiring formation substrate, and the light transmittance required in the initial exposure step.

[0059] The thickness of the temporary support is preferably 5 μm to 100 μm, and from the viewpoint of ease of handling and versatility, more preferably 10 μm to 50 μm.

[0060] [Photosensitive resin layer] The photosensitive transfer material according to the present disclosure includes a photosensitive resin layer. After the photosensitive resin layer is transferred onto a transfer-receiving body, a pattern can be formed on the transfer-receiving body by performing exposure and development.

[0061] In display devices (organic electroluminescence (EL) display devices, liquid crystal display devices, etc.) equipped with a touch panel such as a capacitance-type input device, a conductive layer pattern, such as an electrode pattern corresponding to the sensor of the visible part, and wiring of the peripheral wiring part and the extraction wiring part, is provided inside the touch panel. Generally, a method of forming a patterned layer is widely adopted in which a negative photosensitive resin layer is provided on a substrate using a photosensitive transfer material or the like, and the photosensitive resin layer is exposed to light through a mask having a desired pattern, and then developed.

[0062] The photosensitive resin layer can be obtained, for example, by applying a photosensitive resin composition and drying it. The photosensitive resin layer preferably contains a polymer A, a polymerizable compound B, and a photopolymerization initiator. The photosensitive resin layer preferably contains 10% by mass to 90% by mass of polymer A, 5% by mass to 70% by mass of polymerizable compound B, and 0.01% by mass to 20% by mass of the photopolymerization initiator, relative to the total mass of the photosensitive resin layer. Each component will be explained below in order.

[0063] <Ingredients> (Polymer A) The polymer A is preferably an alkali-soluble resin. An alkali-soluble resin refers to a polymer that is easily soluble in an alkaline substance. In this specification, "alkali-soluble" means that the solubility in 100 g of a 1% by mass aqueous solution of sodium carbonate at 22°C is 0.1 g or more.

[0064] 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, since suppressing swelling of the photosensitive resin layer by the developer results in better resolution.

[0065] There is no particular limitation on the lower limit of the acid value of polymer A. 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, from the viewpoint of more excellent developability.

[0066] The acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of sample. In this specification, the unit of acid value is written as mgKOH / g. The acid value can be calculated, for example, by the mass [mg] of potassium hydroxide required to neutralize 1 g of sample. It can be calculated from the average content of acid groups in the polymer.

[0067] The acid value of polymer A may be adjusted by changing the type of structural unit constituting polymer A and the content of structural units containing an acid group.

[0068] 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 preferred because it improves 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 preferred because it allows for control of the properties of the developed aggregates and the properties of the unexposed film, such as edge fusing and cut-chip resistance, when formed into a photosensitive resin laminate. 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 resin layer easily protrudes from the edge of a roll when the photosensitive resin laminate is wound into a roll. The cut chip property refers to the degree to which chips fly off when an unexposed film is cut with a cutter. If these chips adhere to the upper surface of the photosensitive resin laminate, they will be transferred to a mask in a subsequent exposure step, causing defective products.

[0069] The dispersity 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 the present disclosure, the molecular weight is a value measured using gel permeation chromatography. The dispersity is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight).

[0070] From the viewpoint of suppressing line width thickening and resolution degradation caused by shifts in the focal position during exposure, polymer A preferably contains a structural unit derived from a monomer having an aromatic hydrocarbon group. Examples of aromatic hydrocarbon groups include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group. The content of structural units derived from monomers having an aromatic hydrocarbon group 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. The upper limit of this content is not particularly limited. The content is preferably 95% by mass or less, more preferably 85% by mass or less, based on the total mass of polymer A. When multiple types of polymer A are contained, the content of structural units derived from monomers having an aromatic hydrocarbon group is determined as a weight average value.

[0071] Examples of monomers having an aromatic hydrocarbon group include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer). Among these, the monomer having an aromatic hydrocarbon group is preferably a monomer having an aralkyl group or styrene. When the monomer having an aromatic hydrocarbon group is styrene, the content of the structural units derived from styrene is preferably 20% by mass to 50% by mass, more preferably 25% by mass to 45% by mass, even more preferably 30% by mass to 40% by mass, and particularly preferably 30% by mass to 35% by mass, based on the total mass of polymer A. When the photosensitive resin layer contains multiple types of polymer A, the content of the structural units having an aromatic hydrocarbon group is determined as a weight average value.

[0072] Examples of the aralkyl group include substituted or unsubstituted phenylalkyl groups (excluding benzyl groups); and substituted or unsubstituted benzyl groups. The aralkyl group is preferably a substituted or unsubstituted benzyl group.

[0073] An example of a monomer having a phenylalkyl group is phenylethyl (meth)acrylate.

[0074] Examples of the monomer having a benzyl group include (meth)acrylates having a benzyl group and vinyl monomers having a benzyl group. Examples of the (meth)acrylates having a benzyl group include benzyl (meth)acrylate and chlorobenzyl (meth)acrylate. Examples of the vinyl monomer having a benzyl group include vinylbenzyl chloride and vinylbenzyl alcohol. Among them, the monomer having a benzyl group is preferably benzyl (meth)acrylate. When the monomer having an aromatic hydrocarbon group is benzyl (meth)acrylate, the content of the structural unit derived from benzyl (meth)acrylate is preferably 50% by mass to 95% by mass, more preferably 60% by mass to 90% by mass, even more preferably 70% by mass to 90% by mass, and particularly preferably 75% by mass to 90% by mass, based on the total mass of polymer A.

[0075] The polymer A containing a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably a polymer containing a structural unit derived from a monomer having an aromatic hydrocarbon group and a structural unit derived from at least one monomer selected from the group consisting of a first monomer described below and a second monomer described below.

[0076] The polymer A that does not contain a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably a polymer that contains a structural unit derived from at least one monomer selected from the group consisting of a first monomer and a second monomer, and more preferably a polymer that contains a structural unit derived from at least one first monomer and at least one second monomer.

[0077] The first monomer is a monomer having an anionic group and at least one polymerizable unsaturated group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. Among these, the first monomer is preferably (meth)acrylic acid.

[0078] The content of the structural units derived from the first monomer in polymer A is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and even more preferably 15% by mass to 30% by mass, relative to the total mass of polymer A.

[0079] The second monomer is a monomer that does not have an anionic group and has at least one polymerizable unsaturated group in the 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; vinyl esters such as vinyl acetate; and (meth)acrylonitrile. Among these, the second monomer is preferably methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or n-butyl (meth)acrylate, with methyl (meth)acrylate being particularly preferred.

[0080] The content of the structural units derived from the second monomer in polymer A is preferably 5% by mass to 60% by mass, more preferably 15% by mass to 50% by mass, and even more preferably 20% by mass to 45% by mass, relative to the total mass of polymer A.

[0081] From the viewpoint of suppressing line width thickening and resolution degradation caused by shifts in the focal position during exposure, polymer A preferably contains a structural unit derived from at least one monomer selected from the group consisting of a monomer having an aralkyl group and styrene. Specifically, polymer A is preferably a copolymer containing a structural unit derived from styrene, a structural unit derived from methyl methacrylate, and a structural unit derived from methacrylic acid.

[0082] In a first embodiment, polymer A preferably contains 25% to 40% by mass of structural units derived from a monomer having an aromatic hydrocarbon group, 20% to 35% by mass of structural units derived from a first monomer, and 30% to 45% by mass of structural units derived from a second monomer. In a second embodiment, polymer A preferably contains 70% to 90% by mass of structural units derived from a monomer having an aromatic hydrocarbon group, and 10% to 25% by mass of structural units derived from the first monomer. In a third embodiment, polymer A preferably contains 40% to 60% by mass of structural units derived from a monomer having an aromatic hydrocarbon group, 20% to 35% by mass of structural units derived from the first monomer, and 10% to 25% by mass of structural units derived from the second monomer.

[0083] The polymer A may have a linear structure, a branched structure, or an alicyclic structure in the side chain. A branched structure or an alicyclic structure can be introduced into the side chain of the polymer A by using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain.

[0084] Examples of the monomer containing a group having a branched structure in the 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, sec-iso-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and t-octyl (meth)acrylate. Among these, the monomer containing a group having a branched structure in the side chain is preferably i-propyl (meth)acrylate, i-butyl (meth)acrylate, or t-butyl (meth)acrylate, more preferably i-propyl (meth)acrylate or t-butyl (meth)acrylate.

[0085] Examples of the monomer containing a group having an alicyclic structure in the side chain include (meth)acrylates having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. Specific examples of the monomer containing a group having an alicyclic structure in the side chain include (bicyclo[2.2.1]heptyl-2)(meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, 3-methyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-1-adamantyl (meth)acrylate, 3-ethyladamantyl (meth)acrylate, 3-methyl-5-ethyl-1-adamantyl (meth)acrylate, 3,5,8-triethyl-1-adamantyl (meth)acrylate, and 3,5-dimethyl-8-ethyl-1-adamantyl (meth)acrylate. Mantyl, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, 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[3.1.1]heptyl (meth)acrylate [4.1.0]heptyl, norbornyl (meth)acrylate, isobornyl (meth)acrylate, fenchyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, and cyclohexyl (meth)acrylate. Among them, the monomer containing a group having an alicyclic structure in the side chain is preferably cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fenchyl (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecane (meth)acrylate, and more preferably cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate.

[0086] The photosensitive resin layer may contain one type of polymer A alone or two or more types. When two or more types of polymer A are contained, the photosensitive resin layer preferably contains two types of polymer A containing structural units derived from a monomer having an aromatic hydrocarbon group. The photosensitive resin layer also preferably contains a polymer A1 containing structural units derived from a monomer having an aromatic hydrocarbon group, and a polymer A2 not containing structural units derived from a monomer having an aromatic hydrocarbon group. In the latter case, the content of polymer A1 is preferably 50% by mass or more, more preferably 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more, based on the total mass of polymer A.

[0087] 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 of the above monomers with a solvent such as acetone, methyl ethyl ketone, or isopropanol, and stirring the mixture while heating. After the reaction is complete, further solvent may be added to adjust the concentration to the desired level. Polymerization methods include bulk polymerization, suspension polymerization, and emulsion polymerization, in addition to solution polymerization.

[0088] The glass transition temperature Tg of the polymer A is preferably 30°C to 135°C. By incorporating a polymer A having a Tg of 135°C or less into the photosensitive resin layer, it is possible to suppress line width thickening and resolution degradation when the focus position is shifted during exposure. The Tg of the polymer A is more preferably 130°C or less, even more preferably 120°C or less, and particularly preferably 110°C or less. Furthermore, incorporating a polymer A having a Tg of 30°C or more into the photosensitive resin layer is preferable from the viewpoint of improving edge fuse resistance. The Tg of the polymer A is more preferably 40°C or more, even more preferably 50°C or more, particularly preferably 60°C or more, and most preferably 70°C or more.

[0089] The content of polymer A is preferably in the range of 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, and even more preferably 40% by mass to 60% by mass, relative to the total mass of the photosensitive resin layer. It is preferable that the content of polymer A relative to the total mass of the photosensitive resin layer is 90% by mass or less, since this allows for control of the development time. On the other hand, it is preferable that the content of polymer A relative to the total mass of the photosensitive resin layer is 10% by mass or more, since this improves edge fuse resistance.

[0090] (Polymerizable compound B) The photosensitive resin layer contains a polymerizable compound B having a polymerizable group. In this specification, the term "polymerizable compound" refers to a compound that is polymerized by the action of a polymerization initiator described below, and is different from the polymer A described above.

[0091] The polymerizable group of the polymerizable compound B is not particularly limited as long as it is a group that participates in a polymerization reaction, and examples thereof include a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group. and cationically polymerizable groups such as an epoxy group and an oxetane group.

[0092] The polymerizable group is preferably an ethylenically unsaturated group, more preferably an acryloyl group or a methacryloyl group.

[0093] As the polymerizable compound B, a compound having one or more ethylenically unsaturated groups (i.e., an ethylenically unsaturated compound) is preferred, and a compound having two or more ethylenically unsaturated groups in one molecule (i.e., a polyfunctional ethylenically unsaturated compound) is more preferred, in that the photosensitivity of the photosensitive resin layer is superior.

[0094] In terms of achieving better resolution and releasability, the number of ethylenically unsaturated groups that the ethylenically unsaturated compound has in one molecule is preferably 6 or less, more preferably 3 or less, and even more preferably 2 or less.

[0095] The photosensitive resin layer preferably contains a bifunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule, or a trifunctional ethylenically unsaturated compound having three ethylenically unsaturated groups, in that the photosensitive resin layer has a better balance of photosensitivity, resolution, and releasability, and more preferably contains a bifunctional ethylenically unsaturated compound.

[0096] From the viewpoint of excellent releasability, the content of the bifunctional ethylenically unsaturated compound is preferably 60% by mass or more, more preferably more than 70% by mass, and even more preferably 90% by mass or more, based on the total mass of the polymerizable compound B. The upper limit of the content of the bifunctional ethylenically unsaturated compound is not particularly limited and may be 100% by mass. That is, all of the polymerizable compound B contained in the photosensitive resin layer may be a bifunctional ethylenically unsaturated compound.

[0097] The ethylenically unsaturated compound is preferably a (meth)acrylate compound.

[0098] -Polymerizable compound B1- The photosensitive resin layer preferably contains a polymerizable compound B1 having at least one aromatic ring and two ethylenically unsaturated groups in one molecule.

[0099] In the photosensitive resin layer, the content of polymerizable compound B1 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, based on the total mass of polymerizable compound B, from the viewpoint of superior resolution. There is no particular upper limit for the content of polymerizable compound B1. In terms of releasability, the content of polymerizable compound B1 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, based on the total mass of polymerizable compound B.

[0100] Examples of the aromatic ring contained in the polymerizable compound B1 include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, and an anthracene ring; aromatic heterocycles such as a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring, and a pyridine ring; and condensed rings thereof. The aromatic ring contained in the polymerizable compound B1 is preferably an aromatic hydrocarbon ring, more preferably a benzene ring. The aromatic ring may have a substituent.

[0101] The polymerizable compound B1 preferably has a bisphenol skeleton from the viewpoint of suppressing swelling of the photosensitive resin layer due to a developer and improving resolution.

[0102] The bisphenol skeleton is, for example, bisphenol A (2,2-bis(4-hydroxybenzoyl) Examples of the bisphenol skeleton include a bisphenol A skeleton derived from bisphenol F (2,2-bis(4-hydroxyphenyl)propane), a bisphenol F skeleton derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and a bisphenol B skeleton derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane). Of these, the bisphenol skeleton is preferably a bisphenol A skeleton.

[0103] Examples of the polymerizable compound B1 having a bisphenol skeleton include a compound having a bisphenol skeleton and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol skeleton.

[0104] The bisphenol skeleton and the polymerizable group may be bonded directly or via one or more alkyleneoxy groups. The alkyleneoxy group bonded to the bisphenol skeleton is preferably an ethyleneoxy group or a propyleneoxy group, and more preferably an ethyleneoxy group. The number of alkyleneoxy groups added to the bisphenol skeleton is not particularly limited. The number of alkyleneoxy groups added per molecule is preferably 4 to 16, and more preferably 6 to 14.

[0105] The polymerizable compound B1 having a bisphenol skeleton is described in paragraphs 0072 to 0080 of JP-A-2016-224162, the contents of which are incorporated herein by reference.

[0106] The polymerizable compound B1 is preferably a bifunctional ethylenically unsaturated compound having a bisphenol A skeleton, and more preferably 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane.

[0107] 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)phenyl)propane. Examples of suitable ethoxylated bisphenol A diacrylates include 2,2-bis(4-(methacryloxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.), and ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0108] The polymerizable compound B1 includes a compound represented by the following general formula (I). [ka] In the formula, R 1 and R 2 each independently represent a hydrogen atom or a methyl group, A is C2H4, B is C3H6, n1 and n3 each independently represent an integer of 1 to 39, and n1 + n3 is an integer of 2 to 40, n2 and n4 each independently represent an integer of 0 to 29, and n2 + n4 is an integer of 0 to 30, and the arrangement of the -(AO)- and -(BO)- repeating units may be random or block. In the case of a block, either -(AO)- or -(BO)- may be on the bisphenyl group side.

[0109] n1+n2+n3+n4 is preferably 2 to 20, more preferably 2 to 16, and even more preferably 4 to 12. Furthermore, n2+n4 is preferably 0 to 10, more preferably 0 to 4, even more preferably 0 to 2, and particularly preferably 0.

[0110] The photosensitive resin layer may contain one type of polymerizable compound B1 alone or two or more types of polymerizable compound B1.

[0111] The content of the polymerizable compound B1 is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the photosensitive resin layer, from the viewpoint of achieving better resolution. The upper limit of the content of the polymerizable compound B1 is not particularly limited. The content of the polymerizable compound B1 is preferably 70% by mass or less, more preferably 60% by mass or less, from the viewpoint of improving transferability and edge fuse resistance.

[0112] The photosensitive resin layer may contain a polymerizable compound B other than the polymerizable compound B1. The polymerizable compound B other than the polymerizable compound B1 is not particularly limited and can be appropriately selected from known compounds. For example, the polymerizable compound B other than the polymerizable compound B1 can be a compound having one ethylenically unsaturated group in one molecule (i.e., a monofunctional ethylenically unsaturated compound), a bifunctional ethylenically unsaturated compound having no aromatic ring, or a trifunctional or higher ethylenically unsaturated compound. Compounds include:

[0113] 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.

[0114] Examples of bifunctional ethylenically unsaturated compounds having no aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate.

[0115] Examples of alkylene glycol di(meth)acrylates include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate.

[0116] 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.

[0117] 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. Commercially available products include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0118] Examples of tri- or higher functional ethylenically unsaturated compounds 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.

[0119] 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.

[0120] The photosensitive resin layer preferably contains a polymerizable compound B1 and a tri- or higher functional ethylenically unsaturated compound, more preferably a polymerizable compound B1 and two or more tri- or higher functional ethylenically unsaturated compounds. In this case, the mass ratio of the polymerizable compound B1 to the tri- or higher functional ethylenically unsaturated compounds (total mass of the polymerizable compound B1:total mass of the tri- or higher functional ethylenically unsaturated compounds) is preferably 1:1 to 5:1, more preferably 1.2:1 to 4:1, and even more preferably 1.5:1 to 3:1.

[0121] Examples of alkylene oxide-modified trifunctional or higher ethylenically unsaturated compounds include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20, manufactured by Nippon Kayaku Co., Ltd.; A-9300-1CL, manufactured by Shin-Nakamura Chemical Co., Ltd.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040, manufactured by Nippon Kayaku Co., Ltd.; ATM-35E and A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.; EBECRYL (registered trademark) 135, manufactured by Daicel-Allnex Corporation), ethoxylated glycerin triacrylate (A-GLY-9E, manufactured by Shin-Nakamura Chemical Co., Ltd.), ARONIX (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), ARONIX M-520 (manufactured by Toagosei Co., Ltd.), and ARONIX M-510 (manufactured by Toagosei Co., Ltd.).

[0122] Furthermore, the polymerizable compound B other than the polymerizable compound B1 may be a polymerizable compound having an acid group described in paragraphs 0025 to 0030 of JP-A No. 2004-239942.

[0123] The photosensitive resin layer may contain one type of polymerizable compound B alone or two or more types thereof.

[0124] The content of the polymerizable compound B is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and even more preferably 20% by mass to 50% by mass, based on the total mass of the photosensitive resin layer.

[0125] The weight average molecular weight (Mw) of the polymerizable compound B including the polymerizable compound B1 is preferably from 200 to 3,000, more preferably from 280 to 2,200, and even more preferably from 300 to 2,200.

[0126] (optional ingredient) The photosensitive resin layer may contain components other than the polymer A and the polymerizable compound B.

[0127] -Photopolymerization initiator- The photosensitive resin layer preferably contains a photopolymerization initiator.

[0128] A photopolymerization initiator is a compound that has the effect of initiating polymerization of a polymerizable compound by actinic rays such as ultraviolet rays, visible light, X-rays, etc. The photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used.

[0129] Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator. Among them, the photopolymerization initiator is preferably a photoradical polymerization initiator.

[0130] Examples of the photoradical polymerization initiator include a photopolymerization initiator having an oxime ester skeleton, a photopolymerization initiator having an α-aminoalkylphenone skeleton, a photopolymerization initiator having an α-hydroxyalkylphenone skeleton, a photopolymerization initiator having an acylphosphine oxide skeleton, and a photopolymerization initiator having an N-phenylglycine skeleton.

[0131] From the viewpoints of photosensitivity, visibility of exposed and unexposed areas, and resolution, the photosensitive resin layer preferably contains, as a photoradical polymerization initiator, at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof. Note that the two 2,4,5-triarylimidazole skeletons in the 2,4,5-triarylimidazole dimers and derivatives thereof may be the same or different. Examples of the derivatives of 2,4,5-triarylimidazole dimers include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimers, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimers, )-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.

[0132] The photoradical polymerization initiator may be a polymerization initiator described in paragraphs 0031 to 0042 of JP-A No. 2011-95716 and paragraphs 0064 to 0081 of JP-A No. 2015-14783.

[0133] Examples of the photoradical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), and benzophenone.

[0134] Commercially available photoradical polymerization initiators include, for example, 2,4-bis(trichloromethyl)-6-[2-(4-methylphenyl)ethenyl]-1,3,5-triazine (trade name: TAZ-110, manufactured by Midori Chemical Industry Co., Ltd.), (trade name: TAZ-111, manufactured by Midori Chemical Industry Co., Ltd.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime) (trade name: Irgacure® OXE-01, manufactured by BASF Japan Ltd.), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (trade name: Irgacure® OXE-01, manufactured by BASF Japan Ltd.), and OXE-02, manufactured by BASF Japan Ltd.), Irgacure OXE-03 (manufactured by BASF Japan Ltd.), OXE-04 (manufactured by BASF Japan Ltd.), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins BV), 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 (trade name: Omnirad 127, manufactured by IGM Resins BV), BV), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (trade name: Omnirad 369, IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, IGM Resins BV). BV), 1-hydroxycyclohexyl phenyl ketone (trade name: Omnirad 184, IGM Resins BV), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651, IGM Resins BV), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, IGM Resins BV), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, IGM Resins BV), oxime ester photoinitiator (trade 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) (trade name: B-CIM, manufactured by Hampford Chemical Industry Co., Ltd.), and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.).

[0135] A photocationic polymerization initiator (photoacid generator) is a compound that generates an acid when exposed to actinic rays. There are no particular limitations on the photocationic polymerization initiator, but it is preferable that the photocationic polymerization initiator is a compound that is sensitive to actinic rays with a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid. Even if the compound is not directly sensitive to actinic rays with a wavelength of 300 nm or more, it can be used in combination with a sensitizer. Any compound that reacts to actinic rays with a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer can be preferably used.

[0136] The cationic photopolymerization initiator is preferably a cationic photopolymerization initiator that generates an acid having a pKa of 4 or less, more preferably a cationic photopolymerization initiator that generates an acid having a pKa of 3 or less, and particularly preferably a cationic photopolymerization initiator that generates an acid having a pKa of 2 or less. The lower limit of the pKa is not particularly limited, and is preferably, for example, −10.0.

[0137] Examples of the photocationic polymerization initiator include an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator.

[0138] Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.

[0139] The ionic photocationic polymerization initiator may be an ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of JP-A No. 2014-85643.

[0140] Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triazine compounds, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. The trichloromethyl-s-triazine compounds, diazomethane compounds, and imide sulfonate compounds may be compounds described in paragraphs 0083 to 0088 of JP 2011-221494 A. The oxime sulfonate compounds may be compounds described in paragraphs 0084 to 0088 of WO 2018 / 179640 A.

[0141] The photosensitive resin layer may contain one type of photopolymerization initiator alone or two or more types of photopolymerization initiators.

[0142] The content of the photopolymerization initiator 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, relative to the total mass of the photosensitive resin layer. The upper limit of the content of the photopolymerization initiator is not particularly limited. The content of the photopolymerization initiator is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the photosensitive resin layer.

[0143] -Dye- From the viewpoints of the visibility of exposed and unexposed areas, the pattern visibility after development, and resolution, the photosensitive resin layer preferably contains a dye (hereinafter simply referred to as "dye N") that has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 nm to 780 nm during color development and whose maximum absorption wavelength changes in response to an acid, a base, or a radical. When dye N is contained, adhesion to adjacent layers (for example, a temporary support and an intermediate layer) is improved, resulting in better resolution, although the detailed mechanism is unknown.

[0144] In this specification, the expression "the maximum absorption wavelength of a dye changes in response to an acid, a base, or a radical" may mean any of an embodiment in which a dye in a colored state is decolorized by an acid, a base, or a radical, an embodiment in which a dye in a decolorized state develops color by an acid, a base, or a radical, and an embodiment in which a dye in a colored state changes to a colored state of another hue.

[0145] Specifically, the dye N may be a compound that changes from a decolorized state to a colored state upon exposure, or may be a compound that changes from a colored state to a discolored state upon exposure. In this case, an acid, a base, or a radical is generated in the photosensitive resin layer upon exposure, thereby changing the colored or discolored state. The dye N may be a dye whose color-developing or decoloring state changes when the state (e.g., pH) in the photosensitive resin layer changes due to an acid, a base, or a radical. The dye N may also be a dye whose color-developing or decoloring state changes when it is directly stimulated by an acid, a base, or a radical without being exposed to light.

[0146] Among these, from the viewpoints of the visibility of exposed and unexposed areas and resolution, dye N is preferably a dye whose maximum absorption wavelength changes in response to an acid or a radical, and more preferably a dye whose maximum absorption wavelength changes in response to a radical.

[0147] From the viewpoints of the visibility of exposed and unexposed areas and resolution, the photosensitive resin layer preferably contains both a dye whose maximum absorption wavelength changes in response to radicals as dye N, and a photoradical polymerization initiator.

[0148] From the viewpoint of visibility of exposed and unexposed areas, dye N is preferably a dye that develops color in response to an acid, a base, or a radical.

[0149] An example of the color-developing mechanism of dye N is an embodiment in which a photoradical polymerization initiator, a cationic photopolymerization initiator (photoacid generator), or a photobase generator is added to a photosensitive resin layer, and color is developed by a radical, acid, or base generated from the photoradical polymerization initiator, the cationic photopolymerization initiator, or the photobase generator after exposure.

[0150] From the viewpoint of visibility of exposed and unexposed areas, dye N preferably has a maximum absorption wavelength of 550 nm or more in the wavelength range of 400 nm to 780 nm upon color development, more preferably 550 to 700 nm, and even more preferably 550 to 650 nm.

[0151] Furthermore, dye N may have only one or two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm when it develops color. When dye N has two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm when it develops color, it is sufficient that the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths is 450 nm or longer.

[0152] The maximum absorption wavelength of dye N can be obtained by measuring the transmission spectrum of a solution containing dye N (liquid temperature 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).

[0153] Examples of the dye that develops or loses color upon exposure include leuco compounds. Examples of the dye that loses color upon exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes. Among these, dye N is preferably a leuco compound from the viewpoint of visibility of exposed and unexposed areas.

[0154] Examples of leuco compounds include leuco compounds having a triarylmethane skeleton (triarylmethane-based dyes), leuco compounds having a spiropyran skeleton (spiropyran-based dyes), leuco compounds having a fluoran skeleton (fluoran-based dyes), leuco compounds having a diarylmethane skeleton (diarylmethane-based dyes), leuco compounds having a rhodamine lactam skeleton (rhodamine lactam-based dyes), leuco compounds having an indolylphthalide skeleton (indolylphthalide-based dyes), and leuco compounds having a leucoauramine skeleton (leucoauramine-based dyes).

[0155] Among these, the leuco compound is preferably a triarylmethane dye or a fluoran dye, and more preferably a leuco compound having a triphenylmethane skeleton (triphenylmethane dye) or a fluoran dye.

[0156] From the viewpoint of visibility of exposed and unexposed areas, the leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring. The lactone ring, sultine ring, or sultone ring of the leuco compound changes from a closed state to a ring-open state and develops color, or changes from a ring-open state to a closed state and loses color, upon reaction with a radical generated from a photoradical polymerization initiator or an acid generated from a photocationic polymerization initiator. The leuco compound is preferably a compound having a lactone ring, a sultine ring, or a sultone ring that develops color upon ring-opening by a radical or an acid, and more preferably a compound having a lactone ring that develops color upon ring-opening by a radical or an acid.

[0157] Examples of the dye N include the following dyes and leuco compounds. The dyes used include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, quinaldine red, rose bengal, metanil yellow, thymolsulfophthalein, xylenol blue, methyl orange, paramethyl red, Congo red, benzopurpurin 4B, α-naphthyl red, Nile blue 2B, Nile blue A, methyl violet, malachite green, parafuchsin, Victoria Pure Blue-naphthalenesulfonate, 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.), and Oil Scarlet #308 (manufactured by Orient Chemical Co., Ltd.). Co., Ltd.), Oil Red OG (Orient Chemical Industries Co., Ltd.), Oil Red RR (Orient Chemical Industries Co., Ltd.), Oil Green #502 (Orient Chemical Industries Co., Ltd.), Spiron Red BEH Special (Hodogaya Chemical 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)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0158] Leuco compounds include p,p',p"-hexamethyltriaminotriphenylmethane (leuco crystal violet) and Pergascript Blue. SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl leucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(Np-tolyl-N-ethyl)aminofluoran, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluoran, 3,6-dimethoxyfluoran, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluoran, 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-xylidinofluoran, 3-(N,N-diethylamino)-6-methyl-7-xylidinofluoran, (N,N-diethylamino)-6-methyl-7-chlorofluoran, 3-(N,N-diethylamino)-6-methoxy-7-aminofluoran, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluoran, 3-(N,N-diethylamino)-7-chlorofluoran, 3-(N,N-diethylamino)-7-benzylaminofluoran, 3-(N,N-diethylamino)-7,8-benzofluoran, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluoran, 3-(N,N-dibutylamino)-6-methyl-7-xylidinofluoran, 3-piperidino-6-methyl-7-anilinofluoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 3,3-bis(1-ethyl-2-methylindole-3 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-n-butyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-phthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthen-3-one.

[0159] From the viewpoints of the visibility of exposed and unexposed areas, the pattern visibility after development, and resolution, dye N is preferably a dye whose maximum absorption wavelength changes in response to radicals, and more preferably a dye that develops color in response to radicals.

[0160] Dye N is preferably leuco crystal violet, crystal violet lactone, brilliant green, or Victoria Pure Blue-naphthalene sulfonate.

[0161] The photosensitive resin layer may contain one type of dye N alone or two or more types thereof.

[0162] From the viewpoints of the visibility of exposed and unexposed areas, the pattern visibility after development, and resolution, the content of dye N is preferably 0.1 mass % or more, more preferably 0.1 mass % to 10 mass %, even more preferably 0.1 mass % to 5 mass %, and particularly preferably 0.1 mass % to 1 mass %, relative to the total mass of the photosensitive resin layer.

[0163] The content of dye N means the content of dye when all of the dye N contained in the photosensitive resin layer is in a color-developing state. Hereinafter, a method for quantifying the content of dye N will be described using a dye that develops color by radicals as an example.

[0164] Solutions were prepared by dissolving 0.001 g and 0.01 g of dye in 100 mL of methyl ethyl ketone. A photoradical polymerization initiator (Irgacure OXE01, manufactured by BASF Japan) was added to each solution, and radicals were generated by irradiating the solution with 365 nm light, causing all dyes to develop color. The absorbance of each solution was then measured at 25°C using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) under atmospheric conditions, and a calibration curve was created.

[0165] Next, the absorbance of the solution in which all the dye has developed is measured in the same manner as above, except that 3 g of the photosensitive resin layer is dissolved in methyl ethyl ketone instead of the dye.The content of the dye contained in the photosensitive resin layer is calculated based on the absorbance of the obtained solution containing the photosensitive resin layer and a calibration curve.

[0166] <Thermal crosslinkable compound>

[0033] From the viewpoints of the strength of the cured film obtained and the adhesiveness of the uncured film obtained, the photosensitive resin layer preferably contains a thermally crosslinkable compound. In this specification, a thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is not considered an ethylenically unsaturated compound but is considered a thermally crosslinkable compound. Examples of the thermally crosslinkable compound include methylol compounds and blocked isocyanate compounds. Among these, blocked isocyanate compounds are preferred from the viewpoints of the strength of the resulting cured film and the adhesiveness of the resulting uncured film. Blocked isocyanate compounds react with hydroxyl groups and carboxyl groups, so when 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 film formed decreases and the photosensitivity decreases. This tends to enhance the functionality when the cured resin layer is used as a protective film. The blocked isocyanate compound refers to a compound having a structure in which the isocyanate group of an isocyanate is protected (so-called masked) with a blocking agent.

[0167] 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 a blocked isocyanate means "the temperature of the endothermic peak accompanying the deprotection reaction of the blocked isocyanate when measured by DSC (Differential Scanning Calorimetry) analysis using a differential scanning calorimeter." As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be suitably used. However, the differential scanning calorimeter is not limited to this.

[0168] Examples of blocking agents having a dissociation temperature of 100°C to 160°C include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)] and oxime compounds (compounds having a structure represented by -C(=N-OH)- in the molecule, such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, and cyclohexanoneoxime). Among these, the blocking agent having a dissociation temperature of 100° C. to 160° C. preferably contains an oxime compound, for example, from the viewpoint of storage stability.

[0169] The blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the film and improving the adhesive strength to the transfer target. A blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by protecting hexamethylene diisocyanate by isocyanuration. Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure in which an oxime compound is used as a blocking agent are preferred from the viewpoints that the dissociation temperature can be more easily adjusted to a preferred range and development residues can be reduced compared to compounds not having an oxime structure.

[0170] The blocked isocyanate compound may have a polymerizable group. The polymerizable group is not particularly limited, and any known polymerizable group can be used, with a radical polymerizable group being preferred. Examples of the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloxy group, a (meth)acrylamide group, and a styryl group, as well as groups having an epoxy group such as a glycidyl group. Among these, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloxy group, and even more preferably an acryloxy group.

[0171] As the blocked isocyanate compound, commercially available products can be used. Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, and the like (all manufactured by Showa Denko K.K.), and the blocked Duranate series (e.g., Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, and the like, manufactured by Asahi Kasei Chemicals Corporation). Furthermore, as the blocked isocyanate compound, a compound having the following structure can also be used.

[0172] [ka]

[0173] The thermally crosslinkable compounds may be used alone or in combination of two or more. When the photosensitive resin layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass, relative to the total mass of the photosensitive resin layer.

[0174] <Surfactant> From the viewpoint of thickness uniformity, the photosensitive resin layer preferably contains a surfactant.

[0175] Examples of surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. Of these, nonionic surfactants are preferred.

[0176] Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based nonionic surfactants, and fluorine-based nonionic surfactants.

[0177] From the viewpoint of improving resolution, the photosensitive resin layer preferably contains a fluorine-based nonionic surfactant, which is believed to be because the inclusion of a fluorine-based nonionic surfactant in the photosensitive resin layer inhibits penetration of the etching solution into the photosensitive resin layer, thereby reducing side etching.

[0178] The surfactant may be a surfactant described in paragraphs 0120 to 0125 of International Publication No. 2018 / 179640, a surfactant described in paragraph 0017 of Japanese Patent No. 4502784, and a surfactant described in paragraphs 0060 to 0071 of Japanese Patent Laid-Open No. 2009-237362.

[0179] Commercially available fluorine-based surfactants include, for example, Megafac (trade name) F-171, F-172, F-173, F-176, F-177, F-141, F-142, and F-14. 3, F-144, F-437, F-444, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F- 556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-33 0, MFS-578, MFS-579, MFS-586, MFS-587, 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 (manufactured by DIC Corporation), Florado (product name) FC430, FC431, FC171 (manufactured by Sumitomo 3M Ltd.), Surflon (trade 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 (trade name) PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by AGC Inc.) , 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 Corporation), and the like. In addition, acrylic compounds that have a molecular structure with a functional group containing a fluorine atom and that volatilize when heated by cleaving the functional group containing the fluorine atom can also be used as the fluorosurfactant. Examples of such fluorosurfactants include the Megafac (trade name) DS series manufactured by DIC Corporation (The Chemical Daily, February 22, 2016; The Nikkei Business Daily, February 23, 2016), such as Megafac (trade name) DS-21.

[0180] As the fluorine-based 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. As the fluorine-based surfactant, a block polymer can also be used. As the fluorine-based surfactant, a fluorine-containing polymer compound 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) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups) can also be preferably used. As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used, such as Megafac (trade name) RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation). As the fluorosurfactant, for example, a compound having a linear perfluoroalkyl group having 7 or more carbon atoms may be used. However, from the viewpoint of improving environmental friendliness, it is preferable to use an alternative material to perfluorooctanoic acid (PFOA) or perfluorooctanesulfonic acid (PFOS) as the fluorosurfactant.

[0181] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, 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, Pluronic (trade name) L10, L31, L61, L62, 10R5, 17R2, 25R2 (all manufactured by BASF), Tetronic (trade name) 304, 701, 704, 901, 904, 150R1 (all manufactured by BASF), Solsperse (trade name) 20000 (all manufactured by Lubrizol Japan Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), Paionin (trade name) D-6112, D-6112-W, D-6315 (all manufactured by Takemoto Oil & Fat Co., Ltd.), Examples include Olfine E1010, Surfynol 104, 400, and 440 (all manufactured by Nissin Chemical Industry Co., Ltd.).

[0182] Examples of silicone surfactants include linear polymers consisting of siloxane bonds and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals. Specific examples of silicone surfactants include DOWSIL (trade name) 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Toray Dow Corning Co., Ltd.), as well as X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, and KF -945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (all manufactured by Shin-Etsu Chemical Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), BYK307, BYK323, BYK330 (all manufactured by BYK-Chemie), and the like.

[0183] The photosensitive resin layer may contain one type of surfactant alone or two or more types of surfactants.

[0184] The content of the surfactant is preferably 0.001% by mass to 10% by mass, and more preferably 0.01% by mass to 3% by mass, relative to the total mass of the photosensitive resin layer.

[0185] -Additives- In addition to the above components, the photosensitive resin layer may contain known additives as needed.

[0186] Examples of the additives include radical polymerization inhibitors, sensitizers, plasticizers, heterocyclic compounds, benzotriazoles, carboxybenzotriazoles, resins other than polymer A, and solvents. The photosensitive resin layer may contain one type of each additive alone, or two or more types.

[0187] The photosensitive resin layer may contain a radical polymerization inhibitor.

[0188] Examples of the radical polymerization inhibitor include the thermal polymerization inhibitors described in paragraph 0018 of Japanese Patent No. 4502784. Examples of the radical polymerization inhibitor include phenothiazine, phenoxazine, 4-methoxyphenol, naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. Among these, the radical polymerization inhibitor is preferably phenothiazine, phenoxazine, 4-methoxyphenol, or nitrosophenylhydroxyamine aluminum salt.

[0189] 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.

[0190] 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 Examples of commercially available carboxybenzotriazoles include N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole. Examples of commercially available carboxybenzotriazoles include CBT-1 (manufactured by Johoku Chemical Industry Co., Ltd.).

[0191] The total content of the radical polymerization inhibitor, benzotriazoles, and carboxybenzotriazoles is preferably 0.01% by mass to 3% by mass, and more preferably 0.05% by mass to 1% by mass, relative to the total mass of the photosensitive resin layer. When the content is 0.01% by mass or more, the storage stability of the photosensitive resin composition is excellent. On the other hand, when the content is 3% by mass or less, sensitivity can be maintained and decolorization of the dye can be suppressed.

[0192] The photosensitive resin layer may contain a sensitizer.

[0193] The sensitizer is not particularly limited, and known sensitizers, dyes, and pigments can be used. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

[0194] The photosensitive resin layer may contain one type of sensitizer alone or two or more types of sensitizers.

[0195] When the photosensitive resin layer contains a sensitizer, the content of the sensitizer can be appropriately selected depending on the purpose. From the viewpoints of improving sensitivity to a light source and improving the curing rate by balancing the polymerization rate and chain transfer, the content of the sensitizer is preferably 0.01% by mass to 5% by mass, and more preferably 0.05% by mass to 1% by mass, relative to the total mass of the photosensitive resin layer.

[0196] The photosensitive resin layer may contain at least one selected from the group consisting of plasticizers and heterocyclic compounds.

[0197] Examples of the plasticizer and heterocyclic compound include the compounds described in paragraphs 0097 to 0103 and 0111 to 0118 of WO 2018 / 179640.

[0198] The photosensitive resin layer may contain a resin other than the polymer A.

[0199] Examples of resins other than polymer A include acrylic resins, styrene-acrylic copolymers (with the content of structural units derived from styrene being 40% by mass or less), polyurethanes, polyvinyl alcohols, polyvinyl formals, polyamides, polyesters, epoxy resins, polyacetals, polyhydroxystyrenes, polyimides, polybenzoxazoles, polysiloxanes, polyethyleneimines, polyallylamine, and polyalkylene glycols.

[0200] The photosensitive resin layer may contain a solvent. When a photosensitive resin layer is formed by drying a photosensitive resin composition containing a solvent, the solvent may remain in the photosensitive resin layer.

[0201] The photosensitive resin layer may further contain known additives such as metal oxide particles, antioxidants, chain transfer agents, dispersants, acid multipliers, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic suspending agents.

[0202] Additives that may be contained in the photosensitive resin layer are described in paragraphs 0165 to 0184 of JP-A No. 2014-85643, the contents of which are incorporated herein by reference.

[0203] <Impurities, etc.> The photosensitive resin layer may contain a predetermined amount of impurities. Examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Among these, halide ions, sodium ions, and potassium ions are easily mixed in as impurities, so the following contents are preferred.

[0204] The content of impurities in the photosensitive resin layer is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less, by mass. The content of impurities in the photosensitive resin layer can be 1 ppb or more, or 0.1 ppm or more, by mass.

[0205] Methods for controlling the impurity content within the above range include selecting raw materials for the photosensitive resin layer that contain a small amount of impurities, preventing impurities from being mixed in when the photosensitive resin layer is formed, and removing impurities by washing. By using these methods, the impurity content in the photosensitive resin layer can be controlled within the above range.

[0206] Impurities can be quantitatively determined by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0207] The content of specific compounds, such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane, in the photosensitive resin layer is preferably low. The content of specific compounds in the photosensitive resin layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less, by mass. The lower limit of the content is preferably 10 ppb, more preferably 100 ppb, by mass. The content of specific compounds can be reduced by the same method as for the above-mentioned impurities. The content of specific compounds can also be quantified by known measurement methods.

[0208] The water content in the photosensitive resin layer is preferably 0.01% by mass to 1.0% by mass, and more preferably 0.05% by mass to 0.5% by mass, from the viewpoint of improving reliability and lamination properties.

[0209] <Residual monomer> The photosensitive resin layer may contain residual monomers corresponding to the respective structural units of the alkali-soluble resin described above. From the viewpoints of patterning property and reliability, the content of the residual monomer is preferably 5,000 ppm by mass or less, more preferably 2,000 ppm by mass or less, and even more preferably 500 ppm by mass or less, relative to the total mass of the alkali-soluble resin. Although there is no particular lower limit, it is preferably 1 ppm by mass or more, and more preferably 10 ppm by mass or more. From the viewpoints of patterning ability and reliability, the residual monomer content of each structural unit of the alkali-soluble resin is 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 resin layer. Although there is no particular lower limit, it is preferably 0.1 ppm by mass or more, and more preferably 1 ppm by mass or more.

[0210] It is also preferable that the amount of residual monomers in the synthesis of an alkali-soluble resin by a polymer reaction be within the above range. For example, when an alkali-soluble resin is synthesized by reacting glycidyl acrylate with a carboxylic acid side chain, the content of glycidyl acrylate should be within the above range. It is preferable that The amount of residual monomer can be measured by known methods such as liquid chromatography and gas chromatography.

[0211] <Physical properties etc.> The thickness of the photosensitive resin layer is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. When the thickness of the photosensitive resin layer is 10 μm or less, the developability of the photosensitive resin layer is improved, and the resolution is improved. The lower limit of the thickness of the photosensitive resin layer is, for example, 0.5 μm.

[0212] The thickness of each layer of the photosensitive transfer material is calculated by observing a cross section of the photosensitive transfer material in a direction perpendicular to the main surface with a scanning electron microscope (SEM), measuring the thickness of each layer at 10 or more points based on the obtained observation image, and calculating the average value.

[0213] To obtain better adhesion, the transmittance of the photosensitive resin layer at a wavelength of 365 nm is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more. The upper limit of the transmittance of the photosensitive resin layer at a wavelength of 365 nm is not particularly limited, but is preferably 99.9%.

[0214] <Formation method> The method for forming the photosensitive resin layer is not particularly limited as long as it is a method that can form a layer containing the above components.

[0215] Examples of methods for forming the photosensitive resin layer include a method in which a photosensitive resin composition containing a polymer A, a polymerizable compound B, and a solvent is prepared, the photosensitive resin composition is applied to the surface of a temporary support or the like, and the coating film of the photosensitive resin composition is dried to form the layer.

[0216] The photosensitive resin composition used to form the photosensitive resin layer may be, for example, a composition containing a polymer A, a polymerizable compound B, the optional components described above, and a solvent.

[0217] The photosensitive resin composition preferably contains a solvent in order to adjust the viscosity of the photosensitive resin composition and facilitate the formation of the photosensitive resin layer.

[0218] (solvent) The solvent contained in the photosensitive resin composition is not particularly limited as long as it can dissolve or disperse the polymer A, the polymerizable compound B, and the above-mentioned optional components, and any known solvent can be used.

[0219] Examples of the solvent include alkylene glycol ethers, alkylene glycol ether acetates, alcohols (e.g., methanol and ethanol), ketones (e.g., acetone and methyl ethyl ketone), aromatic hydrocarbons (e.g., toluene), aprotic polar solvents (e.g., N,N-dimethylformamide), cyclic ethers (e.g., tetrahydrofuran), esters, amides, lactones, and mixed solvents containing two or more of these.

[0220] When preparing a photosensitive transfer material having a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer, the photosensitive resin composition preferably contains at least one selected from the group consisting of alkylene glycol ethers and alkylene glycol ether acetates. Among these, the solvent is more preferably a mixed solvent containing at least one selected from the group consisting of alkylene glycol ethers and alkylene glycol ether acetate solvents and at least one selected from the group consisting of ketones and cyclic ethers, and more preferably at least one selected from the group consisting of alkylene glycol ethers and alkylene glycol ether acetates. A mixed solvent containing at least one selected ketone and a cyclic ether is more preferred.

[0221] Examples of alkylene glycol ethers include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers, and dipropylene glycol dialkyl ethers.

[0222] Examples of alkylene glycol ether acetates include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.

[0223] The solvent may be a solvent described in paragraphs 0092 to 0094 of WO 2018 / 179640 and a solvent described in paragraph 0014 of JP 2018-177889 A, the contents of which are incorporated herein by reference.

[0224] The photosensitive resin composition may contain one type of solvent alone or two or more types of solvents. The content of the solvent in the photosensitive resin composition is preferably 50 to 1,900 parts by mass, and more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content in the photosensitive resin composition.

[0225] The method for preparing the photosensitive resin composition is not particularly limited, and examples thereof include a method in which solutions of the components are dissolved in the above-mentioned solvents in advance, and the resulting solutions are mixed in a predetermined ratio to prepare the photosensitive resin composition.

[0226] The photosensitive resin composition is preferably filtered using a filter with a pore size of 0.2 μm to 30 μm before forming the photosensitive resin layer.

[0227] The method for applying the photosensitive resin composition is not particularly limited, and may be any known method, such as slit coating, spin coating, curtain coating, or inkjet coating.

[0228] The photosensitive resin layer may also be formed by applying a photosensitive resin composition onto a cover film, which will be described later, and drying the composition.

[0229] [Thermoplastic resin layer] The photosensitive transfer material according to the present disclosure preferably includes a thermoplastic resin layer between the temporary support and the photosensitive resin layer. When the thermoplastic resin layer is disposed between the temporary support and the photosensitive resin layer, conformability to the substrate in the bonding step is improved, the inclusion of air bubbles between the substrate and the photosensitive transfer material is suppressed, and adhesion to an adjacent layer (e.g., temporary support) is improved.

[0230] <Ingredients> (alkali-soluble resin) The thermoplastic resin layer contains an alkali-soluble resin as the thermoplastic resin. In this specification, "alkali-soluble" means that the solubility in 100 g of a 1% by mass aqueous solution of sodium carbonate at 22°C is 0.1 g or more.

[0231] Examples of alkali-soluble resins include acrylic resin, polystyrene, and styrene-acrylic resin. Examples of the polymerizable copolymer include vinyl copolymers, polyurethanes, polyvinyl alcohols, polyvinyl formals, polyamides, polyesters, epoxy resins, polyacetals, polyhydroxystyrenes, polyimides, polybenzoxazoles, polysiloxanes, polyethyleneimines, polyallylamine, and polyalkylene glycols.

[0232] As the alkali-soluble resin, an acrylic resin is preferred from the viewpoint of developability and adhesion to adjacent layers.

[0233] Here, the acrylic resin means a resin having at least one type of structural unit selected from the group consisting of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid esters, and structural units derived from (meth)acrylic acid amides.

[0234] The acrylic resin preferably contains a total content of constituent units derived from (meth)acrylic acid, constituent units derived from (meth)acrylic acid ester, and constituent units derived from (meth)acrylic acid amide of 50% by mass or more relative to the total mass of the acrylic resin.

[0235] In particular, the total content of the structural units derived from (meth)acrylic acid and the structural units derived from (meth)acrylic acid esters is preferably 30% by mass to 100% by mass, and more preferably 50% by mass to 100% by mass, relative to the total mass of the acrylic resin.

[0236] The alkali-soluble resin is preferably a polymer having an acid group, such as a carboxy group, a sulfo group, a phosphate group, or a phosphonate group, with a carboxy group being preferred.

[0237] From the viewpoint of developability, the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more, and more preferably a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more.

[0238] The upper limit of the acid value of the alkali-soluble resin is not particularly limited, but the acid value of the alkali-soluble resin is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less.

[0239] The carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited, and can be appropriately selected from known resins.

[0240] Examples of carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or more include alkali-soluble resins that are carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or more among the polymers described in paragraph 0025 of JP-A No. 2011-95716, carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or more among the polymers described in paragraphs 0033 to 0052 of JP-A No. 2010-237589, and carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or more among the binder polymers described in paragraphs 0053 to 0068 of JP-A No. 2016-224162.

[0241] The content of the structural unit having a carboxy group in the carboxy group-containing acrylic resin is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and even more preferably 12% by mass to 30% by mass, relative to the total mass of the acrylic resin.

[0242] From the viewpoints of developability and adhesion to adjacent layers, the alkali-soluble resin is particularly preferably an acrylic resin having a structural unit derived from (meth)acrylic acid.

[0243] The alkali-soluble resin may have a reactive group. The reactive group may be an addition-polymerizable group. Any group capable of polycondensation may be used, and examples thereof include ethylenically unsaturated groups; polycondensable groups such as hydroxy groups and carboxy groups; and polyaddition reactive groups such as epoxy groups and (blocked) isocyanate groups.

[0244] The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably from 10,000 to 100,000, and even more preferably from 20,000 to 50,000.

[0245] The thermoplastic resin layer may contain one kind of alkali-soluble resin alone or two or more kinds of alkali-soluble resins. From the viewpoints of developability and adhesion to adjacent layers, the content of the alkali-soluble resin is preferably 10% by mass to 99% by mass, more preferably 20% by mass to 90% by mass, even more preferably 40% by mass to 80% by mass, and particularly preferably 50% by mass to 70% by mass, relative to the total mass of the thermoplastic resin layer.

[0246] (dye) The thermoplastic resin layer preferably contains a dye (also simply referred to as "dye B") whose maximum absorption wavelength during color development is 450 nm or longer in the wavelength range of 400 nm to 780 nm and whose maximum absorption wavelength changes in response to an acid, a base, or a radical. Preferred aspects of dye B are the same as those of dye N, except for the points described below.

[0247] From the viewpoints of visibility of exposed and unexposed areas and resolution, dye B is preferably a dye whose maximum absorption wavelength changes in response to an acid or radical, and more preferably a dye whose maximum absorption wavelength changes in response to an acid.

[0248] From the viewpoints of visibility and resolution of exposed and unexposed areas, the thermoplastic layer preferably contains both a dye whose maximum absorption wavelength changes in response to an acid as dye B, and a compound that generates an acid when exposed to light, as described below.

[0249] The thermoplastic resin layer may contain one type of dye B alone or two or more types thereof.

[0250] From the viewpoint of visibility of exposed and unexposed areas, the content of dye B is preferably 0.2 mass% or more, more preferably 0.2 mass% to 6 mass%, even more preferably 0.2 mass% to 5 mass%, and particularly preferably 0.25 mass% to 3.0 mass%, relative to the total mass of the thermoplastic resin layer.

[0251] Here, the content of dye B means the content of dye when all of the dye B contained in the thermoplastic resin layer is in a color-developing state. A method for quantifying the content of dye B will be described below using a dye that develops color by radicals as an example.

[0252] Solutions were prepared by dissolving 0.001 g and 0.01 g of dye in 100 mL of methyl ethyl ketone. A photoradical polymerization initiator (Irgacure OXE01, manufactured by BASF Japan) was added to each solution, and radicals were generated by irradiating with 365 nm light, causing all dyes to develop color. The absorbance of each solution was then measured at 25°C using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) under atmospheric conditions, and a calibration curve was created.

[0253] Next, the absorbance of the solution in which all the dye has developed is measured in the same manner as above, except that 0.1 g of the thermoplastic resin layer is dissolved in methyl ethyl ketone instead of the dye. The amount of the dye contained in the thermoplastic resin layer is calculated based on the absorbance of the obtained solution containing the thermoplastic resin layer and a calibration curve.

[0254] (Compounds that generate acids, bases, or radicals when exposed to light) The thermoplastic resin layer may contain a compound that generates an acid, a base or a radical when exposed to light (also simply referred to as "compound C").

[0255] Compound C is preferably a compound that generates an acid, a base, or a radical when exposed to actinic rays such as ultraviolet light and visible light.

[0256] Compound C may be a known photoacid generator, photobase generator, or photoradical polymerization initiator (photoradical generator). Of these, compound C is preferably a photoacid generator.

[0257] -Photoacid generator- From the viewpoint of resolution, the thermoplastic resin layer preferably contains a photoacid generator. Examples of the photoacid generator include the cationic photopolymerization initiators that may be contained in the photosensitive resin layer described above, and preferred embodiments are the same except for the points described below.

[0258] From the viewpoints of sensitivity and resolution, the photoacid generator is preferably at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds, and from the viewpoints of sensitivity, resolution, and adhesion, it is more preferably an oxime sulfonate compound. The photoacid generator is also preferably a photoacid generator having the following structure:

[0259] [ka]

[0260] -Photoradical polymerization initiator- The thermoplastic resin layer may contain a photoradical polymerization initiator. Examples of the photoradical polymerization initiator include the photoradical polymerization initiators that may be contained in the photosensitive resin layer described above, and the preferred embodiments are also the same.

[0261] -Photobase generator- 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, and examples thereof include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-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.

[0262] The thermoplastic resin layer may contain one type of compound C alone, or two or more types thereof. The content of compound C is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoints of visibility and resolution of exposed and unexposed areas.

[0263] (plasticizer) The thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion to adjacent layers, and developability.

[0264] The plasticizer preferably has a smaller molecular weight (weight average molecular weight (Mw) in the case of an oligomer or polymer) than the alkali-soluble resin. The molecular weight (weight average molecular weight (Mw)) of the plasticizer is preferably 200 to 2,000.

[0265] The plasticizer is not particularly limited as long as it is a compound that is compatible with the alkali-soluble resin and exhibits plasticity. From the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, more preferably a polyalkylene glycol compound. The alkyleneoxy group contained in the plasticizer more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.

[0266] From the viewpoints of resolution and storage stability, the plasticizer preferably contains a (meth)acrylate compound. From the viewpoints of compatibility, resolution, and adhesion to adjacent layers, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound.

[0267] Examples of the (meth)acrylate compound used as the plasticizer include the (meth)acrylate compounds described above as the polymerizable compound B contained in the photosensitive resin layer.

[0268] In the photosensitive transfer material, when a thermoplastic resin layer and a photosensitive resin layer are laminated in direct contact with each other, it is preferable that the thermoplastic resin layer and the photosensitive resin layer contain the same (meth)acrylate compound. When the thermoplastic resin layer and the photosensitive resin layer each contain the same (meth)acrylate compound, component diffusion between the layers is suppressed, and storage stability is improved.

[0269] When the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, it is preferable that the (meth)acrylate compound does not polymerize even in the exposed area after exposure, from the viewpoint of adhesion to adjacent layers.

[0270] Furthermore, from the viewpoints of resolution, adhesion to adjacent layers, and developability, the (meth)acrylate compound used as a plasticizer is preferably a polyfunctional (meth)acrylate compound having two or more (meth)acryloyl groups in one molecule.

[0271] Furthermore, the (meth)acrylate compound used as the plasticizer is preferably a (meth)acrylate compound having an acid group or a urethane (meth)acrylate compound.

[0272] The thermoplastic resin layer may contain one type of plasticizer alone or two or more types of plasticizers.

[0273] From the viewpoints of resolution, adhesion to adjacent layers, and developability, the content of the plasticizer is preferably 1% by mass to 70% by mass, more preferably 10% by mass to 60% by mass, and particularly preferably 20% by mass to 50% by mass, relative to the total mass of the thermoplastic resin layer.

[0274] (surfactant) From the viewpoint of thickness uniformity, the thermoplastic resin layer preferably contains a surfactant. Examples of the surfactant include the surfactants that may be contained in the photosensitive resin layer described above, and preferred embodiments are also the same.

[0275] The thermoplastic resin layer may contain one type of surfactant alone or two or more types of surfactants.

[0276] The content of the surfactant is preferably 0.001% by mass to 10% by mass, and more preferably 0.01% by mass to 3% by mass, relative to the total mass of the thermoplastic resin layer.

[0277] (sensitizer) The thermoplastic resin layer may contain a sensitizer. The sensitizer is not particularly limited, and examples thereof include the sensitizers that may be contained in the photosensitive resin layer described above.

[0278] The thermoplastic resin layer may contain one type of sensitizer alone or two or more types of sensitizers.

[0279] The content of the sensitizer can be selected appropriately depending on the purpose, but from the viewpoint of improving sensitivity to the light source and visibility of exposed and unexposed areas, it is preferably in the range of 0.01% by mass to 5% by mass, and more preferably in the range of 0.05% by mass to 1% by mass, relative to the total mass of the thermoplastic resin layer.

[0280] (additives, etc.) The thermoplastic resin layer may contain known additives in addition to the above components, as necessary. The thermoplastic resin layer is described in paragraphs

[0189] to

[0193] of JP 2014-85643 A, the contents of which are incorporated herein by reference.

[0281] <Physical properties etc.> The thickness of the thermoplastic resin layer is not particularly limited, but from the viewpoint of adhesion with adjacent layers, it is preferably 1 μm or more, more preferably 2 μm or more. The upper limit of the thickness of the thermoplastic resin layer is not particularly limited. From the viewpoint of developability and resolution, the thickness of the thermoplastic resin layer is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less.

[0282] <Formation method> The method for forming the thermoplastic resin layer is not particularly limited as long as it is a method that can form a layer containing the above components.

[0283] Examples of methods for forming the thermoplastic resin layer include a method in which a thermoplastic resin composition containing the above-mentioned components and a solvent is prepared, the thermoplastic resin composition is applied to the surface of a temporary support or the like, and the coating film of the thermoplastic resin composition is dried to form the layer.

[0284] The thermoplastic resin composition preferably contains a solvent in order to adjust the viscosity of the thermoplastic resin composition and facilitate the formation of the thermoplastic resin layer.

[0285] (solvent) The solvent contained in the thermoplastic resin composition is not particularly limited as long as it can dissolve or disperse the above components contained in the thermoplastic resin layer.

[0286] Examples of the solvent 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 also the same.

[0287] The solvent contained in the thermoplastic resin composition may be one type alone or two or more types.

[0288] The content of the solvent in the thermoplastic resin composition is preferably 50 to 1,900 parts by mass, and more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content in the thermoplastic resin composition.

[0289] The preparation of the thermoplastic resin composition and the formation of the thermoplastic resin layer may be carried out in accordance with the above-mentioned method for preparing the photosensitive resin composition and the method for forming the photosensitive resin layer.

[0290] For example, a solution is prepared in advance by dissolving each component contained in the thermoplastic resin layer in the above-mentioned solvent, and the resulting solution is mixed in a predetermined ratio to prepare a thermoplastic resin composition.The obtained thermoplastic resin composition is then applied to the surface of a temporary support, and the coating of the thermoplastic resin composition is dried to form a thermoplastic resin layer.

[0291] Alternatively, after forming a photosensitive resin layer and an intermediate layer on a cover film described below, a thermoplastic resin layer may be formed on the surface of the intermediate layer.

[0292] [Middle class] The photosensitive transfer material preferably includes an intermediate layer between the thermoplastic resin layer and the photosensitive resin layer, which can prevent components from mixing when multiple layers are applied and during storage after application.

[0293] The intermediate layer is preferably a water-soluble layer from the viewpoints of developability and suppressing mixing of components when applying a plurality of layers and during storage after application. In this specification, "water-soluble" means that the solubility in 100 g of water at a liquid temperature of 22°C and a pH of 7.0 is 0.1 g or more.

[0294] An example of the intermediate layer is an oxygen-blocking layer having an oxygen-blocking function, which is described as a "separation layer" in JP-A-5-72724. When the intermediate layer is an oxygen-blocking layer, the sensitivity during exposure is improved, the time load of the exposure machine is reduced, and productivity is improved.

[0295] The oxygen-blocking layer used as the intermediate layer may be appropriately selected from known layers described in the above publications, etc. Among them, the intermediate layer is preferably an oxygen-blocking layer that exhibits low oxygen permeability and disperses or dissolves in water or an alkaline aqueous solution (a 1% by mass aqueous solution of sodium carbonate at 22°C).

[0296] The intermediate layer preferably contains a resin. Examples of resins contained in the intermediate layer include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamides, and copolymers thereof.

[0297] The resin contained in the intermediate layer is preferably a water-soluble resin. Furthermore, from the viewpoint of suppressing mixing of components between multiple layers, it is preferable that the resin contained in the intermediate layer is a resin different from both the polymer A contained in the photosensitive resin layer and the thermoplastic resin (alkali-soluble resin) contained in the thermoplastic resin layer.

[0298] The intermediate layer is used to provide oxygen barrier properties and to prevent the formation of multiple layers during application and storage after application. From the viewpoint of suppressing mixing of components, it is preferable that the composition contains polyvinyl alcohol, and it is more preferable that the composition contains both polyvinyl alcohol and polyvinylpyrrolidone.

[0299] The intermediate layer may contain one kind of the above resin alone, or may contain two or more kinds of them.

[0300] The resin content in the intermediate layer is not particularly limited, but from the viewpoint of oxygen barrier properties and suppressing mixing of components when applying multiple layers and during storage after application, it is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, even more preferably 80% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass, relative to the total mass of the intermediate layer. The intermediate layer may also contain additives such as surfactants, if necessary.

[0301] The thickness of the intermediate layer is not particularly limited, but is preferably 0.1 μm to 5 μm, and more preferably 0.5 μm to 3 μm.

[0302] When the thickness of the intermediate layer is within the above range, the oxygen barrier property is not reduced, and mixing of components can be suppressed when multiple layers are applied and during storage after application. Furthermore, when the thickness of the intermediate layer is within the above range, an increase in the time required to remove the intermediate layer during development can be suppressed.

[0303] The method for forming the intermediate layer is not particularly limited, and examples thereof include a method of preparing an intermediate layer composition containing the above-mentioned resin and any additives, applying it to the surface of the thermoplastic resin layer or the photosensitive resin layer, and drying the coating of the intermediate layer composition to form the intermediate layer.

[0304] The intermediate layer composition preferably contains a solvent to adjust the viscosity of the intermediate layer composition and facilitate the formation of the intermediate layer.

[0305] The solvent contained in the intermediate layer composition is not particularly limited as long as it can dissolve or disperse the above 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.

[0306] Examples of water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, with alcohols having 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred.

[0307] [Cover film] The photosensitive transfer material preferably includes a cover film in contact with the surface of the photosensitive resin layer that does not face the temporary support. Hereinafter, in this specification, the surface of the photosensitive resin layer facing the temporary support is also referred to as the "first surface", and the surface opposite to the first surface is also referred to as the "second surface".

[0308] Examples of materials for the cover film include resin films and paper, and from the viewpoints of strength and flexibility, resin films are preferred.

[0309] Examples of the resin film include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among these, the resin film is preferably a polyethylene film, a polypropylene film, or a polyethylene terephthalate film.

[0310] The thickness of the cover film is not particularly limited, but is preferably 5 μm to 100 μm, and more preferably 10 μm to 50 μm.

[0311] The arithmetic mean roughness Ra of the surface of the cover film in contact with the photosensitive resin layer (hereinafter also referred to simply as "surface of the cover 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. By ensuring that the Ra value of the surface of the cover film is within the above range, it is believed that the uniformity of the layer thickness of the photosensitive resin layer and the formed resin pattern is improved.

[0312] The lower limit of the Ra value of the surface of the cover film is not particularly limited, but the Ra value of the surface of the cover film is preferably 0.001 μm or more.

[0313] The Ra value of the surface of the cover film is measured by the following method. Using a 3D optical profiler (New View7300, manufactured by Zygo), the surface of the cover film is measured under the following conditions to obtain the surface profile of the optical film. The measurement and analysis software used is the Microscope Application of MetroPro ver. 8.3.2. Next, the Surface Map screen is displayed in the analysis software, and histogram data is obtained on the Surface Map screen. The arithmetic mean roughness is calculated from the obtained histogram data, and the Ra value of the cover film surface is obtained. When a cover film is attached to the photosensitive transfer material, the cover film is peeled off from the photosensitive transfer material, and the Ra value of the surface on the peeled side is measured.

[0314] Furthermore, a photosensitive transfer material can be produced by laminating a cover film to a photosensitive resin layer or the like. The method for laminating the cover film to the photosensitive resin layer or the like is not particularly limited, and known methods can be used. Examples of a device for laminating the cover film to the photosensitive resin layer include known laminators such as a vacuum laminator and an auto-cut laminator. The laminator is preferably equipped with any heatable roller such as a rubber roller and is capable of applying pressure and heat.

[0315] The photosensitive transfer material may include layers other than the above-mentioned layers (hereinafter also referred to as "other layers"), such as a contrast enhancement layer. The contrast enhancement layer is described in paragraph 0134 of WO 2018 / 179640. The other layers are described in paragraphs 0194 to 0196 of JP 2014-85643 A. The contents of these publications are incorporated herein by reference.

[0316] The total thickness of each layer in the photosensitive transfer material, excluding the temporary support and cover film, is preferably 20 μm or less, more preferably 10 μm or less, even more preferably 8 μm or less, and particularly preferably 2 μm or more and 8 μm or less, from the viewpoints of resolution and adhesion to the substrate. Furthermore, from the viewpoints of resolution and adhesion to the substrate, the total thickness of the photosensitive resin layer, intermediate layer, and thermoplastic resin layer in the photosensitive transfer material is preferably 20 μm or less, more preferably 10 μm or less, even more preferably 8 μm or less, and particularly preferably 2 μm or more and 8 μm or less.

[0317] <Relationship between temporary support, photosensitive resin layer and cover film> The photosensitive transfer material according to the present disclosure comprises: the breaking elongation of the cured film obtained by curing the photosensitive resin layer at 120°C is 15% or more; the arithmetic mean roughness Ra of the surface of the temporary support on the photosensitive resin layer side is 50 nm or less; The arithmetic mean roughness Ra of the surface of the cover film on the photosensitive resin layer side is preferably 150 nm or less.

[0318] Furthermore, the photosensitive transfer material according to the present disclosure preferably satisfies the following formula (R1). X×Y<1,500 Formula (R1) In the above formula (R1), X represents the breaking elongation (%) of the cured film obtained by curing the photosensitive resin layer at 120°C, and Y represents the arithmetic mean roughness Ra (nm) of the surface of the temporary support on the photosensitive resin layer side. X×Y is more preferably 750 or less.

[0319] It is preferable that the breaking elongation at 120°C is at least twice as large as the breaking elongation at 23°C of the cured film obtained by curing the photosensitive resin layer. The breaking elongation was measured by exposing a 20 μm thick photosensitive resin layer to 120 mJ / cm irradiated with an ultra-high pressure mercury lamp. 2 After curing by exposure to 400mJ / cm with a high-pressure mercury lamp 2The cured film is then subjected to additional exposure at 145°C for 30 minutes, and the film is then subjected to a tensile test.

[0320] Furthermore, the photosensitive transfer material according to the present disclosure preferably satisfies the following formula (R2). Y≦Z formula (R2) Here, in the above formula (R2), Y represents the value (nm) of the arithmetic mean roughness Ra of the surface of the temporary support facing the photosensitive resin layer, and Z represents the value (nm) of the arithmetic mean roughness Ra of the surface of the cover film facing the photosensitive resin layer.

[0321] [Method for producing photosensitive transfer material] The method for producing the photosensitive transfer material according to the present disclosure is not particularly limited, and known production methods, for example, known methods for forming each layer, can be used.

[0322] Hereinafter, a method for producing a photosensitive transfer material according to the present disclosure will be described with reference to Fig. 1. However, the photosensitive transfer material according to the present disclosure is not limited to the configuration shown in Fig. 1. Fig. 1 is a schematic cross-sectional view showing an example of the layer structure of one embodiment of the photosensitive transfer material according to the present disclosure. The photosensitive transfer material 20 shown in Fig. 1 has a configuration in which a temporary support 11, a thermoplastic resin layer 13, an intermediate layer 15, a photosensitive resin layer 17, and a cover film 19 are laminated in this order. The layers to be transferred, that is, the thermoplastic resin layer 13, the intermediate layer 15, and the photosensitive resin layer 17, are collectively referred to as the transfer layer 12.

[0323] Examples of methods for manufacturing the photosensitive transfer material 20 include the steps of applying a thermoplastic resin composition to the surface of the temporary support 11 and then drying the coating of the thermoplastic resin composition to form a thermoplastic resin layer 13; applying an intermediate layer composition to the surface of the thermoplastic resin layer 13 and then drying the coating of the intermediate layer composition to form an intermediate layer 15; applying a photosensitive resin composition to the surface of the intermediate layer 15 and then drying the coating of the photosensitive resin composition to form a photosensitive resin layer 17; and pressing a cover film 19 onto the photosensitive resin layer 17.

[0324] When the photosensitive resin layer is provided directly on the temporary support, the photosensitive resin composition is applied to the surface of the temporary support.

[0325] In the above-mentioned production method, a thermoplastic resin composition containing at least one solvent selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, and a thermoplastic resin composition containing at least one solvent selected from the group consisting of water and a water-miscible organic solvent are used. It is preferable to use an intermediate layer composition having the above-mentioned structure and a photosensitive resin composition containing polymer A, polymerizable compound B, and at least one solvent selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. This can prevent mixing of the components contained in thermoplastic resin layer 13 and the components contained in intermediate layer 15 during application of the intermediate layer composition to the surface of thermoplastic resin layer 13 and / or during storage of a laminate having a coating film of the intermediate layer composition. It can also prevent mixing of the components contained in intermediate layer 15 and the components contained in photosensitive resin layer 17 during application of the photosensitive resin composition to the surface of intermediate layer 15 and / or during storage of a laminate having a coating film of the photosensitive resin composition.

[0326] A method for producing a photosensitive transfer material according to the present disclosure preferably includes a step of providing a cover film 19 in contact with the second surface of the photosensitive resin layer 17, thereby producing a photosensitive transfer material 20 comprising a temporary support 11, a thermoplastic resin layer 13, an intermediate layer 15, a photosensitive resin layer 17, and a cover film 19.

[0327] After producing the photosensitive transfer material 20, the photosensitive transfer material 20 may be wound up to prepare and store a roll of the photosensitive transfer material. The roll of the photosensitive transfer material can be provided in its original form for the step of laminating the photosensitive transfer material to a substrate in a roll-to-roll system, which will be described later.

[0328] In addition, the photosensitive transfer material of the first embodiment may also preferably be in a form in which the photosensitive resin layer is a colored resin layer containing a pigment. In addition to the above-mentioned applications, the colored resin layer is suitable for applications such as forming colored pixels or black matrices of color filters used in liquid crystal display devices (LCDs) and solid-state imaging devices (e.g., CCDs (charge-coupled devices) and CMOSs ​​(complementary metal oxide semiconductors)). In order to protect the liquid crystal display window of recent electronic devices, a cover glass having a black frame-shaped light-shielding layer formed on the periphery of the back surface of a transparent glass substrate or the like is sometimes attached. A colored resin layer can be used to form such a light-shielding layer. The aspects of the colored resin layer other than the pigment are the same as those described above.

[0329] <Pigments> The pigment used in the colored resin layer may be appropriately selected according to the desired hue, and may be selected from black pigments, white pigments, and pigments of chromatic colors other than black and white. In particular, when a black pattern is to be formed, a black pigment is preferably selected as the pigment.

[0330] As the black pigment, any known black pigment (such as an organic pigment or an inorganic pigment) can be appropriately selected as long as the effects of the present disclosure are not impaired. Among these, from the viewpoint of optical density, suitable black pigments include, for example, carbon black, titanium oxide, titanium carbide, iron oxide, and graphite, with carbon black being particularly preferred. As the carbon black, from the viewpoint of surface resistance, carbon black at least a portion of the surface of which is coated with a resin is preferred.

[0331] From the viewpoint of dispersion stability, the particle size of the black pigment is preferably 0.001 μm to 0.1 μm, more preferably 0.01 μm to 0.08 μm, in terms of number average particle size. Here, the particle size refers to the diameter of a circle whose area is equal to the area of ​​a pigment particle, calculated from a photograph of the pigment particle taken with an electron microscope, and the number average particle size is the average value obtained by calculating the particle size for 100 random particles and averaging the particle sizes of the 100 particles.

[0332] As a pigment other than the black pigment, the white pigment described in paragraphs 0015 and 0114 of JP-A No. 2005-007765 can be used. The inorganic pigment is preferably titanium oxide, zinc oxide, lithopone, precipitated calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate, more preferably titanium oxide or zinc oxide, and even more preferably titanium oxide. The inorganic pigment is more preferably rutile or anatase titanium oxide, and particularly preferably rutile titanium oxide. The surface of titanium oxide may be subjected to a silica treatment, alumina treatment, titania treatment, zirconia treatment, or organic treatment, or may be subjected to two or more of these treatments, which suppresses the catalytic activity of titanium oxide and improves heat resistance, fading resistance, etc. From the viewpoint of reducing the thickness of the photosensitive resin layer after heating, the surface treatment of the titanium oxide is preferably at least one of alumina treatment and zirconia treatment, and particularly preferably both alumina treatment and zirconia treatment.

[0333] Furthermore, when the photosensitive resin layer is a colored resin layer, it is also preferable that the photosensitive resin layer further contains a chromatic pigment other than a black pigment and a white pigment, from the viewpoint of transferability. When a chromatic pigment is contained, 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 better dispersibility. Examples of chromatic pigments include Victoria Pure Blue BO (Color Index (CI) 42595), Auramine (CI 41000), Fat Black HB (CI 26150), 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 Fast Blue (CI Pigment Red 146), and Permanent Yellow GR (CI Pigment Yellow 17). Examples of pigments that can be used include CI Pigment Blue 15), Monolight Fast Black B (CI Pigment Black 1) and 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. Of these, CI Pigment Red 177 is preferred.

[0334] When the photosensitive resin layer contains a pigment, the pigment content is preferably more than 3 mass% and not more than 40 mass%, more preferably more than 3 mass% and not more than 35 mass%, even more preferably more than 5 mass% and not more than 35 mass%, and particularly preferably 10 mass% or more and not more than 35 mass% relative to the total mass of the photosensitive resin layer.

[0335] When the photosensitive resin layer contains pigments other than black pigments (white pigments and chromatic pigments), the content of the pigments other than black pigments is preferably 30% by mass or less, more preferably 1% by mass to 20% by mass, and even more preferably 3% by mass to 15% by mass, relative to the black pigment.

[0336] In addition, when the photosensitive resin layer contains a black pigment and is formed from a photosensitive resin composition, the black pigment (preferably carbon black) is preferably introduced into the photosensitive resin composition in the form of a pigment dispersion. The dispersion may be prepared by previously mixing a black pigment and a pigment dispersant, adding the mixture to an organic solvent (or vehicle), and dispersing the mixture using a disperser. The pigment dispersant may be selected depending on the pigment and solvent, and for example, a commercially available dispersant may be used. The vehicle is the medium in which the pigment is dispersed when the pigment dispersion is prepared. It refers to a liquid component that includes a binder component that holds the black pigment in a dispersed state, and a solvent component (organic solvent) that dissolves and dilutes the binder component.

[0337] The dispersing machine is not particularly limited, and examples thereof include known dispersing machines such as a kneader, a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill. Furthermore, fine pulverization may be performed by utilizing frictional force through mechanical grinding. For details about dispersing machines and fine pulverization, please refer to the descriptions in "Pigment Dictionary" (Kunizo Asakura, 1st Edition, Asakura Shoten, 2000, pp. 438 and 310).

[0338] [Photosensitive Transfer Material of Second Embodiment] An example of the photosensitive transfer material of the second embodiment will be described below. 2 has, in this order, a temporary support 1, a transfer layer 2 including a photosensitive resin layer 3 and a refractive index adjusting layer 5, and a cover film 7. The photosensitive resin layer 3 and the refractive index adjusting layer 5, which are the layers to be transferred, are also referred to as the transfer layer 2. Furthermore, although the photosensitive transfer material 10 shown in FIG. 2 has a refractive index adjusting layer 5 disposed thereon, the refractive index adjusting layer 5 does not necessarily have to be disposed. Each element constituting the photosensitive transfer material of the second embodiment will be described below. The temporary support and cover film used in the photosensitive transfer material of the second embodiment are the same as the temporary support and cover film in the photosensitive transfer material of the first embodiment, and the preferred aspects are also the same.

[0339] [Photosensitive resin layer] The photosensitive transfer material has a photosensitive resin layer. After the photosensitive resin layer is transferred onto the transfer-receiving body, it is exposed to light and developed, thereby forming a pattern on the transfer-receiving body.

[0340] Components that can be contained in the photosensitive resin layer will be described in detail below.

[0341] <Polymer C> The photosensitive resin layer preferably contains a polymer C. The polymer C is preferably an alkali-soluble resin. Examples of alkali-soluble resins include (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenolic resins, ester resins, urethane resins, epoxy acrylate resins obtained by reacting an epoxy resin with (meth)acrylic acid, and acid-modified epoxy acrylate resins obtained by reacting an epoxy acrylate resin with an acid anhydride.

[0342] One preferred embodiment of the alkali-soluble resin is a (meth)acrylic resin, which has excellent alkali developability and film formability.

[0343] In this specification, the term "(meth)acrylic resin" refers to a resin having structural units derived from (meth)acrylic compounds. The content of structural units derived from (meth)acrylic compounds is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on the total structural units of the (meth)acrylic resin.

[0344] The (meth)acrylic resin may be composed solely of structural units derived from (meth)acrylic compounds, or may contain structural units derived from polymerizable monomers other than (meth)acrylic compounds. That is, the upper limit of the content of structural units derived from (meth)acrylic compounds is 100% by mass or less of all structural units of the (meth)acrylic resin.

[0345] Examples of the (meth)acrylic compound include (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylamide, and (meth)acrylonitrile. Examples of (meth)acrylic acid esters include (meth)acrylic acid alkyl esters, (meth)acrylic acid tetrahydrofurfuryl esters, (meth)acrylic acid dimethylaminoethyl esters, (meth)acrylic acid diethylaminoethyl esters, (meth)acrylic acid glycidyl esters, (meth)acrylic acid benzyl esters, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, and (meth)acrylic acid alkyl esters are preferred. Examples of (meth)acrylamides include acrylamides such as diacetone acrylamide.

[0346] Examples of the (meth)acrylic acid alkyl ester include (meth)acrylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, and dodecyl (meth)acrylate.

[0347] As the (meth)acrylic acid ester, a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms is preferred, and methyl (meth)acrylate or ethyl (meth)acrylate is more preferred.

[0348] The (meth)acrylic resin may have a structural unit other than the structural unit derived from the (meth)acrylic compound. The polymerizable monomer that forms the structural unit is not particularly limited as long as it is a compound other than a (meth)acrylic compound that is copolymerizable with a (meth)acrylic compound, and examples thereof include styrene compounds that may have a substituent at the α-position or on the aromatic ring, such as styrene, vinyltoluene, and α-methylstyrene; vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether; maleic acid monoesters such as maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, and monoisopropyl maleate; fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, and crotonic acid. These polymerizable monomers may be used alone or in combination of two or more.

[0349] In order to improve alkaline developability, the (meth)acrylic resin preferably contains a structural unit having an acid group, such as a carboxy group, a sulfo group, a phosphate group, or a phosphonate group. In particular, the (meth)acrylic resin more preferably has a structural unit having a carboxy group, and even more preferably has a structural unit derived from the above-mentioned (meth)acrylic acid.

[0350] The content of structural units having an acid group in the (meth)acrylic resin (preferably structural units derived from (meth)acrylic acid) is preferably 10% by mass or more relative to the total mass of the (meth)acrylic resin in terms of excellent developability. While there is no particular upper limit, it is preferably 50% by mass or less, more preferably 40% by mass or less, in terms of excellent alkali resistance.

[0351] Furthermore, the (meth)acrylic resin more preferably has a structural unit derived from the above-mentioned alkyl (meth)acrylate ester.

[0352] (Meth)acrylic acid alkyl ester-derived constituent units in (meth)acrylic resins The content of this unit is preferably 50% by mass to 90% by mass, more preferably 60% by mass to 90% by mass, and even more preferably 65% ​​by mass to 90% by mass, based on all structural units of the (meth)acrylic resin.

[0353] As the (meth)acrylic resin, a resin having both a structural unit derived from (meth)acrylic acid and a structural unit derived from a (meth)acrylic acid alkyl ester is preferred, and a resin composed only of a structural unit derived from (meth)acrylic acid and a structural unit derived from a (meth)acrylic acid alkyl ester is more preferred. Furthermore, as the (meth)acrylic resin, an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate is also preferred.

[0354] Furthermore, from the viewpoint of resolution, the (meth)acrylic resin preferably has at least one selected from the group consisting of structural units derived from methacrylic acid and structural units derived from a methacrylic acid alkyl ester, and more preferably has both structural units derived from methacrylic acid and structural units derived from a methacrylic acid alkyl ester.

[0355] From the viewpoint of resolution, the total content of the structural units derived from methacrylic acid and the structural units derived from alkyl methacrylate in the (meth)acrylic resin is preferably 40% by mass or more, more preferably 60% by mass or more, based on the total structural units of the (meth)acrylic resin. The upper limit is not particularly limited, and may be 100% by mass or less, preferably 80% by mass or less.

[0356] From the viewpoint of resolution, the (meth)acrylic resin also preferably contains at least one selected from the group consisting of structural units derived from methacrylic acid and structural units derived from methacrylic acid alkyl esters, and at least one selected from the group consisting of structural units derived from acrylic acid and structural units derived from acrylic acid alkyl esters. From the viewpoint of resolution, the total content of the structural units derived from methacrylic acid and the structural units derived from a methacrylic acid alkyl ester is preferably in a mass ratio of 60 / 40 to 80 / 20 relative to the total content of the structural units derived from acrylic acid and the structural units derived from a acrylic acid alkyl ester.

[0357] The (meth)acrylic resin preferably has an ester group at the end, in order to provide excellent developability of the photosensitive resin layer after transfer. The terminals of the (meth)acrylic resin are composed of moieties derived from the polymerization initiator used in the synthesis. A (meth)acrylic resin having an ester group at its terminal can be synthesized by using a polymerization initiator that generates a radical having an ester group.

[0358] Furthermore, from the viewpoint of developability, for example, the polymer C is preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more. Furthermore, polymer C is more preferably a resin having a carboxy group with an acid value of 60 mgKOH / g or more (so-called carboxy group-containing resin), and even more preferably a (meth)acrylic resin having a carboxy group with an acid value of 60 mgKOH / g or more (so-called carboxy group-containing (meth)acrylic resin), because polymer C is easily thermally crosslinked with the crosslinking component by heating and forms a strong film. When the polymer C is a resin having a carboxy group, the three-dimensional crosslinking density can be increased by, for example, adding a thermally crosslinkable compound such as a blocked isocyanate compound to cause thermal crosslinking. Furthermore, when the carboxy group of the resin having a carboxy group is dehydrated and made hydrophobic, the wet heat resistance can be improved.

[0359] The carboxyl group-containing (meth)acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited as long as it satisfies the above-mentioned acid value condition, and can be appropriately selected from known (meth)acrylic resins.

[0360] For example, among the polymers described in paragraph 0025 of JP-A No. 2011-095716, carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or more, and among the polymers described in paragraphs 0033 to 0052 of JP-A No. 2010-237589, carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or more can be preferably used.

[0361] Another preferred embodiment of polymer C is a styrene-acrylic copolymer. In this specification, the term "styrene-acrylic copolymer" refers to a resin having structural units derived from a styrene compound and structural units derived from a (meth)acrylic compound, and the total content of the structural units derived from the styrene compound and the structural units derived from the (meth)acrylic compound is preferably 30% by mass or more, and more preferably 50% by mass or more, of all structural units of the copolymer.

[0362] The content of the structural units derived from the styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 5 to 80% by mass, based on all structural units of the copolymer.

[0363] The content of the structural units derived from the (meth)acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% to 95% by mass, based on all structural units of the copolymer.

[0364] From the viewpoint of moisture permeability and strength of the resulting cured film, polymer C preferably has an aromatic ring structure, and more preferably has a structural unit having an aromatic ring structure.

[0365] Examples of monomers that form structural units having an aromatic ring structure include styrene compounds such as styrene, tert-butoxystyrene, methylstyrene, and α-methylstyrene, as well as benzyl (meth)acrylate. Of these, styrene compounds are preferred, and styrene is more preferred. Furthermore, from the viewpoint of the moisture permeability and strength of the resulting cured film, polymer C more preferably has a structural unit represented by the following formula (S) (a structural unit derived from styrene).

[0366] [ka]

[0367] When polymer C has a structural unit having an aromatic ring structure, the content of the structural unit having an aromatic ring structure is set to 1 / 200 of the total structural units of polymer C from the viewpoint of the moisture permeability and strength of the resulting cured film. The content is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 70% by mass, and further preferably 20% by mass to 60% by mass.

[0368] Furthermore, from the viewpoint of moisture permeability and strength of the resulting cured film, the content of the structural units having an aromatic ring structure in polymer C is preferably 5 mol % to 70 mol %, more preferably 10 mol % to 60 mol %, and even more preferably 20 mol % to 60 mol %, based on all structural units of polymer C.

[0369] Furthermore, from the viewpoint of moisture permeability and strength of the resulting cured film, the content of the structural unit represented by the above formula (S) in polymer C is preferably 5 mol % to 70 mol %, more preferably 10 mol % to 60 mol %, even more preferably 20 mol % to 60 mol %, and particularly preferably 20 mol % to 50 mol %, based on all structural units of polymer C.

[0370] In this specification, when the content of a "structural unit" is specified by a molar ratio, the "structural unit" is considered to have the same meaning as a "monomer unit." In addition, in this specification, the "monomer unit" may be modified after polymerization by a polymer reaction or the like. The same applies hereinafter.

[0371] From the viewpoints of suppressing development residues, the strength of the resulting cured film, and the adhesiveness of the resulting uncured film, it is preferable that the polymer C has an aliphatic hydrocarbon ring structure. That is, it is preferable that the polymer C has a structural unit having an aliphatic hydrocarbon ring structure. In particular, it is more preferable that the polymer C has a ring structure in which two or more aliphatic hydrocarbon rings are fused.

[0372] Examples of the ring that constitutes the aliphatic hydrocarbon ring structure in the structural unit having an aliphatic hydrocarbon ring structure include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, and an isoborone ring. Among these, from the viewpoints of suppressing development residues, strength of the resulting cured film, and adhesiveness of the resulting uncured film, a ring in which two or more aliphatic hydrocarbon rings are condensed is preferred, and a tetrahydrodicyclopentadiene ring (tricyclo[5.2.1.0]) is particularly preferred. 2,6 ]decane ring) is more preferred. Examples of monomers that form a structural unit having an aliphatic hydrocarbon ring structure include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate. Furthermore, from the viewpoints of suppressing development residues, the strength of the resulting cured film, and the adhesion of the resulting uncured film, polymer C more preferably has a structural unit represented by the following formula (Cy), and more preferably has a structural unit represented by the above formula (S) and a structural unit represented by the following formula (Cy).

[0373] [ka]

[0374] In the formula (Cy), R Mrepresents a hydrogen atom or a methyl group, and R Cy represents a monovalent group having an aliphatic hydrocarbon ring structure.

[0375] R in formula (Cy) M is preferably a methyl group. R in formula (Cy) Cy is preferably a monovalent group having an aliphatic hydrocarbon ring structure of 5 to 20 carbon atoms, more preferably a monovalent group having an aliphatic hydrocarbon ring structure of 6 to 16 carbon atoms, and even more preferably a monovalent group having an aliphatic hydrocarbon ring structure of 8 to 14 carbon atoms, from the viewpoints of suppression of development residues, strength of the resulting cured film, and adhesiveness of the resulting uncured film. R in formula (Cy) Cy The aliphatic hydrocarbon ring structure in may be a monocyclic structure or a polycyclic structure. Also, R in formula (Cy) Cy From the viewpoints of suppressing development residues, the strength of the resulting cured film, and the adhesiveness of the resulting uncured film, the aliphatic hydrocarbon ring structure in the above is preferably a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure, or an isoborone ring structure, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, and even more preferably a tetrahydrodicyclopentadiene ring structure. Furthermore, R in formula (Cy) Cy From the viewpoints of suppressing development residues, the strength of the resulting cured film, and the adhesiveness of the resulting uncured film, the aliphatic hydrocarbon ring structure in the above is preferably a ring structure in which two or more aliphatic hydrocarbon rings are condensed, and more preferably a ring in which two to four aliphatic hydrocarbon rings are condensed. Furthermore, R in formula (Cy) CyFrom the viewpoints of suppressing development residues, the strength of the resulting cured film, and the adhesiveness of the resulting uncured film, is preferably a group in which the oxygen atom of —C(═O)O— in formula (Cy) is directly bonded to an aliphatic hydrocarbon ring structure, i.e., an aliphatic hydrocarbon ring group, more preferably a cyclohexyl group or a dicyclopentanyl group, and even more preferably a dicyclopentanyl group.

[0376] Polymer C may have one type of structural unit having an aliphatic hydrocarbon ring structure, or may have two or more types of structural units.

[0377] When polymer C has a structural unit having an aliphatic hydrocarbon ring structure, the content of the structural unit having an aliphatic hydrocarbon ring structure is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 80% by mass, and even more preferably 20% by mass to 70% by mass, relative to all structural units of polymer C, from the viewpoints of suppressing development residues, the strength of the resulting cured film, and the adhesiveness of the resulting uncured film.

[0378] Furthermore, the content of the structural units having an aliphatic hydrocarbon ring structure in polymer C is preferably 5 mol % to 70 mol %, more preferably 10 mol % to 60 mol %, and even more preferably 20 mol % to 50 mol %, relative to all structural units of polymer C, from the viewpoints of suppressing development residues, the strength of the resulting cured film, and the adhesion of the resulting uncured film.

[0379] Furthermore, the content of the structural unit represented by the above formula (Cy) in polymer C is preferably 5 mol % to 70 mol %, more preferably 10 mol % to 60 mol %, and even more preferably 20 mol % to 50 mol %, relative to all structural units of polymer C, from the viewpoints of suppressing development residues, the strength of the resulting cured film, and the adhesion of the resulting uncured film.

[0380] When polymer C has structural units having an aromatic ring structure and structural units having an aliphatic hydrocarbon ring structure, the total content of structural units having an aromatic ring structure and structural units having an aliphatic hydrocarbon ring structure is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and even more preferably 40% by mass to 75% by mass, relative to all structural units of polymer C, from the viewpoints of suppressing development residues, the strength of the resulting cured film, and the adhesiveness of the resulting uncured film.

[0381] Furthermore, from the viewpoints of suppressing development residues, the strength of the resulting cured film, and the adhesion of the resulting uncured film, the total content of structural units having an aromatic ring structure and structural units having an aliphatic hydrocarbon ring structure in polymer C is preferably 10 mol % to 80 mol %, more preferably 20 mol % to 70 mol %, and even more preferably 40 mol % to 60 mol %, relative to all structural units of polymer C.

[0382] Furthermore, from the viewpoints of suppressing development residues, the strength of the resulting cured film, and the adhesion of the resulting uncured film, the total content of the structural units represented by the formula (S) and the structural units represented by the formula (Cy) in polymer C is preferably 10 mol % to 80 mol %, more preferably 20 mol % to 70 mol %, and even more preferably 40 mol % to 60 mol %, relative to all structural units of polymer C.

[0383] Furthermore, from the viewpoints of suppressing development residues, the strength of the resulting cured film, and the adhesion of the resulting uncured film, it is preferable that the molar amount nS of the structural unit represented by the above formula (S) in polymer C and the molar amount nCy of the structural unit represented by the above formula (Cy) satisfy the relationship shown in the following formula (SCy), more preferably satisfying the following formula (SCy-1), and even more preferably satisfying the following formula (SCy-2). 0.2≦nS / (nS+nCy)≦0.8 Formula (SCy) 0.30≦nS / (nS+nCy)≦0.75 Formula (SCy-1) 0.40≦nS / (nS+nCy)≦0.70 Formula (SCy-2)

[0384] From the viewpoints of developability and adhesion to a substrate, the polymer C preferably contains a structural unit having an acid group. Examples of the acid group include a carboxy group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, with a carboxy group being preferred. As the structural unit having an acid group, a structural unit derived from (meth)acrylic acid shown below is preferred, and a structural unit derived from methacrylic acid is more preferred.

[0385] [ka]

[0386] The polymer C may have one type of structural unit having an acid group, or two or more types of structural units having an acid group. When polymer C has a structural unit having an acid group, the content of the structural unit having an acid group is preferably 5% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and even more preferably 10% by mass to 30% by mass, based on all structural units of polymer C, from the viewpoints of developability and adhesion to a substrate. Furthermore, from the viewpoints of developability and adhesion to a substrate, the content of the structural units having an acid group in polymer C is preferably 5 mol % to 70 mol %, more preferably 10 mol % to 50 mol %, and even more preferably 20 mol % to 40 mol %, based on the total structural units of polymer C. Furthermore, from the viewpoints of developability and adhesion to a substrate, the content of the (meth)acrylic acid-derived structural units in polymer C is preferably 5 mol % to 70 mol %, more preferably 10 mol % to 50 mol %, and even more preferably 20 mol % to 40 mol %, based on the total structural units of polymer C.

[0387] From the viewpoints of curability and the strength of the resulting cured film, polymer C preferably has a reactive group, and more preferably has a structural unit having a reactive group.

[0388] The reactive group is preferably a radically polymerizable group, more preferably an ethylenically unsaturated group. When the polymer C has an ethylenically unsaturated group, the polymer C preferably has a structural unit having an ethylenically unsaturated group in a side chain.

[0389] In this specification, the term "main chain" refers to the relatively longest bond chain in the molecule of the polymer compound that constitutes the resin, and the term "side chain" refers to an atomic group branching off from the main chain. The ethylenically unsaturated group is more preferably an allyl group or a (meth)acryloxy group. Examples of structural units having a reactive group include, but are not limited to, those shown below.

[0390] [ka]

[0391] The polymer C may have one type of structural unit having a reactive group, or may have two or more types of structural units.

[0392] When polymer C has a structural unit having a reactive group, the content of the structural unit having a reactive group is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 50% by mass, and even more preferably 20% by mass to 40% by mass, based on all structural units of polymer C, from the viewpoints of curability and the strength of the resulting cured film.

[0393] Furthermore, from the viewpoints of curability and the strength of the resulting cured film, the content of the structural units having a reactive group in polymer C is preferably 5 mol % to 70 mol %, more preferably 10 mol % to 60 mol %, and even more preferably 20 mol % to 50 mol %, based on the total structural units of polymer C.

[0394] Examples of a method for introducing a reactive group into polymer C include a method of reacting a functional group such as a hydroxy group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, or a sulfo group with a compound such as an epoxy compound, a blocked isocyanate compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, or a carboxylic acid anhydride.

[0395] A preferred example of a method for introducing a reactive group into polymer C is to synthesize a polymer having a carboxy group by polymerization, and then react some of the carboxy groups of the resulting resin with glycidyl (meth)acrylate by a polymer reaction to introduce a (meth)acryloxy group into the polymer. This method allows for the production of polymer C having a (meth)acryloxy group in its side chain.

[0396] The polymerization reaction is preferably carried out at a temperature of 70°C to 100°C, and more preferably at a temperature of 80°C to 90°C. The polymerization initiator used in the polymerization reaction is preferably an azo-based initiator, and more preferably, for example, V-601 (trade name) or V-65 (trade name) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. The polymerization reaction is preferably carried out at a temperature of 80°C to 110°C. In the polymerization reaction, it is preferable to use a catalyst such as an ammonium salt.

[0397] As the polymer C, the following resins are preferred in terms of achieving better effects in the present disclosure. Note that the content ratios (a to d) of each structural unit and the weight average molecular weight Mw shown below are for illustrative purposes only. The number of times can be changed as needed.

[0398] [ka]

[0399] In the above resin, it is preferable that a is 20% to 60% by mass, b is 10% to 50% by mass, c is 5.0% to 25% by mass, and d is 10% to 50% by mass.

[0400] [ka]

[0401] In the above resin, it is preferable that a is 20% to 60% by mass, b is 10% to 50% by mass, c is 5.0% to 25% by mass, and d is 10% to 50% by mass.

[0402] [ka]

[0403] In the above resin, it is preferable that a is 30% to 65% by mass, b is 1.0% to 20% by mass, c is 5.0% to 25% by mass, and d is 10% to 50% by mass.

[0404] [ka]

[0405] In the above compounds, it is preferable that a is 1.0% to 20% by mass, b is 20% to 60% by mass, c is 5.0% to 25% by mass, and d is 10% to 50% by mass.

[0406] Furthermore, polymer C may contain a polymer having a structural unit with a carboxylic acid anhydride structure (hereinafter also referred to as "polymer C1"). The carboxylic acid anhydride structure may be either a chain carboxylic acid anhydride structure or a cyclic carboxylic acid anhydride structure, but is preferably a cyclic carboxylic acid anhydride structure. The ring of the cyclic carboxylic acid anhydride structure is preferably a 5- to 7-membered ring, more preferably a 5- or 6-membered ring, and even more preferably a 5-membered ring.

[0407] The structural unit having a carboxylic acid anhydride structure is a structural unit containing, in the main chain, a divalent group obtained by removing two hydrogen atoms from a compound represented by the following formula P-1, or a compound represented by the following formula P-1 Preferably, the structural unit is a monovalent group obtained by removing one hydrogen atom from the above, which is bonded to the main chain directly or via a divalent linking group.

[0408] [ka]

[0409] In formula P-1, R A1a represents a substituent, n 1a R A1a may be the same or different, and Z 1a represents a divalent group forming a ring containing -C(=O)-OC(=O)-, and n 1a represents an integer greater than or equal to 0.

[0410] R A1a Examples of the substituent represented by the formula include an alkyl group. Z 1a As the alkylene group, an alkylene group having 2 to 4 carbon atoms is preferable, an alkylene group having 2 or 3 carbon atoms is more preferable, and an alkylene group having 2 carbon atoms is even more preferable. n 1a represents an integer greater than or equal to 0. Z 1a When represents an alkylene group having 2 to 4 carbon atoms, n 1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0. n 1a If represents an integer of 2 or more, there are multiple R A1a may be the same or different. A1a may be bonded to each other to form a ring, but preferably do not bond to each other to form a ring.

[0411] As a structural unit having a carboxylic acid anhydride structure, a structural unit derived from an unsaturated carboxylic acid anhydride is preferred, a structural unit derived from an unsaturated cyclic carboxylic acid anhydride is more preferred, a structural unit derived from an unsaturated aliphatic cyclic carboxylic acid anhydride is even more preferred, a structural unit derived from maleic anhydride or itaconic anhydride is particularly preferred, and a structural unit derived from maleic anhydride is most preferred.

[0412] Specific examples of structural units having a carboxylic acid anhydride structure are listed below, but the structural units having a carboxylic acid anhydride structure are not limited to these specific examples. In the following structural units, Rx represents a hydrogen atom, a methyl group, a CH2OH group, or a CF3 group, and Me represents a methyl group.

[0413] [ka]

[0414] [ka]

[0415] The structural unit having a carboxylic acid anhydride structure in polymer C1 may be of one type alone, or may be of two or more types.

[0416] The total content of structural units having a carboxylic acid anhydride structure is preferably 0 mol % to 60 mol %, more preferably 5 mol % to 40 mol %, and even more preferably 10 mol % to 35 mol %, based on all structural units of polymer C1.

[0417] The photosensitive resin layer may contain only one type of polymer C1, or may contain two or more types. When the photosensitive resin layer contains polymer C1, from the viewpoints of resolution and developability, the content of polymer C1 is preferably 0.1% by mass to 30% by mass, more preferably 0.2% by mass to 20% by mass, even more preferably 0.5% by mass to 20% by mass, and even more preferably 1% by mass to 20% by mass, relative to the total mass of the photosensitive resin layer.

[0418] The weight average molecular weight (Mw) of polymer C is preferably 5,000 or more, more preferably 10,000 or more, further preferably from 10,000 to 50,000, and particularly preferably from 20,000 to 30,000, from the viewpoint of improving resolution and developability.

[0419] The acid value of polymer C is preferably from 10 mgKOH / g to 200 mgKOH / g, more preferably from 60 mgKOH / g to 200 mgKOH / g, still more preferably from 60 mgKOH / g to 150 mgKOH / g, and particularly preferably from 60 mgKOH / g to 110 mgKOH / g. The acid value of the polymer C is a value measured according to the method described in JIS K0070:1992. From the viewpoint of developability, the dispersity (weight average molecular weight / number average molecular weight) of polymer C is preferably from 1.0 to 6.0, more preferably from 1.0 to 5.0, even more preferably from 1.0 to 4.0, and particularly preferably from 1.0 to 3.0.

[0420] The photosensitive resin layer may contain only one type of polymer C, or may contain two or more types. From the viewpoints of photosensitivity, resolution, and developability, the content of polymer C is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and even more preferably 30% by mass to 70% by mass, relative to the total mass of the photosensitive resin layer.

[0421] <Polymerizable compound D> The photosensitive resin layer may contain a polymerizable compound D. The polymerizable compound D is a compound having a polymerizable group. Examples of the polymerizable group include a radically polymerizable group and a cationic polymerizable group, and the radically polymerizable group is preferred.

[0422] The polymerizable compound D preferably contains a polymerizable compound having an ethylenically unsaturated group (hereinafter also simply referred to as "ethylenically unsaturated compound"). The ethylenically unsaturated group is preferably a (meth)acryloxy group. The polymerizable compound D in this specification is a compound other than the polymer C, and preferably has a molecular weight of less than 5,000. Moreover, preferred embodiments of the polymerizable compound D used in the photosensitive resin layer of the second embodiment include the preferred embodiments of the polymerizable compound B used in the photosensitive resin layer of the first embodiment described above.

[0423] One preferred embodiment of the ethylenically unsaturated compound is a compound represented by the following formula (M) (also simply referred to as "compound M"). Q 2 -R 1 -Q 1 Formula (M) In formula (M), Q 1 and Q 2 each independently represents a (meth)acryloyloxy group, R 1 represents a divalent linking group having a chain structure.

[0424] Q in formula (M) 1 and Q 2 In terms of ease of synthesis, Q 1 and Q 2 are preferably the same group. Also, Q in formula (M) 1 and Q 2 is preferably an acryloyloxy group from the viewpoint of reactivity. R in formula (M) 1 From the viewpoints of suppressing development residues, rust prevention, and bending resistance of the resulting cured film, alkylene groups, alkyleneoxyalkylene groups (-L 1 -OL 1 -),also is a polyalkyleneoxyalkylene group (-(L 1 -O) p -L 1 -) is preferred, a hydrocarbon group having 2 to 20 carbon atoms or a polyalkyleneoxyalkylene group is more preferred, an alkylene group having 4 to 20 carbon atoms is further preferred, and a linear alkylene group having 6 to 18 carbon atoms is particularly preferred. The hydrocarbon group may have a chain structure at least in part, and the portion other than the chain structure is not particularly limited and may be, for example, a branched, cyclic, or linear alkylene group having 1 to 5 carbon atoms, an arylene group, an ether bond, or a combination thereof. An alkylene group or a group combining two or more alkylene groups and one or more arylene groups is preferred, an alkylene group is more preferred, and a linear alkylene group is even more preferred. In addition, the above L 1 each independently represents an alkylene group, preferably an ethylene group, a propylene group, or a butylene group, more preferably an ethylene group or a 1,2-propylene group. p represents an integer of 2 or more, and is preferably an integer of 2 to 10.

[0425] Also, Q in compound M 1 and Q 2 The number of atoms in the shortest linking chain connecting As used herein, "Q 1 and Q 2 The number of atoms in the shortest chain connecting the 1 Connect to R 1 Q from atoms in 2 Connect to R 1 is the number of atoms in the shortest chain that connects all atoms in

[0426] Specific examples of compound M include 1,3-butanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, di(meth)acrylate of hydrogenated bisphenol A, di(meth)acrylate of hydrogenated bisphenol F, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene glycol / propylene glycol) di(meth)acrylate, and polybutylene glycol di(meth)acrylate. The above ester monomers can also be used as a mixture. Among the above compounds, from the viewpoints of suppressing development residues, rust prevention, and bending resistance of the resulting cured film, at least one compound selected from the group consisting of 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate is preferred, at least one compound selected from the group consisting of 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate is more preferred, and at least one compound selected from the group consisting of 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate is even more preferred.

[0427] One preferred embodiment of the ethylenically unsaturated compound is a di- or higher functional ethylenically unsaturated compound. In this specification, the term "difunctional or higher functional ethylenically unsaturated compound" refers to a compound having two or more ethylenically unsaturated groups in one molecule. The ethylenically unsaturated group in the ethylenically unsaturated compound is preferably a (meth)acryloyl group. As the ethylenically unsaturated compound, a (meth)acrylate compound is preferred.

[0428] The difunctional ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds. Examples of the difunctional ethylenically unsaturated compound other than the compound M include tricyclodecane dimethanol di(meth)acrylate and 1,4-cyclohexanediol di(meth)acrylate.

[0429] Commercially available bifunctional ethylenically unsaturated compounds include tricyclodecane dimethanol diacrylate (trade name: NK Ester A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (trade name: NK Ester DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (trade name: NK Ester A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), and 1,6-hexanediol diacrylate (trade name: NK Ester A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0430] The tri- or higher functional ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds. Examples of tri- or higher functional ethylenically unsaturated compounds include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerin tri(meth)acrylate skeleton.

[0431] Examples of the ethylenically unsaturated compound include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel-Allnex Corporation, etc.), and ethoxylated glycerin triacrylate (NK Ester A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.).

[0432] The ethylenically unsaturated compound also includes a urethane (meth)acrylate compound. Examples of urethane (meth)acrylates include urethane di(meth)acrylates, such as propylene oxide-modified urethane di(meth)acrylates and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates. Further, the urethane (meth)acrylate may be a trifunctional or higher functional urethane (meth)acrylate. The lower limit of the number of functional groups is preferably 6 or more, and more preferably 8 or more. The upper limit of the number of functional groups is preferably 20 or less. Examples of trifunctional or higher functional urethane (meth)acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), AH-600 (trade name) manufactured by Kyoeisha Chemical Co., Ltd., and UA-306H, UA-306T, UA-306I, UA-510H, and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).

[0433] One preferred embodiment of the ethylenically unsaturated compound is an ethylenically unsaturated compound having an acid group. Acid groups include phosphate groups, sulfo groups, and carboxy groups. Of these, the acid group is preferably a carboxy group. Examples of the ethylenically unsaturated compound having an acid group include trifunctional to tetrafunctional ethylenically unsaturated compounds having an acid group [those in which a carboxy group has been introduced into a pentaerythritol tri- and tetraacrylate (PETA) skeleton (acid value: 80 mg KOH / g to 120 mg KOH / g)], and pentafunctional to hexafunctional ethylenically unsaturated compounds having an acid group [those in which a carboxy group has been introduced into a dipentaerythritol penta- and hexaacrylate (DPHA) skeleton (acid value: 25 mg KOH / g to 70 mg KOH / g)]. These tri- or higher functional ethylenically unsaturated compounds having an acid group may be used in combination with a difunctional ethylenically unsaturated compound having an acid group, if necessary.

[0434] The ethylenically unsaturated compound having an acid group is preferably at least one selected from the group consisting of di- or higher functional ethylenically unsaturated compounds having a carboxy group and carboxylic acid anhydrides thereof. When the ethylenically unsaturated compound having an acid group is at least one selected from the group consisting of di- or higher functional ethylenically unsaturated compounds having a carboxy group and carboxylic acid anhydrides thereof, the developability and film strength are further improved. The di- or higher functional ethylenically unsaturated compound having a carboxy group is not particularly limited and can be appropriately selected from known compounds. Examples of difunctional or higher ethylenically unsaturated compounds having a carboxy group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and Aronix (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.).

[0435] As the ethylenically unsaturated compound having an acid group, the polymerizable compound having an acid group described in paragraphs 0025 to 0030 of JP-A No. 2004-239942 is preferred, the contents of which are incorporated herein by reference.

[0436] Examples of the ethylenically unsaturated compound include compounds obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid, compounds obtained by reacting a glycidyl group-containing compound with an α,β-unsaturated carboxylic acid, urethane monomers such as (meth)acrylate compounds having a urethane bond, phthalic acid compounds such as γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-o-phthalate, and β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, and alkyl (meth)acrylates. These may be used alone or in combination of two or more.

[0437] Examples of compounds obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid include bisphenol A (meth)acrylate compounds such as 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane; polyethylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups; and polypropylene having 2 to 14 propylene oxide groups. Glycol di(meth)acrylate, polyethylene polypropylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups and 2 to 14 propylene oxide groups, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy tri(meth)acrylate, trimethylolpropane diethoxy tri(meth)acrylate, trimethylolpropane triethoxy tri(meth)acrylate, trimethylolpropane tetraethoxy tri(meth)acrylate, Examples include ethylolpropane pentaethoxytri(meth)acrylate, di(trimethylolpropane)tetraacrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Among these, ethylenically unsaturated compounds having a tetramethylolmethane structure or a trimethylolpropane structure are preferred, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane)tetraacrylate is more preferred.

[0438] Examples of the ethylenically unsaturated compound include caprolactone-modified ethylenically unsaturated compounds (e.g., KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd.), alkylene oxide-modified ethylenically unsaturated compounds (e.g., KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel-Allnex Corporation), and ethoxylated glycerin triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0439] As the ethylenically unsaturated compound, one containing an ester bond is also preferred from the viewpoint of excellent developability. The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule. From the viewpoint of excellent curability and developability, however, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferred, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane)tetraacrylate is more preferred. From the viewpoint of providing reliability, the ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms and the above-mentioned ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure. Examples of ethylenically unsaturated compounds having an aliphatic structure with 6 or more carbon atoms include 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate.

[0440] One preferred embodiment of the ethylenically unsaturated compound is an ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure (preferably a bifunctional ethylenically unsaturated compound). The above-mentioned ethylenically unsaturated compound is preferably an ethylenically unsaturated compound having a ring structure in which two or more aliphatic hydrocarbon rings are fused (preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure), more preferably a bifunctional ethylenically unsaturated compound having a ring structure in which two or more aliphatic hydrocarbon rings are fused, and even more preferably tricyclodecane dimethanol di(meth)acrylate. As the aliphatic hydrocarbon ring structure, a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure, or an isoborone structure is preferred from the viewpoints of the moisture permeability and bending resistance of the resulting cured film and the adhesiveness of the resulting uncured film.

[0441] The molecular weight of the ethylenically unsaturated compound is preferably from 200 to 3,000, more preferably from 250 to 2,600, still more preferably from 280 to 2,200, and particularly preferably from 300 to 2,200. The content of ethylenically unsaturated compounds with a molecular weight of 300 or less among the ethylenically unsaturated compounds contained in the photosensitive resin layer is The content of the substance is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less.

[0442] As one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer preferably contains a difunctional or higher ethylenically unsaturated compound, more preferably a trifunctional or higher ethylenically unsaturated compound, and even more preferably a trifunctional or tetrafunctional ethylenically unsaturated compound.

[0443] In addition, as one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer preferably contains a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and a polymer having a structural unit having an aliphatic hydrocarbon ring structure.

[0444] Furthermore, as one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer preferably contains a compound represented by formula (M) and an ethylenically unsaturated compound having an acid group, more preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, and even more preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a succinic acid modified product of dipentaerythritol pentaacrylate.

[0445] Furthermore, as one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer preferably contains a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a thermally crosslinkable compound described later, and more preferably contains a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a blocked isocyanate compound described later.

[0446] In addition, as one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer preferably contains a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth)acrylate compound) and a trifunctional or higher functional ethylenically unsaturated compound (preferably a trifunctional or higher functional (meth)acrylate compound) from the viewpoints of suppressing development residues and rust prevention. The mass ratio of the content of the difunctional ethylenically unsaturated compound to the content of the tri- or higher functional ethylenically unsaturated compound is preferably 10:90 to 90:10, more preferably 30:70 to 70:30. The content of the difunctional ethylenically unsaturated compound relative to the total amount of all ethylenically unsaturated compounds is preferably from 20% to 80% by mass, more preferably from 30% to 70% by mass. The content of the bifunctional ethylenically unsaturated compound in the photosensitive resin layer is preferably 10% by mass to 60% by mass, more preferably 15% by mass to 40% by mass, based on the total mass of the photosensitive resin layer.

[0447] In addition, as one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer preferably contains a compound M and a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure from the viewpoint of rust prevention. Furthermore, as one preferred embodiment of the photosensitive resin layer, from the viewpoints of substrate adhesion, suppression of development residues, and rust prevention, the photosensitive resin layer preferably contains compound M and an ethylenically unsaturated compound having an acid group, more preferably contains compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and an ethylenically unsaturated compound having an acid group, still more preferably contains compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a tri- or higher functional ethylenically unsaturated compound, and an ethylenically unsaturated compound having an acid group, and particularly preferably contains compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a tri- or higher functional ethylenically unsaturated compound, an ethylenically unsaturated compound having an acid group, and a urethane (meth)acrylate compound. In addition, as one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer is made of 1,9-nonanediol diacrylate and carbodiimide from the viewpoints of substrate adhesion, suppression of development residues, and rust prevention. The copolymer preferably contains a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, more preferably 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, and even more preferably 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, dipentaerythritol hexaacrylate, and an ethylenically unsaturated compound having a carboxylic acid group, and particularly preferably 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, an ethylenically unsaturated compound having a carboxylic acid group, and a urethane acrylate compound.

[0448] The photosensitive resin layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound. The content of the difunctional or higher functional ethylenically unsaturated compound in the ethylenically unsaturated compound is preferably 60% by mass to 100% by mass, more preferably 80% by mass to 100% by mass, and even more preferably 90% by mass to 100% by mass, based on the total content of all ethylenically unsaturated compounds contained in the photosensitive resin layer.

[0449] The ethylenically unsaturated compounds may be used alone or in combination of two or more. The content of the ethylenically unsaturated compound in the photosensitive resin layer is preferably 1% by mass to 70% by mass, more preferably 5% by mass to 70% by mass, even more preferably 5% by mass to 60% by mass, and particularly preferably 5% by mass to 50% by mass, relative to the total mass of the photosensitive resin layer.

[0450] <Polymerization initiator> The photosensitive resin layer contains a polymerization initiator. The polymerization initiator is preferably a photopolymerization initiator. Preferred aspects of the polymerization initiator used in the photosensitive resin layer of the second embodiment include the preferred aspects of the polymerization initiator used in the photosensitive resin layer of the first embodiment described above. The polymerization initiator may be used alone or in combination of two or more kinds. The content of the polymerization initiator 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 resin layer, and the upper limit thereof is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the photosensitive resin layer.

[0451] <Heterocyclic compounds> The photosensitive resin layer may contain a heterocyclic compound. The heterocyclic ring contained in the heterocyclic compound may be either a monocyclic or polycyclic heterocyclic ring. Examples of heteroatoms contained in the heterocyclic compound include a nitrogen atom, an oxygen atom, and a sulfur atom. The heterocyclic compound preferably contains at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably contains a nitrogen atom.

[0452] Examples of heterocyclic compounds include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, and pyrimidine compounds. Among the above, the heterocyclic compound is preferably at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzimidazole compounds, and benzoxazole compounds, and more preferably at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, and benzoxazole compounds. More preferred is at least one compound selected from the following group:

[0453] Preferred specific examples of the heterocyclic compound are shown below. Examples of the triazole compound and benzotriazole compound include the following compounds.

[0454] [ka]

[0455] [ka]

[0456] Examples of the tetrazole compound include the following compounds.

[0457] [ka]

[0458] [ka]

[0459] Examples of the thiadiazole compound include the following compounds:

[0460] [ka]

[0461] Examples of the triazine compound include the following compounds:

[0462] [ka]

[0463] Examples of rhodanine compounds include the following compounds:

[0464] [ka]

[0465] Examples of the thiazole compound include the following compounds:

[0466] [ka]

[0467] Examples of the benzothiazole compound include the following compounds:

[0468] [ka]

[0469] Examples of the benzimidazole compound include the following compounds:

[0470] [ka]

[0471] [ka]

[0472] Examples of the benzoxazole compound include the following compounds:

[0473] [ka]

[0474] The heterocyclic compounds may be used alone or in combination of two or more. When the photosensitive resin layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01% by mass to 20.0% by mass, more preferably 0.10% by mass to 10.0% by mass, even more preferably 0.30% by mass to 8.0% by mass, and particularly preferably 0.50% by mass to 5.0% by mass, relative to the total mass of the photosensitive resin layer.

[0475] <Aliphatic thiol compounds> The photosensitive resin layer may contain an aliphatic thiol compound. When the photosensitive resin layer contains an aliphatic thiol compound, the aliphatic thiol compound undergoes an ene-thiol reaction with the ethylenically unsaturated compound, thereby suppressing the cure shrinkage of the film formed and alleviating stress.

[0476] The aliphatic thiol compound is preferably a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, a di- or higher functional aliphatic thiol compound). Among the above, polyfunctional aliphatic thiol compounds are more preferred as the aliphatic thiol compounds in terms of the adhesion of the pattern to be formed (particularly the adhesion after exposure). In this specification, the term "polyfunctional aliphatic thiol compound" refers to an aliphatic compound having two or more thiol groups (also called "mercapto groups") in the molecule.

[0477] The polyfunctional aliphatic thiol compound is preferably a low molecular weight compound having a molecular weight of at least 100. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and even more preferably 150 to 1,000.

[0478] The number of functional groups in the polyfunctional aliphatic thiol compound is preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 6, from the viewpoint of adhesion of the pattern to be formed.

[0479] Examples of polyfunctional aliphatic thiol compounds include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, trimethylolethane tris(3-mercaptobutyrate), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, trimethylolpropane tris(3-mercaptopropionyloxy)ethyl ester), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), ethylene glycol bisthiopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2'-(ethylenedithio)diethanethiol, meso-2,3-dimercaptosuccinic acid, and di(mercaptoethyl)ether.

[0480] Among the above, the polyfunctional aliphatic thiol compound is preferably at least one compound selected from the group consisting of trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0481] Examples of monofunctional aliphatic thiol compounds include 1-octanethiol and 1-dodecathiol. Examples of suitable mercaptopropionates include methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, n-octyl 3-mercaptopropionate, methoxybutyl 3-mercaptopropionate, and stearyl 3-mercaptopropionate.

[0482] The photosensitive resin layer may contain one kind of aliphatic thiol compound alone, or may contain two or more kinds of aliphatic thiol compounds. When the photosensitive resin layer contains an aliphatic thiol compound, the content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5% by mass to 50% by mass, even more preferably 5% by mass to 30% by mass, and particularly preferably 8% by mass to 20% by mass, relative to the total mass of the photosensitive resin layer.

[0483] <Thermal crosslinkable compound> The photosensitive resin layer preferably contains a thermally crosslinkable compound from the viewpoints of the strength of the resulting cured film and the adhesiveness of the resulting uncured film. As the thermally crosslinkable compound used in the photosensitive resin layer of the second embodiment, the thermally crosslinkable compound described above in the photosensitive resin layer of the first embodiment is suitably used. The thermally crosslinkable compound may be used alone or in combination of two or more kinds. When the photosensitive resin layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass, relative to the total mass of the photosensitive resin layer.

[0484] <Surfactant> The photosensitive resin layer may contain a surfactant. As the surfactant used in the photosensitive resin layer of the second embodiment, the surfactants described above in the photosensitive resin layer of the first embodiment are suitably used. The surfactants may be used alone or in combination of two or more. When the photosensitive resin layer contains a surfactant, the content of the surfactant is preferably 0.01% by mass to 3.0% by mass, more preferably 0.01% by mass to 1.0% by mass, and even more preferably 0.05% by mass to 0.80% by mass, relative to the total mass of the photosensitive resin layer.

[0485] <Radical polymerization inhibitor> The photosensitive resin layer may contain a radical polymerization inhibitor. As the radical polymerization inhibitor used in the photosensitive resin layer of the second embodiment, the radical polymerization inhibitors described above in the photosensitive resin layer of the first embodiment are suitably used. The radical polymerization inhibitor may be used alone or in combination of two or more kinds. When the photosensitive resin layer contains a radical polymerization inhibitor, the content of the radical polymerization inhibitor is preferably 0.01% by mass to 3% by mass, and more preferably 0.05% by mass to 1% by mass, relative to the total mass of the photosensitive resin layer. When the content is 0.01% by mass or more, the storage stability of the photosensitive resin layer is improved. On the other hand, when the content is 3% by mass or less, the sensitivity is maintained and the decolorization of the dye is suppressed more effectively.

[0486] <Hydrogen donor compounds> The photosensitive resin layer may contain a hydrogen donor compound. The hydrogen donor compound has the effect of further improving the sensitivity of the photopolymerization initiator to actinic rays and suppressing inhibition of polymerization of the polymerizable compound by oxygen. Examples of hydrogen donor compounds include amines and amino acid compounds.

[0487] As the amines, for example, those described in "Journal of Po 10, p. 3173 (1972), JP-B-020189 / 1969, JP-A-51-082102, JP-A-52-134692, JP-A-59-138205, JP-A-60-084305, JP-A-62-018537, JP-A-64-033104, and Research Disclosure No. 33825. More specific examples include 4,4'-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (also known as leuco crystal violet), triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, and p-methylthiodimethylaniline. Among these, from the viewpoints of sensitivity, curing speed, and curability, the amine is preferably at least one selected from the group consisting of 4,4'-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane.

[0488] Examples of the amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Among these, N-phenylglycine is preferred as the amino acid compound from the viewpoints of sensitivity, curing speed, and curability.

[0489] Further, examples of the hydrogen donor compound include organometallic compounds (such as tributyltin acetate) described in JP-B-48-042965, hydrogen donors described in JP-B-55-034414, and sulfur compounds (such as trithiane) described in JP-A-6-308727.

[0490] The hydrogen donor compounds may be used alone or in combination of two or more. When the photosensitive resin layer contains a hydrogen donor compound, the content of the hydrogen donor compound is preferably 0.01% by mass to 10.0% by mass, more preferably 0.01% by mass to 8.0% by mass, and even more preferably 0.03% by mass to 5.0% by mass, relative to the total mass of the photosensitive resin layer, from the viewpoint of improving the curing rate through a balance between the polymerization growth rate and chain transfer.

[0491] <Impurities, etc.> The photosensitive resin layer may contain a predetermined amount of impurities. The impurities in the photosensitive resin layer of the second embodiment are the same as the preferable aspects of the impurities described above in the photosensitive resin layer of the first embodiment.

[0492] <Residual monomer> The photosensitive resin layer may contain residual monomers corresponding to the respective structural units of the polymer C described above. The residual monomers corresponding to each structural unit of polymer C in the photosensitive resin layer of the second embodiment are the same as the preferred aspects of the residual monomers corresponding to each structural unit of polymer A described above in the photosensitive resin layer of the first embodiment.

[0493] <Other ingredients> The photosensitive resin layer may contain components other than those already described (hereinafter also referred to as "other components"). Examples of the other components include colorants, antioxidants, and particles (e.g., metal oxide particles). Examples of the other components also include other additives described in paragraphs 0058 to 0071 of JP-A No. 2000-310706.

[0494] -particle- The particles are preferably metal oxide particles. The metals in the metal oxide particles also include metalloids such as B, Si, Ge, As, Sb, and Te. The average primary particle size of the particles is, for example, preferably from 1 nm to 200 nm, more preferably from 3 nm to 80 nm, from the viewpoint of the transparency of the cured film. The average primary particle size of particles is calculated by measuring the particle sizes of 200 random particles using an electron microscope and calculating the arithmetic mean of the measurement results. If the particle shape is not spherical, the particle size is taken to be the longest side.

[0495] When the photosensitive resin layer contains particles, it may contain only one type of particles or two or more types of particles differing in metal type, size, etc. The photosensitive resin layer preferably does not contain particles, or if it does contain particles, the particle content is preferably more than 0% by mass and not more than 35% by mass relative to the total mass of the photosensitive resin layer. Furthermore, the photosensitive resin layer more preferably does not contain particles, or the particle content is more than 0% by mass and not more than 10% by mass relative to the total mass of the photosensitive resin layer. Furthermore, the photosensitive resin layer more preferably does not contain particles, or the particle content is more than 0% by mass and not more than 5% by mass relative to the total mass of the photosensitive resin layer. Furthermore, the photosensitive resin layer more preferably does not contain particles, or the particle content is more than 0% by mass and not more than 1% by mass relative to the total mass of the photosensitive resin layer, and it is particularly preferable that the photosensitive resin layer does not contain particles.

[0496] -Coloring agent- The photosensitive resin layer may contain a colorant (pigment, dye, etc.), but preferably does not substantially contain a colorant, for example, from the viewpoint of transparency. When the photosensitive resin layer contains a colorant, the content of the colorant is preferably less than 1% by mass, more preferably less than 0.1% by mass, based on the total mass of the photosensitive resin layer.

[0497] -Antioxidants- Examples of antioxidants include 3-pyrazolidones such as 1-phenyl-3-pyrazolidone (also known as phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorohydroquinone; paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, and paraphenylenediamine. Among these, from the viewpoints of storage stability and curability, 3-pyrazolidones are preferred as the antioxidant, and 1-phenyl-3-pyrazolidone is more preferred.

[0498] When the photosensitive resin layer contains an antioxidant, the content of the antioxidant is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and even more preferably 0.01% by mass or more, relative to the total mass of the photosensitive resin layer. There is no particular upper limit, but it is preferably 1% by mass or less.

[0499] <Thickness of photosensitive resin layer> The thickness of the photosensitive resin layer is not particularly limited, but from the viewpoints of developability and resolution, it is preferably 30 μm or less, more preferably 20 μm or less, even more preferably 15 μm or less, particularly preferably 10 μm or less, and most preferably 5.0 μm or less. The lower limit is preferably 0.60 μm or more, more preferably 1.5 μm or more, from the viewpoint of excellent strength of the film obtained by curing the photosensitive resin layer.

[0500] <Refractive index of photosensitive resin layer> The refractive index of the photosensitive resin layer is preferably from 1.47 to 1.56, and more preferably from 1.49 to 1.54.

[0501] <Color of photosensitive resin layer> The photosensitive resin layer is preferably achromatic. Specifically, the total reflection (incident angle 8°, light source: D-65 (2° field of view)) is preferably in accordance with CIE1976 (L * ,a * ,b * ) color space, L * The value is preferably 10 to 90, and a * The value is preferably -1.0 to 1.0, and b * The value is preferably between -1.0 and 1.0.

[0502] The pattern obtained by curing the photosensitive resin layer (cured film of the photosensitive resin layer) is preferably achromatic. Specifically, total reflection (incident angle 8°, light source: D-65 (2° field of view)) is * ,a * ,b * ) color space, the L * The value is preferably 10 to 90, and the pattern a *The value is preferably -1.0 to 1.0, and the b * The value is preferably between -1.0 and 1.0.

[0503] <Moisture permeability of photosensitive resin layer> The moisture permeability of the pattern (cured film of the photosensitive resin layer) obtained by curing the photosensitive resin layer at a layer thickness of 40 μm is set to 500 g / (m) from the viewpoint of rust prevention. 2 24hr) or less, and 300g / (m 2 24hr) or less is more preferable, and 100g / (m 2 It is more preferable that the time is 24 hours or less. The moisture permeability was measured by exposing the photosensitive resin layer to i-rays at an exposure dose of 300 mJ / cm 2 After exposure to light at 1000 K, the photosensitive resin layer is post-baked at 145° C. for 30 minutes to harden the photosensitive resin layer, and the hardness is measured on the hardened film.

[0504] [Refractive index adjusting layer] The photosensitive transfer material preferably has a refractive index adjusting layer. The refractive index adjusting layer may be a known refractive index adjusting layer, and examples of materials contained in the refractive index adjusting layer include alkali-soluble resins, ethylenically unsaturated compounds, metal salts, and particles. The method for controlling the refractive index of the refractive index adjusting layer is not particularly limited, and examples thereof include a method of using a resin having a predetermined refractive index alone, a method of using a resin and particles, and a method of using a complex of a metal salt and a resin.

[0505] Examples of the alkali-soluble resin and the ethylenically unsaturated compound include the alkali-soluble resin and the ethylenically unsaturated compound described above in the section "Photosensitive Resin Layer."

[0506] Examples of particles include metal oxide particles and metal particles. The type of metal oxide particles is not particularly limited, and known metal oxide particles can be used. The metals in the metal oxide particles include semimetals such as B, Si, Ge, As, Sb, and Te.

[0507] The average primary particle size of the particles is, for example, preferably from 1 nm to 200 nm, more preferably from 3 nm to 80 nm, from the viewpoint of the transparency of the cured film. The average primary particle size of particles is calculated by measuring the particle sizes of 200 random particles using an electron microscope and calculating the arithmetic mean of the measurement results. If the particle shape is not spherical, the particle size is taken to be the longest side.

[0508] Specifically, the metal oxide particles are preferably at least one selected from the group consisting of zirconium oxide particles (ZrO2 particles), Nb2O5 particles, titanium oxide particles (TiO2 particles), silicon dioxide particles (SiO2 particles), and composite particles thereof. Among these, at least one type of metal oxide particles selected from the group consisting of zirconium oxide particles and titanium oxide particles is more preferred, for example, from the viewpoint that the refractive index can be easily adjusted.

[0509] Commercially available metal oxide particles include calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F04), calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F74), and calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F74). Examples of suitable zirconium oxide particles include zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F75), calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F76), zirconium oxide particles (Nanouse OZ-S30M, manufactured by Nissan Chemical Industries, Ltd.), and zirconium oxide particles (Nanouse OZ-S30K, manufactured by Nissan Chemical Industries, Ltd.).

[0510] The particles may be used alone or in combination of two or more types. The content of particles in the refractive index adjusting layer is preferably 1% by mass to 95% by mass, more preferably 20% by mass to 90% by mass, and even more preferably 40% by mass to 85% by mass, based on the total mass of the refractive index adjusting layer. When titanium oxide is used as the metal oxide particles, the content of the titanium oxide particles is preferably 1% by mass to 95% by mass, more preferably 20% by mass to 90% by mass, and even more preferably 40% by mass to 85% by mass, relative to the total mass of the refractive index adjusting layer.

[0511] The refractive index of the refractive index-matching layer is preferably higher than the refractive index of the photosensitive resin layer. The refractive index of the refractive index-matching layer is preferably 1.50 or more, more preferably 1.55 or more, even more preferably 1.60 or more, and particularly preferably 1.65 or more. The upper limit of the refractive index of the refractive index-matching layer is preferably 2.10 or less, more preferably 1.85 or less, and particularly preferably 1.78 or less.

[0512] The thickness of the refractive index adjusting layer is preferably 50 nm to 500 nm, more preferably 55 nm to 110 nm, and even more preferably 60 nm to 100 nm.

[0513] <Relationship between temporary support, photosensitive resin layer and cover film> In the second embodiment as well, it is preferable that the relationships among the temporary support, the photosensitive resin layer, and the cover film described in the first embodiment are satisfied.

[0514] <Method for producing photosensitive transfer material according to the second embodiment> The method for producing the photosensitive transfer material of the second embodiment is not particularly limited, and known methods can be used. Examples of a method for manufacturing the photosensitive transfer material 10 shown in Figure 2 include a method including the steps of applying a photosensitive resin composition to the surface of the temporary support 1 to form a coating film, and then drying this coating film to form the photosensitive resin layer 3, and applying a composition for forming a refractive index adjustment layer to the surface of the photosensitive resin layer 3 to form a coating film, and then drying this coating film to form the refractive index adjustment layer 5.

[0515] The photosensitive transfer material 10 is produced by pressing the cover film 7 onto the refractive index adjusting layer 5 of the laminate produced by the above-mentioned production method. As a manufacturing method for the photosensitive transfer material of the first embodiment, it is preferable to include a step of providing a cover film 7 so that it is in contact with the surface of the refractive index adjusting layer 5 opposite the side having the temporary support 1, thereby manufacturing a photosensitive transfer material 10 having a temporary support 1, a photosensitive resin layer 3, a refractive index adjusting layer 5, and a cover film 7. After the photosensitive transfer material 10 is produced by the above-mentioned production method, the photosensitive transfer material 10 is wound up. The photosensitive transfer material in the form of a roll can be provided in the form as it is for the step of laminating the material to a substrate in a roll-to-roll system, which will be described later.

[0516] In addition, the method for manufacturing the photosensitive transfer material 10 may be a method in which a refractive index adjustment layer 5 is formed on a cover film 7, and then a photosensitive resin layer 3 is formed on the surface of the refractive index adjustment layer 5. In addition, the manufacturing method of the above-mentioned photosensitive transfer material 10 may be a method in which a photosensitive resin layer 3 is formed on a temporary support 1, a refractive index adjustment layer 5 is separately formed on a cover film 7, and the refractive index adjustment layer 5 is bonded to the photosensitive resin layer 3.

[0517] The photosensitive resin composition and the method for forming the photosensitive resin layer in the second embodiment are the same as the photosensitive resin composition and the method for forming the photosensitive resin layer described above in the first embodiment, and the preferred aspects are also the same.

[0518] <Composition for forming refractive index adjusting layer and method for forming refractive index adjusting layer> The composition for forming the refractive index adjusting layer preferably contains the various components for forming the refractive index adjusting layer described above and a solvent. Note that in the composition for forming the refractive index adjusting layer, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the refractive index adjusting layer described above. The solvent is not particularly limited as long as it can dissolve or disperse the components contained in the refractive index adjusting layer, and at least one selected from the group consisting of water and water-miscible organic solvents is preferred, and water or a mixed solvent of water and a water-miscible organic solvent is more preferred. Examples of water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, with alcohols having 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred. The solvents may be used alone or in combination of two or more. The content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.

[0519] The method for forming the refractive index adjusting layer is not particularly limited as long as it is a method capable of forming a layer containing the above components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.).

[0520] Furthermore, by laminating a cover film to the refractive index adjusting layer, the photosensitive transfer material of the second embodiment can be produced. The method for bonding the cover film to the refractive index adjusting layer is not particularly limited, and known methods can be used. Examples of a device for laminating the cover film to the refractive index-adjusting layer include known laminators such as a vacuum laminator and an auto-cut laminator. The laminator is preferably equipped with any heatable roller such as a rubber roller and is capable of applying pressure and heat.

[0521] [Method for manufacturing a resin pattern and a circuit wiring] The method for producing a resin pattern is not particularly limited as long as it is a method for producing a resin pattern using the above-mentioned photosensitive transfer material.

[0522] The method for producing a resin pattern includes a step of laminating a surface of the photosensitive resin layer of the photosensitive transfer material that does not face the temporary support (i.e., the second surface) to a substrate (hereinafter referred to as “lamination”). It is preferable that the method includes, in this order, a step of exposing the photosensitive resin layer to pattern light (hereinafter also referred to as an "exposure step"), a step of developing the photosensitive resin layer after the pattern light exposure step to form a resin pattern (hereinafter also referred to as a "development step").

[0523] The method for producing the circuit wiring is not particularly limited as long as it is a method for producing the circuit wiring using the above-mentioned photosensitive transfer material.

[0524] It is preferable that the method for manufacturing circuit wiring is a method including the above-mentioned laminating step, the above-mentioned exposure step, the above-mentioned development step, and a step of etching the substrate in areas where the resin pattern is not arranged (hereinafter also referred to as the "etching step").

[0525] Each step included in the method for manufacturing a resin pattern and the method for manufacturing a circuit wiring will be described below. Unless otherwise specified, the content described for each step included in the method for manufacturing a resin pattern also applies to each step included in the method for manufacturing a circuit wiring.

[0526] [Laminating process] The method for producing the resin pattern preferably includes a lamination step. In the lamination step, it is preferable to bring a substrate (or the conductive layer, if provided on the surface of the substrate) into contact with the second surface of the photosensitive resin layer, and to press the photosensitive transfer material and the substrate together. In this embodiment, the adhesion between the second surface of the photosensitive resin layer and the substrate is improved, so that the patterned photosensitive resin layer after exposure and development can be suitably used as an etching resist when etching.

[0527] When the photosensitive transfer material has a cover film, the cover film may be removed from the surface of the photosensitive resin layer before lamination.

[0528] Furthermore, in the case where the photosensitive transfer material further comprises a layer other than the cover film on the second surface of the photosensitive resin layer (for example, at least one layer selected from the group consisting of a high refractive index layer and a low refractive index layer), the lamination step is carried out in such a manner that the second surface of the photosensitive resin layer and the substrate are laminated via that layer.

[0529] The method for pressing the substrate and the photosensitive transfer material together is not particularly limited, and known transfer methods and lamination methods can be used.

[0530] The photosensitive transfer material is preferably bonded to the substrate by placing the substrate on the second surface side of the photosensitive resin layer and applying pressure and heat using a roll or other means. For bonding, known laminators such as a laminator, a vacuum laminator, and an auto-cut laminator, which can further increase productivity, can be used.

[0531] The method for producing a resin pattern and the method for producing a circuit wiring, which include the lamination step, are preferably carried out by a roll-to-roll method.

[0532] The roll-to-roll method will be described below. The roll-to-roll method is a method in which a substrate that can be wound up and unwound is used as the substrate, and includes a step of unwinding the substrate or a structure including the substrate (also referred to as an "unwinding step") before any of the steps included in the method for manufacturing a resin pattern or the method for manufacturing circuit wiring, and a step of winding up the substrate or a structure including the substrate (also referred to as a "winding step") after any of the steps, and at least any of the steps (preferably all of the steps, or all of the steps other than the heating step) are performed while the substrate or the structure including the substrate is being transported.

[0533] The unwinding method in the unwinding step and the winding method in the winding step are not particularly limited, and any known method may be used in a manufacturing method that employs a roll-to-roll system.

[0534] <Substrate> A known substrate can be used as the substrate used in forming a resin pattern using the photosensitive transfer material according to the present disclosure. The substrate is preferably a substrate having a conductive layer, more preferably a substrate having a conductive layer on the surface of a base material.

[0535] The substrate may have any layer other than the conductive layer, if necessary.

[0536] Examples of the base material that constitutes the substrate include glass, silicon, and resin films. The substrate is preferably transparent. In this specification, "transparent" means that the transmittance of light with a wavelength of 400 nm to 700 nm is 80% or more. The refractive index of the substrate is preferably 1.50 to 1.52.

[0537] Examples of transparent glass substrates include tempered glass, such as Gorilla Glass from Corning Inc. Furthermore, materials described in JP-A-2010-86684, JP-A-2010-152809, and JP-A-2010-257492 can be used as the transparent glass substrate.

[0538] When a resin film is used as the substrate, the substrate is preferably a resin film with small optical distortion and / or high transparency, such as polyethylene terephthalate (PET) film, polyethylene naphthalate film, polycarbonate film, triacetyl cellulose film, and cycloolefin polymer film.

[0539] When manufacturing by a roll-to-roll method, the substrate is preferably a resin film. When manufacturing circuit wiring for a touch panel by a roll-to-roll method, the substrate is preferably a resin sheet.

[0540] The conductive layer of the substrate may be a conductive layer used for general circuit wiring or touch panel wiring.

[0541] From the viewpoints of electrical conductivity and fine line formability, the conductive layer is preferably at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, more preferably a metal layer, and even more preferably a copper layer or a silver layer.

[0542] The substrate may have one conductive layer or two or more conductive layers. When the substrate has two or more conductive layers, the substrate preferably has conductive layers made of two or more different materials.

[0543] Materials for the conductive layer include metals and conductive metal oxides.

[0544] Metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au.

[0545] Examples of conductive metal oxides include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide) and SiO2. In this context, "conductivity" means that the volume resistivity is 1×10 6 The volume resistivity of conductive metal oxides is less than 1×10 4 It is preferably less than Ωcm.

[0546] When a resin pattern is produced using a substrate having a plurality of conductive layers, at least one of the plurality of conductive layers preferably contains a conductive metal oxide.

[0547] The conductive layer is preferably an electrode pattern corresponding to a sensor of a visual recognition section used in a capacitive touch panel or wiring of a peripheral extraction section.

[0548] [Exposure process] The method for producing a resin pattern preferably includes, after the laminating step, a step of pattern-exposing the photosensitive resin layer (exposure step).

[0549] The detailed arrangement and specific size of the pattern in the pattern exposure are not particularly limited. At least a part of the pattern (preferably the electrode pattern and / or lead wiring portion of the touch panel) preferably includes thin lines having a width of 20 μm or less, more preferably thin lines having a width of 10 μm or less. This can improve the display quality of a display device (e.g., a touch panel) equipped with an input device having circuit wiring manufactured by the circuit wiring manufacturing method, and reduce the area occupied by the lead wiring.

[0550] The light source used for exposure is not particularly limited as long as it irradiates light with a wavelength (e.g., 365 nm or 405 nm) that can expose the photosensitive resin layer, and can be appropriately selected and used. Examples of light sources include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (light emitting diodes).

[0551] The exposure dose was 5 mJ / cm 2 ~200mJ / cm 2 and preferably 10 mJ / cm 2 ~100mJ / cm 2 It is more preferable that:

[0552] In the exposure step, pattern exposure may be performed after peeling the temporary support from the photosensitive resin layer, or pattern exposure may be performed via the temporary support and then the temporary support may be peeled off. When exposure is performed after peeling the temporary support, exposure may be performed by bringing the mask and the photosensitive resin layer into contact with each other, or by bringing the mask and the photosensitive resin layer close together without contacting each other. When exposure is performed without peeling the temporary support, exposure may be performed by bringing the mask and the temporary support into contact with each other, or by bringing the mask and the temporary support close together without contacting each other. In order to prevent contamination of the mask due to contact between the photosensitive resin layer and the mask and to avoid the influence of foreign matter attached to the mask on the exposure, it is preferable to perform pattern exposure without peeling off the temporary support. The exposure method is a contact exposure method in the case of contact exposure, and a proximity exposure method, in the case of non-contact exposure, and a lens system may also be used. A lens-based or mirror-based projection exposure method, or a direct exposure method using an exposure laser or the like can be appropriately selected and used. In the case of a lens-based or mirror-based projection exposure method, an exposure machine having an appropriate lens numerical aperture (NA) can be used depending on the required resolution and depth of focus. In the case of a direct exposure method, the photosensitive resin layer may be directly exposed, or reduced projection exposure may be performed on the photosensitive resin layer through a lens. Furthermore, exposure may be performed not only under atmospheric pressure but also under reduced pressure or vacuum. Furthermore, exposure may be performed with a liquid such as water interposed between the light source and the photosensitive resin layer.

[0553] [Development process] The method for producing a resin pattern preferably includes, after the exposure step, a step of developing the exposed photosensitive resin layer to form a resin pattern (development step).

[0554] When the photosensitive transfer material has a thermoplastic resin and an intermediate layer, the unexposed area is The thermoplastic resin layer and the intermediate layer in the exposed area are also removed together with the photosensitive resin layer in the unexposed area. In the developing step, the thermoplastic resin layer and the intermediate layer in the exposed area may also be removed by dissolving or dispersing in the developer.

[0555] The exposed photosensitive resin layer can be developed using a developer.

[0556] The developer is not particularly limited as long as it can remove the non-image areas (non-exposed areas) of the photosensitive resin layer, and known developers such as those described in JP-A No. 5-72724 can be used.

[0557] The developer is preferably an alkaline aqueous solution containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol / L to 5 mol / L. The developer may contain at least one selected from the group consisting of water-soluble organic solvents and surfactants. The developer is also preferably the developer described in paragraph 0194 of WO 2015 / 093271.

[0558] The development method is not particularly limited, and may be any of puddle development, shower development, shower and spin development, and dip development. Shower development is a development treatment in which a developer is sprayed onto the exposed photosensitive resin layer by showering, thereby removing the unexposed areas.

[0559] After the development step, it is preferable to remove development residues by spraying a cleaning agent by showering and scrubbing with a brush.

[0560] The temperature of the developer is not particularly limited, but is preferably 20°C to 40°C.

[0561] [Etching process] The method for manufacturing circuit wiring preferably includes a step (etching step) of etching the substrate in areas where the resin patterns are not arranged in a laminate in which the resin patterns manufactured by the manufacturing method including the laminating step, the exposing step, and the developing step are laminated in this order.

[0562] In the etching step, the resin pattern formed from the photosensitive resin layer is used as an etching resist to etch the substrate.

[0563] As the etching method, known methods can be applied, for example, the method described in paragraphs 0209 to 0210 of JP 2017-120435 A, the method described in paragraphs 0048 to 0054 of JP 2010-152155 A, a wet etching method in which the substrate is immersed in an etching solution, and a dry etching method such as plasma etching can be mentioned.

[0564] The etching solution used in the wet etching may be an acidic or alkaline etching solution that is appropriately selected depending on the target to be etched.

[0565] Examples of acidic etching solutions include aqueous solutions of an acidic component selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, and aqueous solutions of a mixture 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.

[0566] Alkaline etching solutions include sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (such as tetramethylammonium hydroxide). and a mixed aqueous solution of an alkaline component and a salt (for example, potassium permanganate). The alkaline component may be a combination of multiple alkaline components.

[0567] [Removal process] In the method for manufacturing circuit wiring, it is preferable to carry out a step of removing the remaining resin pattern (removal step).

[0568] The removal step is not particularly limited and can be carried out as needed, but is preferably carried out after the etching step.

[0569] The method for removing the remaining resin pattern is not particularly limited, but includes a method of removing it by chemical treatment, and a method of removing it using a remover is preferred as a method of removing the remaining resin pattern.

[0570] A method for removing the photosensitive resin layer includes immersing the substrate with the remaining resin pattern in a stirring removal liquid, the liquid temperature of which is preferably 30°C to 80°C, more preferably 50°C to 80°C, for 1 minute to 30 minutes.

[0571] Examples of the removal solution include a removal solution obtained by dissolving an inorganic or organic alkaline component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixture thereof. Examples of the inorganic alkaline component include sodium hydroxide and potassium hydroxide. Examples of the organic alkaline component include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

[0572] Alternatively, the remaining resin pattern may be removed by a known method such as a spray method, a shower method, or a puddle method using a remover.

[0573] [Other steps] The method for manufacturing a circuit wiring may include any other steps (other steps) in addition to the steps described above, such as, but not limited to, the following steps.

[0574] Furthermore, examples of the exposure step, development step, and other steps that can be applied to the method for manufacturing circuit wiring include the steps described in paragraphs 0035 to 0051 of JP-A No. 2006-23696.

[0575] <Cover film peeling process> When the photosensitive transfer material has a cover film, the method for producing a resin pattern preferably includes a step of peeling the cover film from the photosensitive transfer material. The method for peeling the cover film is not particularly limited, and known methods can be applied.

[0576] <Step of reducing visible light reflectance> The method for manufacturing circuit wiring may include a step of performing a treatment to reduce the visible light reflectance of a part or all of the conductive layers provided on the substrate.

[0577] An example of a treatment for reducing the visible light reflectance is oxidation treatment. When the substrate has a conductive layer containing copper, the visible light reflectance of the conductive layer can be reduced by oxidizing the copper to copper oxide and blackening the conductive layer.

[0578] The treatment for reducing the visible light reflectance is described in JP 2014-150118 A. Nos. 0017 to 0025, and paragraphs 0041, 0042, 0048, and 0058 of JP-A-2013-206315, the contents of which are incorporated herein by reference.

[0579] <Step of forming an insulating film, step of forming a new conductive layer on the surface of the insulating film> The method for manufacturing a circuit wiring preferably includes the steps of forming an insulating film on the surface of the circuit wiring and forming a new conductive layer on the surface of the insulating film. By these steps, a second electrode pattern insulated from the first electrode pattern can be formed.

[0580] The step of forming the insulating film is not particularly limited, and may include a known method for forming a permanent film. Alternatively, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having insulating properties.

[0581] The step of forming a new conductive layer on the insulating film is not particularly limited, and for example, a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.

[0582] A preferred method for manufacturing circuit wiring involves using a substrate having multiple conductive layers on both surfaces of a base material, and sequentially or simultaneously forming circuits on the conductive layers formed on both surfaces of the base material. This configuration allows the formation of touch panel circuit wiring in which a first conductive pattern is formed on one surface of the base material and a second conductive pattern is formed on the other surface. It is also preferred to form such touch panel circuit wiring from both surfaces of the base material using a roll-to-roll process.

[0583] [Circuit wiring applications] The circuit wiring manufactured by the circuit wiring manufacturing method can be applied to various devices. Examples of devices equipped with the circuit wiring manufactured by the above manufacturing method include input devices, preferably touch panels, and more preferably capacitive touch panels. Furthermore, the input devices can be applied to display devices such as organic electroluminescence (EL) display devices and liquid crystal display devices.

[0584] [Touch panel manufacturing method] The method for producing a touch panel is not particularly limited as long as it is a method for producing a touch panel using the above-mentioned photosensitive transfer material.

[0585] It is preferable that the method for manufacturing a touch panel includes the above-mentioned bonding step, the above-mentioned exposure step, the above-mentioned development step, and a step of etching the substrate in areas where the resin pattern is not arranged (hereinafter also referred to as the "etching step").

[0586] Specific aspects of each step in the method for manufacturing a touch panel, and the order in which each step is performed, are as described above in the section "Method for manufacturing circuit wiring," and the same applies to preferred aspects. The method for manufacturing a touch panel may refer to a known method for manufacturing a touch panel, except that the touch panel wiring is formed by the above method. The method for manufacturing a touch panel may also include any other steps (other steps) in addition to the above steps.

[0587] An example of a mask pattern used in manufacturing a touch panel is shown in FIGS. In the pattern A shown in FIG. 3 and the pattern B shown in FIG. 4, GR is a non-image portion (light-shielding portion), EX is an image portion (exposed portion), and DL is a virtual frame for alignment. In a manufacturing method of a touch panel, for example, by exposing the photosensitive resin layer through a mask having the pattern A shown in FIG. 3, A touch panel can be manufactured in which circuit wiring having pattern A is formed. Specifically, it can be manufactured by the method shown in Figure 1 of WO 2016 / 190405. In one example of the manufactured touch panel, the central part of the exposed area EX (the pattern part where the electrodes are connected) is the part where the transparent electrode (touch panel electrode) is formed, and the peripheral part (thin line part) of the exposed area EX is the part where the wiring of the peripheral extraction part is formed.

[0588] The touch panel manufacturing method described above produces a touch panel having at least touch panel wiring. The touch panel preferably has a transparent substrate, electrodes, and an insulating layer or a protective layer.

[0589] Examples of detection methods for touch panels include known methods such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, an optical method, etc. Among these, the capacitance method is preferred as the detection method for touch panels. Examples of detection methods for touch panels include known methods such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method, among which the capacitance method is preferred.

[0590] Examples of touch panel types include so-called in-cell types (for example, those shown in Figures 5, 6, 7, and 8 of JP-A-2012-517051), so-called on-cell types (for example, those shown in Figure 19 of JP-A-2013-168125 and those shown in Figures 1 and 5 of JP-A-2012-89102), OGS (One Glass Solution) types, TOL (Touch-on-Lens) types (for example, those shown in Figure 2 of JP-A-2013-54727), various out-cell types (so-called GG, G1 / G2, GFF, GF2, GF1, and G1F, etc.), and other configurations (for example, those shown in Figure 6 of JP-A-2013-164871). An example of a touch panel is described in paragraph 0229 of JP 2017-120435 A.

[0591] [Polyethylene terephthalate film] The polyethylene terephthalate film of the present disclosure has a minimum number of foreign particles with a major diameter of 3 μm or more of 0.5 particles / mm 2 In particular, the polyethylene terephthalate film of the present disclosure has a film thickness of 0.5 pieces / mm or less, and the film thickness is 0.5 pieces / mm or less. 2 Furthermore, among foreign particles having a major diameter of 3 μm or more, those having a major diameter of 1580 cm or less by laser Raman spectroscopy are preferred. -1 and 1360 cm -1 The number of foreign particles at which two peaks are observed is 0.5 particles / mm 2 Furthermore, it is preferable that the number of foreign particles having a brightness 10% or more lower than that of the surrounding normal area among foreign particles having a major diameter of 3 μm or more is 0.5 particles / mm 2 It is preferable that:

[0592] The polyethylene terephthalate film of the present disclosure has a minimum number of foreign particles with a major diameter of 3 μm or more of 0.5 particles / mm 2 The polyethylene terephthalate film of the present disclosure is suitable as a temporary support for a photosensitive transfer material because of the following: A photosensitive transfer material using the polyethylene terephthalate film of the present disclosure can produce a resin pattern with reduced defects. [Example]

[0593] The following examples further illustrate the embodiments of the present invention. The materials, amounts used, proportions, processing details, and processing procedures shown in the following examples can be changed 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.

[0594] <Preparation of Photosensitive Resin Composition> The components used to prepare the photosensitive resin composition are as follows: [Polymer A] Polymer A was synthesized according to the following method. In the synthesis method of polymer A, the following abbreviations represent the following compounds, respectively. St: Styrene (Fujifilm Wako Pure Chemical Industries, Ltd.) MAA: methacrylic acid (Fujifilm Wako Pure Chemical Industries, Ltd.) MMA: Methyl methacrylate (Fujifilm Wako Pure Chemical Industries, Ltd.) V-601: 2,2'-azobis(isobutyrate) dimethyl (Fujifilm Wako Pure Chemical Industries, Ltd., polymerization initiator) PGMEA: Propylene glycol monomethyl ether acetate

[0595] PGMEA (116.5 parts) was placed in a three-necked flask and heated to 90°C under a nitrogen atmosphere. While maintaining the liquid temperature in the three-necked flask at 90°C ± 2°C, a mixture of St (52.0 parts), MMA (19.0 parts), MAA (29.0 parts), V-601 (4.0 parts) and PGMEA (116.5 parts) was added dropwise to the three-necked flask over 2 hours. After the addition was complete, the mixture was stirred for 2 hours while maintaining the liquid temperature at 90°C ± 2°C, yielding a composition containing 30.0% by mass of polymer A. The acid value of polymer A was 189 mgKOH / g, the weight-average molecular weight was 1.03g, and the saturation point was 1.07g. The molecular weight was 60,000 and the glass transition temperature was 131°C.

[0596] [Polymerizable compound B] Polymerizable compound B-1: NK Ester BPE-500 (2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd.) Polymerizable compound B-2: Dimethacrylate of polyethylene glycol with an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide attached to both ends of bisphenol A. Polymerizable compound B-3: NK Ester A-TMPT (trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) Polymerizable compound B-4: SR454 (ethoxylated (3) trimethylolpropane triacrylate, manufactured by Arkema) Polymerizable compound B-5: NK Ester A-9300-1CL (ε-caprolactone-modified tris-(2-acryloxyethyl) isocyanurate, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0597] [Photopolymerization initiator] B-CIM (photoradical polymerization initiator, 2-(2-chlorophenyl)-4,5-diphenylimidazole dimer, manufactured by Hampford)

[0598] [Sensitizer] SB-PI 701 (4,4'-bis(diethylamino)benzophenone, manufactured by Sanyo Trading Co., Ltd.)

[0599] [Dye N] Dye N-1: LCV (Leuco Crystal Violet, manufactured by Tokyo Chemical Industry Co., Ltd., a dye that develops color by radicals) Dye N-2: Brilliant Green (Tokyo Chemical Industry Co., Ltd.)

[0600] [Rust inhibitor] Mixture of 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole (quality Quantity ratio 1:1)

[0601] [Antioxidants] Irganox 245 (ethylene bis(oxyethylene) bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate), manufactured by BASF)

[0602] [Polymerization inhibitor] N-nitrosophenylhydroxylamine aluminum salt (Fujifilm Wako Pure Chemical Industries, Ltd.)

[0603] A photosensitive resin composition was prepared by mixing the following components. ·Polymer A (solids concentration 30.0%): 51.00 parts ·Polymerizable compound B-1: 15.00 parts ·Polymerizable compound B-2: 10.00 parts ·Polymerizable compound B-3: 5.00 parts ·Polymerizable compound B-4: 5.00 parts ·Polymerizable compound B-5: 9.77 parts Photopolymerization initiator: 3.00 parts Sensitizer: 0.30 parts ·Dye N-1: 0.60 parts ·Dye N-2: 0.02 parts Rust inhibitor: 0.10 parts Antioxidant: 0.20 parts Polymerization inhibitor: 0.01 parts Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.): 100.00 parts PGMEA (Showa Denko): 50.00 parts Methanol (Mitsubishi Gas Chemical Co., Ltd.): 10.00 parts

[0604] <Preparing the temporary support> A polyethylene terephthalate (PET) film with a thickness of 100 μm was prepared as a temporary support. Specifically, the mesh size of the metal filter used in the manufacturing process of the temporary support was changed to 10 μm, 5 μm, 2 μm, and 1 μm, and the recovery position when recovering the manufactured temporary support was changed, thereby obtaining the six supports shown in Table 1. The number of foreign matters contained in each support was measured. The measurement method is as follows. In Table 1, at least one element selected from the group consisting of F, Mg, Si, Ca, Ti, Fe, and Sb is defined as a "specific element," and the number of foreign matters was measured by laser Raman spectroscopy at 1580 cm -1 and 1360 cm -1 2 One peak was designated as a "specific peak."

[0605] (Number of foreign particles with a major diameter of 3 μm or more) First, the temporary support was observed with a polarizing microscope (product name "BX60" with a "U-POT" filter and a "U-AN360" filter inserted to form a simple polarizing microscope, 10x objective lens, manufactured by Olympus Corporation), and the portion where polarization was disturbed was identified as a foreign substance. In addition, the major diameter of the foreign substance was measured with an optical microscope (product name "BX60" with a 100x objective lens, manufactured by Olympus Corporation) and the observation area was 250 mm2 The number of foreign particles with a major axis of 3 μm or more contained in the sample was counted. If the foreign particle contained a void, the major axis was measured including the void. The major axis refers to the length of the longest part of the region that constitutes the foreign particle.

[0606] (Number of foreign particles with a major axis of 3 μm or more that contain at least one element selected from the group consisting of F, Mg, Si, Ca, Ti, Fe, and Sb) First, the temporary support is placed under a polarizing microscope (product name "BX60" with a "U-POT" filter and "U The specimens were observed under a simple polarizing microscope (with a "BX60" filter inserted, 10x objective lens, manufactured by Olympus) and the areas where the polarization was disturbed were identified as foreign bodies. The major diameters of the foreign bodies were also measured under an optical microscope (product name "BX60", 100x objective lens, manufactured by Olympus) and foreign bodies with major diameters of 3 μm or more were identified. The observation area was 250 mm. 2 Foreign matter with a major axis of 3 μm or more contained in the sample was cut using a microtome and subjected to elemental analysis by the SEM-EDX method using a SEM-EDX device (product name "JSM-7200F", manufactured by JEOL Ltd.). The area was compared with the normal area around the foreign matter, and the number of foreign matters in which at least one element selected from the group consisting of F, Mg, Si, Ca, Ti, Fe, and Sb was detected was counted.

[0607] (1580cm in laser Raman spectroscopy) -1 and 1360 cm -1 Two peaks (Number of foreign objects with a major diameter of 3 μm or more) First, the temporary support was observed with a polarizing microscope (product name "BX60" with a "U-POT" filter and a "U-AN360" filter inserted to form a simple polarizing microscope, 10x objective lens, manufactured by Olympus Corporation), and areas where polarization disturbance occurred were identified as foreign matter. Furthermore, the major diameter of the foreign matter was measured with an optical microscope (product name "BX60" with a 100x objective lens, manufactured by Olympus Corporation), and foreign matter with a major diameter of 3 μm or more was identified. Observation area: 250 mm 2Foreign matter with a major axis of 3 μm or more contained in the sample was cut with a microtome and analyzed by laser Raman spectroscopy using a laser Raman spectrophotometer (product name "NRS-7500", manufactured by JASCO Corporation). Analysis was performed using an objective lens with a numerical aperture (NA) of 0.90 and a magnification of 100x, with an excitation wavelength of 785 nm. The difference spectrum between the foreign matter and the normal area around the foreign matter was taken, and the peak intensity at 1580 cm -1 and 1360 cm -1 The number of foreign particles where the two peaks were observed was counted.

[0608] (Number of foreign objects with a major axis of 3 μm or larger whose brightness is 10% or more lower than the brightness of the surrounding normal area) First, the temporary support was observed with a polarizing microscope (product name "BX60" with a "U-POT" filter and a "U-AN360" filter inserted to form a simple polarizing microscope, 10x objective lens, manufactured by Olympus Corporation), and areas where polarization disturbance occurred were identified as foreign matter. Furthermore, the major diameter of the foreign matter was measured with an optical microscope (product name "BX60" with a 100x objective lens, manufactured by Olympus Corporation), and foreign matter with a major diameter of 3 μm or more was identified. Observation area: 250 mm 2 The brightness of foreign matter with a major axis of 3 μm or more contained in the sample was measured, as well as the brightness of the normal area surrounding the foreign matter. The number of foreign matter whose brightness was 10% or more lower than the brightness of the normal area surrounding the foreign matter was then counted. The brightness of the foreign matter and the normal area surrounding the foreign matter was measured using the V value displayed in the HSV color system on images obtained by observing the foreign matter using an optical microscope in transmission mode.

[0609] [Table 1]

[0610] <Preparation of photosensitive transfer material> [Example 1] The photosensitive resin composition was applied onto the temporary support 5 using a slit nozzle so that the coating width was 1.0 m and the layer thickness after drying was 10 μm. The coating film of the photosensitive resin composition was dried at 80° C. for 40 seconds to form a photosensitive resin layer, and a photosensitive transfer material was obtained.

[0611] [Examples 2 to 8, Comparative Examples 1 to 3] Photosensitive transfer materials were obtained in the same manner as in Example 1, except that the type of temporary support and the thickness of the photosensitive resin layer were changed as shown in Table 2.

[0612] The photosensitive transfer materials obtained in the examples and comparative examples were used to evaluate wiring defects and resolution. The evaluation results are shown in Table 2. Note that for comparative example 3, the resolution was low and a 10 μm line and space pattern could not be created, so wiring defects could not be measured and this is indicated as "-" in Table 2.

[0613] <Wiring defect> First, a copper layer having a thickness of 200 nm was formed on a polyethylene terephthalate (PET) film having a thickness of 100 μm by sputtering, thereby preparing a PET substrate with a copper layer. After unwinding the photosensitive transfer material in roll form, the photosensitive transfer material and the PET substrate with the copper layer were laminated together so that the photosensitive resin layer and the copper layer were in contact with each other. The lamination process was carried out under the conditions of a roll temperature of 120°C, a linear pressure of 1.0 MPa, and a linear speed of 0.5 m / min. The photosensitive resin layer was exposed to light from the temporary support side of the obtained laminate through a photomask using an ultra-high pressure mercury lamp (main exposure wavelength: 365 nm). The photomask used for exposure had a line and space pattern with a width ratio (duty ratio) of the transmission area to the light-shielding area of ​​1:1 and a line width (and space width) of 10 μm. After peeling off the temporary support from the exposed laminate, the laminate was subjected to shower development for 30 seconds using a 1.0% aqueous sodium carbonate solution at a liquid temperature of 25°C. The copper layer was then etched for 60 seconds using a ferric chloride etching solution (manufactured by Kanto Chemical Co., Ltd.) to produce a wiring pattern with a width of 10 μm. A 1000 mm optical microscope (product name "BX60", 100x objective lens, manufactured by Olympus Corporation) was used to measure the copper layer. 2The area was observed and the number of defects in the wiring pattern was counted. A part where half or more of the line width was missing was considered to be defective. The evaluation criteria were as follows: 3 or more is a level that is not problematic for practical use. 5: 0 defects. 4: One or two defects. 3: There are 3 to 5 defects. 2: There are 6 to 10 defects 1: 11 or more defects.

[0614] <resolution> First, a copper layer having a thickness of 200 nm was formed on a polyethylene terephthalate (PET) film having a thickness of 100 μm by sputtering, thereby preparing a PET substrate with a copper layer. After unwinding the photosensitive transfer material in roll form, the photosensitive transfer material and the PET substrate with the copper layer were laminated together so that the photosensitive resin layer and the copper layer were in contact with each other. The lamination process was carried out under the conditions of a roll temperature of 120°C, a linear pressure of 1.0 MPa, and a linear speed of 0.5 m / min. The photosensitive resin layer was exposed to light from the temporary support side of the resulting laminate through a photomask using an ultra-high pressure mercury lamp (dominant exposure wavelength: 365 nm). The photomask used for exposure had a line and space pattern in which the ratio of the width of the transmission area to the width of the light-shielding area (duty ratio) was 1:1 and the line width (and space width) varied in 1 μm increments from 1 μm to 20 μm. The exposure dose to the photosensitive resin layer was adjusted so that the line width of the resin pattern formed by exposure to irradiation light that passed through an area of ​​the photomask where the line width and space width of the line and space pattern were 20 μm would be 20 μm. After peeling off the temporary support from the exposed laminate, the laminate was exposed to a liquid temperature of 25°C and 1.0% Shower development was performed for 30 seconds using an aqueous sodium carbonate solution, removing the unexposed photosensitive resin layer from the laminate, and producing a resin pattern with the above-mentioned stepwise line-and-space pattern on the surface of the copper layer.

[0615] The formed resin pattern was observed for each line width using a scanning electron microscope (product name "S-4800", manufactured by Hitachi High-Technologies Corporation) to check the pattern shape and the presence or absence of residue of the photosensitive resin layer in the space portions. The smallest line width of the resin pattern in which the cured photosensitive resin layer did not peel off in the line portions and there was no residue of the photosensitive resin layer was determined as the resolution. The evaluation criteria are as follows: 5: The resolution is 4 μm or less. 4: Resolution is 5 μm or 6 μm. 3: Resolution is 7 μm or 8 μm. 2: The resolution is 9 μm or 10 μm. 1: Resolution is 11 μm or greater.

[0616] [Table 2]

[0617] As shown in Table 2, in Examples 1 to 8, the number of foreign particles with a major diameter of 3 μm or more contained in the temporary support was 0.5 particles / mm 2 It was found that there were few defects in the wiring pattern because the

[0618] On the other hand, in Comparative Examples 1 to 3, the number of foreign particles with a major diameter of 3 μm or more contained in the temporary support was 0.5 pieces / mm 2 Because the wiring pattern was larger than the standard, it was found that there were many defects in the wiring pattern.

[0619] Moreover, in Example 4, the thickness of the photosensitive resin layer is 10 μm or less, and therefore the resolution is higher than that of Example 1.

[0620] <Preparation of Photosensitive Resin Compositions A-1 to A-10> Photosensitive resin compositions A-1 to A-10 were prepared by mixing the components shown in Table 3 below.

[0621] [Synthesis of Polymer C] (Alkali-soluble resin P-1 solution) -Polymerization process- Propylene glycol monomethyl ether acetate (manufactured by Sanwa Chemical Industry Co., Ltd., product name PGM-Ac) (60 g) and propylene glycol monomethyl ether (manufactured by Sanwa Chemical Industry Co., Ltd., product name PGM) (240 g) were introduced into a 2000 mL flask. The resulting liquid was heated to 90°C while being stirred at a stirring speed of 250 rpm (rounds per minute; the same applies hereinafter). To prepare the dropping solution (1), methacrylic acid (manufactured by Mitsubishi Rayon, trade name Acryester M 107.1 g of methyl methacrylate (manufactured by Mitsubishi Gas Chemical Company, trade name MMA) (5.46 g), and cyclohexyl methacrylate (manufactured by Mitsubishi Gas Chemical Company, trade name CHMA) (231.42 g) were mixed and diluted with PGM-Ac (60 g) to obtain a dropping solution (1). The dropping liquid (2) was prepared by dissolving dimethyl 2,2'-azobis(2-methylpropionate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name V-601) (9.637 g) in PGM-Ac (136.56 g). Dropping liquid (1) and dropping liquid (2) were simultaneously added dropwise over 3 hours to the 2000 mL flask (specifically, a 2000 mL flask containing a liquid heated to 90°C). Next, the container for dropping liquid (1) was washed with PGM-Ac (12 g), and the washings were added dropwise to the 2000 mL flask. Next, the container for dropping liquid (2) was washed with PGM-Ac (6 g), and the washings were added dropwise to the 2000 mL flask. During these additions, the reaction solution in the 2000 mL flask was kept at 90°C and stirred at a stirring speed of 250 rpm. Further, as a post-reaction, stirring was carried out at 90°C for 1 hour. To the reaction solution after the post-reaction, V-601 (2.401 g) was added as the first additional initiator addition. Furthermore, the V-601 container was washed with PGM-Ac (6 g), and the washings were introduced into the reaction solution. Then, the mixture was stirred at 90 °C for 1 hour. Next, V-601 (2.401 g) was added to the reaction solution as the second additional initiator addition. The V-601 container was then washed with PGM-Ac (6 g), and the washings were added to the reaction solution. The mixture was then stirred at 90°C for 1 hour. Next, V-601 (2.401 g) was added to the reaction mixture as the third additional initiator addition. Furthermore, the V-601 container was washed with PGM-Ac (6 g), and the washings were added to the reaction mixture. The mixture was then stirred at 90°C for 3 hours.

[0622] -Additional process- After stirring at 90°C for 3 hours, PGM-Ac (178.66 g) was introduced into the reaction solution. Next, tetraethylammonium bromide (Fujifilm Wako Pure Chemical Industries, Ltd.) (1.8 g) and hydroquinone monomethyl ether (Fujifilm Wako Pure Chemical Industries, Ltd.) (0.8 g) were added to the reaction solution. Furthermore, each vessel was washed with PGM-Ac (6 g), and the washings were introduced into the reaction solution. Then, the temperature of the reaction solution was raised to 100°C. Next, glycidyl methacrylate (NOF Corporation, trade name: Blenmer G) (76.03 g) was added dropwise to the reaction solution over 1 hour. The Blenmer G vessel was washed with PGM-Ac (6 g), and the washings were introduced into the reaction solution. After this, the mixture was stirred at 100°C for 6 hours as an addition reaction. The reaction mixture was then cooled and filtered through a 100 mesh filter to obtain 1158 g of alkali-soluble resin P-1 (solid concentration: 36.3% by mass). The resulting alkali-soluble resin P-1 had a weight-average molecular weight of 27,000, a number-average molecular weight of 15,000, and an acid value of 95 mgKOH / g.

[0623] The structural formula of alkali-soluble resin P-1 is shown below: The molar ratio of the repeating units in the formula, starting from the left repeating unit, was 51.5:2:26.5:20.

[0624] [ka]

[0625] (Alkali-soluble resin P-2 solution) 82.4 g of propylene glycol monomethyl ether was placed in a flask and heated to 90°C under a nitrogen stream. A solution of 38.4 g of styrene, 30.1 g of dicyclopentanyl methacrylate, and 34.0 g of methacrylic acid dissolved in 20 g of propylene glycol monomethyl ether, and a solution of 5.4 g of polymerization initiator V-601 (Fujifilm Wako Pure Chemical Industries, Ltd.) dissolved in 43.6 g of propylene glycol monomethyl ether acetate were simultaneously added dropwise over 3 hours. After the dropwise addition was completed, 0.75 g of V-601 was added three times every hour. The reaction was then continued for another 3 hours. The mixture was then diluted with 58.4 g of propylene glycol monomethyl ether acetate and 11.7 g of propylene glycol monomethyl ether. The reaction mixture was heated to 100°C under an air stream, and 0.53 g of tetraethylammonium bromide and 0.26 g of p-methoxyphenol were added. To this was added dropwise 25.5 g of glycidyl methacrylate (Blenmer GH manufactured by NOF Corporation) over 20 minutes. This was allowed to react at 100°C for 7 hours to obtain a solution of alkali-soluble resin P-2. The solids concentration of the obtained solution was 36.5 mass%. The alkali-soluble resin P-2 had a weight-average molecular weight of 17,000, a number-average molecular weight of 6,200, a polydispersity of 2.4, and an acid value of 94.5 mg KOH / g. The amount of residual monomer measured using gas chromatography was less than 0.1 mass% of the polymer solids for all monomers.

[0626] The structural formula of alkali-soluble resin P-2 is shown below: The molar ratio of the repeating units in the formula, starting from the left repeating unit, was 41.0:15.2:23.9:19.9.

[0627] [ka]

[0628] (Alkali-soluble resin P-3 solution) 113.5 g of propylene glycol monomethyl ether was placed in a flask and heated to 90°C under a nitrogen stream. A solution of 172 g of styrene, 4.7 g of methyl methacrylate, and 112.1 g of methacrylic acid dissolved in 30 g of propylene glycol monomethyl ether, and a solution of 27.6 g of polymerization initiator V-601 (Fujifilm Wako Pure Chemical Industries, Ltd.) dissolved in 57.7 g of propylene glycol monomethyl ether were simultaneously added dropwise over 3 hours. After the dropwise addition was completed, 2.5 g of V-601 was added three times every hour. The reaction was then continued for another 3 hours. The mixture was then diluted with 160.7 g of propylene glycol monomethyl ether acetate and 233.3 g of propylene glycol monomethyl ether. The reaction mixture was heated to 100°C under an air stream, and 1.8 g of tetraethylammonium bromide and 0.86 g of p-methoxyphenol were added. To this was added dropwise 71.9 g of glycidyl methacrylate (Blenmer G manufactured by NOF Corporation) over 20 minutes. This was allowed to react at 100°C for 7 hours to obtain a solution of alkali-soluble resin P-3. The solid concentration of the obtained solution was 36.2 mass%. The weight-average molecular weight of alkali-soluble resin P-3 was 18,000, the number-average molecular weight was 7,800, the dispersity was 2.3, and the acid value of the polymer was 124 mgKOH / g. Measured using gas chromatography. The measured amount of residual monomer was less than 0.1% by mass based on the polymer solid content for all monomers.

[0629] The structural formula of alkali-soluble resin P-3 is shown below: The molar ratio of the repeating units in the formula, starting from the left repeating unit, was 55.1:26.5:1.6:16.8.

[0630] [ka]

[0631] (Alkali-soluble resin P-4 solution) By changing the type and amount of monomer used in the synthesis of alkali-soluble resin P-3, a 36.2% solids solution of alkali-soluble resin P-4 (solvent: propylene glycol monomethyl ether acetate) was prepared. The resulting alkali-soluble resin P-4 had a weight-average molecular weight of 18,000, a number-average molecular weight of 7,800, a polydispersity of 2.3, and an acid value of 114 mgKOH / g.

[0632] The structural formula of alkali-soluble resin P-4 is shown below: The molar ratio of the repeating units in the formula, starting from the left repeating unit, was 55.1:24.6:1.6:17.0:1.7.

[0633] [ka]

[0634] [Table 3]

[0635] In Table 3, Compound B and Compound C have the following structures:

[0636] (Compound B)

[0637] [ka]

[0638] (Compound C)

[0639] [ka]

[0640] <Preparation of Compositions B-1 to B-4 for Forming Refractive Index Adjusting Layer> The components shown in Table 4 below were mixed to prepare compositions B-1 to B-4 for forming a refractive index-adjusting layer.

[0641] [Table 4]

[0642] <Preparation of photosensitive transfer material> [Examples 9 to 24] On the temporary support 5, a coating width of 1.0 m and a layer thickness after drying of The photosensitive resin composition was applied so that the values ​​shown in Table 5 were obtained. The coating of the photosensitive resin composition was dried at 80°C for 40 seconds to form a photosensitive resin layer. Furthermore, a composition for forming a refractive index adjusting layer was applied onto the photosensitive resin composition using a slit nozzle so that the coating width was 1.0 m and the layer thickness after drying was the value shown in Table 5. The coating of the composition for forming a refractive index adjusting layer was dried at 80°C for 40 seconds to form a photosensitive resin layer, and a photosensitive transfer material was obtained.

[0643] [Comparative Examples 4 to 19] A photosensitive transfer material was obtained in the same manner as in Examples 9 to 24, except that the photosensitive resin composition was applied onto the temporary support 1.

[0644] [Table 5]

[0645] The photosensitive transfer material thus obtained was evaluated for pinhole defects. The evaluation results are shown in Table 6.

[0646] <Pinhole defect> First, a 100-nm-thick indium tin oxide (ITO) layer was formed on a 100-μm-thick polyethylene terephthalate (PET) film by sputtering, thereby producing a PET substrate with an ITO layer. After unwinding the roll-type photosensitive transfer material, the photosensitive transfer material and the PET substrate with ITO layer are The photosensitive resin layer and the ITO layer were attached to each other at a roll temperature of 120°C, a linear pressure of 1.0 MPa, and a linear speed of 0.5 m / min. The photosensitive resin layer was exposed to light from an ultra-high pressure mercury lamp (main wavelength: 365 nm) through a photomask from the temporary support side of the obtained laminate. The exposure dose for the photosensitive resin layer was adjusted so that the line width of the resin pattern formed by exposure with irradiation light that passed through the region where the line width and space width of the line and space pattern were 20 μm was 20 μm. After peeling off the temporary support from the exposed laminate, the laminate was subjected to shower development for 30 seconds using a 1.0% by mass aqueous solution of sodium carbonate at a liquid temperature of 25°C. A solid resist pattern was obtained over the entire surface. 2 The area was observed and the number of pinhole defects in the resist pattern was counted. Pinholes with a diameter of 4 μm or more were considered pinhole defects. The evaluation criteria were as follows: 3 or more is a level that presents no practical problems. 4: 2 or fewer defects. 3: There are 3 to 5 defects. 2: There are 6 to 10 defects 1: 11 or more defects.

[0647] [Table 6]

[0648] The photosensitive transfer material according to the present disclosure can be suitably used in various applications requiring precise microfabrication by photolithography. After patterning the photosensitive resin layer, etching may be performed using the photosensitive resin layer as a coating, or electroforming mainly using electroplating may be performed. The cured film obtained by patterning may also be used as a permanent film. The cured film may be used, for example, as an interlayer insulating film, a wiring protective film, or a wiring protective film having an index matching layer. The photosensitive transfer material according to the present disclosure can also be used as a material for forming various wirings such as semiconductor packages, printed circuit boards, and sensor boards, as well as a material for forming contacts. The film can be suitably used as a material for forming conductive films such as switch panels, electromagnetic wave shielding materials, film heaters, liquid crystal sealants, micromachines, and structures in the microelectronics field.

[0649] The disclosures of Japanese Patent Application No. 2020-081212 filed on May 1, 2020, Japanese Patent Application No. 2020-171962 filed on October 12, 2020, and Japanese Patent Application No. 2020-207767 filed on December 15, 2020 are incorporated herein by reference in their entirety. In addition, all documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually indicated to be incorporated by reference.

Claims

1. A temporary support and a photosensitive resin layer disposed on the temporary support, The number of foreign particles having a major diameter of 3 μm or more contained in the temporary support is 0.5 / mm ２ A photosensitive transfer material, which is:

2. the number of foreign matters having a major axis of 3 μm or more and containing at least one element selected from the group consisting of F, Mg, Si, Ca, Ti, Fe, and Sb contained in the temporary support is 0.5 / mm ２ 2. The photosensitive transfer material according to claim 1, wherein:

3. Among the foreign matters contained in the temporary support with a major axis of 3 μm or more, those having a diameter of 1580 cm or less as measured by laser Raman spectroscopy －１ and 1360 cm -１ The number of foreign particles where two peaks are observed is 0.5 pieces / mm ２ 2. The photosensitive transfer material according to claim 1, wherein:

4. Among the foreign particles contained in the temporary support having a major diameter of 3 μm or more, the number of foreign particles whose brightness is 10% or more lower than the brightness of the surrounding normal region is 0.5 particles / mm ２ 2. The photosensitive transfer material according to claim 1, wherein:

5. the temporary support is a single layer containing a resin, 5. The photosensitive transfer material according to claim 1, wherein the photosensitive resin layer is disposed directly on the temporary support.

6. 6. The photosensitive transfer material according to claim 1, wherein the photosensitive resin layer has a thickness of 10 μm or less.

7. a step of laminating a surface of the photosensitive resin layer in the photosensitive transfer material according to any one of claims 1 to 6, the surface not facing the temporary support, to a substrate; a step of pattern-exposing the photosensitive resin layer in the photosensitive transfer material after the laminating step; and developing the photosensitive resin layer after the pattern exposure step to form a resin pattern.

8. a step of laminating a surface of the photosensitive resin layer in the photosensitive transfer material according to any one of claims 1 to 6, the surface not facing the temporary support, to a substrate; a step of pattern-exposing the photosensitive resin layer in the photosensitive transfer material after the laminating step; a step of developing the photosensitive resin layer after the pattern exposure step to form a resin pattern; and etching the substrate in the area where the resin pattern is not disposed.

9. a step of laminating a surface of the photosensitive resin layer in the photosensitive transfer material according to any one of claims 1 to 6, the surface not facing the temporary support, to a substrate; a step of pattern-exposing the photosensitive resin layer in the photosensitive transfer material after the laminating step; a step of developing the photosensitive resin layer after the pattern exposure step to form a resin pattern; and etching the substrate in an area where the resin pattern is not disposed.

10. The number of foreign particles with a major diameter of 3 μm or more is 0.5 / mm ２ Polyethylene terephthalate film:

11. The number of foreign particles with a major axis of 3 μm or more containing at least one element selected from the group consisting of F, Mg, Si, Ca, Ti, Fe, and Sb is 0.5 / mm ２ The polyethylene terephthalate film of claim 10, wherein:

12. Among the foreign particles having a major diameter of 3 μm or more, those having a diameter of 1580 cm or less by laser Raman spectroscopy －１ and 1360 cm －１ The number of foreign particles at which the two peaks are observed is 0.5 particles / mm ２ The polyethylene terephthalate film of claim 10, wherein:

13. Among the foreign particles having a major diameter of 3 μm or more, the number of foreign particles whose brightness is 10% or more lower than the brightness of the surrounding normal area is 0.5 particles / mm ２ The polyethylene terephthalate film of claim 10, wherein:

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