Manufacturing method for laminates, manufacturing method for circuit wiring boards, transfer film

Abstract

To provide a method for manufacturing a laminate which can suppress excessive adhesion between a photosensitive layer and a photomask after exposure, and is also excellent in resolution of a pattern formed by the photosensitive layer.SOLUTION: A method for manufacturing a laminate includes the steps of: bonding a transfer film having a temporary support, an intermediate layer and a photosensitive layer and a substrate, so that a surface opposite to the intermediate layer side of the photosensitive layer of the transfer film comes in contact with the substrate; peeling the temporary support, between the temporary support and the intermediate layer; bringing the exposed intermediate layer into contact with a mask and performing exposure treatment, further performing development treatment after exposure, and forming a pattern, wherein surface free energy of the surface on the side of the temporary support of the intermediate layer is 68.0 mJ / m2 or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for manufacturing a laminate, a method for manufacturing a circuit wiring board, and a transfer film. [Background technology]

[0002] Pattern formation methods using transfer films are widely used because they require fewer steps to obtain a predetermined pattern. Specifically, this method involves placing a photosensitive layer on a substrate using a transfer film, exposing this photosensitive layer through a mask, and then developing it to form a pattern.

[0003] For example, Patent Document 1 discloses "a method for exposing a photosensitive composition layer to ultraviolet light, characterized in that a support (A), a negative-type photosensitive composition layer (B) having a thickness of 1 to 35 μm, and a protective layer (C) are laminated to the metal-coated surface of a metal-coated insulating board having a metal conductor layer on one or both sides, such that the negative-type photosensitive composition layer (B) is in close contact with the metal-coated surface of the metal-coated insulating board, and the support is peeled off before exposure and the image of the photomask is projected through a lens." [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Patent No. 4477077 [Overview of the project] [Problems that the invention aims to solve]

[0005] The inventors of the present invention investigated an exposure method in which a support (temporary support) is peeled off before exposure, and a photomask is applied to the photosensitive composition layer (photosensitive layer) exposed by the peeling, with reference to the exposure method described in Patent Document 1. They found that when peeling off the photomask after exposure, the photosensitive layer and the photomask sometimes adhere excessively, making peeling difficult. Poor peelability between the photosensitive layer and the photomask after exposure can lead to various problems such as reduced workability due to difficulty in peeling, and mask contamination due to adhesion of the photosensitive layer forming material. Therefore, they found that it is necessary to suppress excessive adhesion between the photosensitive layer and the photomask after exposure. On the other hand, if exposure is performed by placing the photomask on the temporary support without removing the temporary support in order to suppress excessive adhesion between the photosensitive layer and the photomask, the exposure light source is separated from the photosensitive layer due to the presence of the temporary support. This can lead to a problem where it is difficult to form a fine pattern with suppressed residue in areas corresponding to the recesses of the pattern (for example, areas corresponding to the unexposed parts in the case of a negative-type photosensitive layer) (in other words, the resolution tends to be poor). Therefore, when considering methods to suppress excessive adhesion between the photosensitive layer and the photomask after exposure, it is necessary to ensure excellent resolution.

[0006] Therefore, the object of the present invention is to provide a method for manufacturing a laminate that can suppress excessive adhesion between the photosensitive layer and the photomask after exposure, and also has excellent resolution of the pattern formed from the photosensitive layer. Furthermore, the present invention also aims to provide a method for manufacturing a circuit wiring board. Furthermore, the present invention aims to provide a transfer film suitable for an exposure method in which a temporary support is peeled off before exposure, which can suppress excessive adhesion between the photosensitive layer and the photomask after exposure, and also has excellent resolution. [Means for solving the problem]

[0007] The inventors have found that the above problem can be solved by the following configuration.

[0008] [1] A step of bonding the transfer film and the substrate such that the surface of the photosensitive layer of the transfer film having a temporary support, an intermediate layer, and a photosensitive layer is in contact with the substrate, Between the above-mentioned temporary support and the above-mentioned intermediate layer, the process involves peeling off the temporary support, The process includes bringing the exposed intermediate layer into contact with a mask and performing an exposure treatment, and further performing a development treatment after exposure to form a pattern. The surface free energy of the surface on the temporary support side of the intermediate layer is 68.0 mJ / m 2 The following is a method for manufacturing a laminate. [2] The method for manufacturing a laminate according to [1], wherein the arithmetic mean roughness Ra of the surface of the intermediate layer on the temporary support side is 50 nm or less. [3] The surface free energy on the intermediate layer side of the above-mentioned temporary support is 25.0 to 50.0 mJ / m 2 The method for manufacturing a laminate according to [1] or [2]. [4] A method for producing a laminate according to any one of [1] to [3], wherein the intermediate layer contains polyvinyl alcohol. [5] The method for producing the laminate according to [4], wherein the polyvinyl alcohol content is 5 to 95% by mass relative to the total mass of the intermediate layer. [6] A method for producing a laminate according to any one of [1] to [5], wherein the intermediate layer further contains polyvinylpyrrolidone. [7] A method for producing a laminate according to any one of [1] to [6], wherein the intermediate layer further comprises one or more compounds X selected from the group consisting of water-soluble cellulose derivatives, polyethers, phenol derivatives, and glycerin. [8] The method for producing the laminate according to [7], wherein the content of compound X is 0.1% by mass or more and less than 30% by mass with respect to the total mass of the intermediate layer. [9] A method for producing a laminate according to [7] or [8], wherein the compound X contains hydroxypropyl methylcellulose.

[10] A method for manufacturing a laminate according to any one of [1] to [9], wherein the thickness of the intermediate layer is 3.0 μm or less.

[11] A method for manufacturing a laminate according to any one of [1] to

[10] , wherein the thickness of the photosensitive layer is 2.0 to 20 μm.

[12] A method for manufacturing circuit wiring, which includes a method for manufacturing a laminate described in any of [1] to

[11] , A process of forming a seed layer on a substrate to form a substrate with a seed layer, A step of laminating the transfer film and the substrate with the seed layer such that the surface of the photosensitive layer of the transfer film having a temporary support, an intermediate layer, and a photosensitive layer is in contact with the substrate with the seed layer, thereby obtaining a substrate with a photosensitive layer having the substrate, the seed layer, the photosensitive layer, the intermediate layer, and the temporary support in this order, Between the above-mentioned temporary support and the above-mentioned intermediate layer, the process involves peeling off the temporary support, The process involves bringing the exposed intermediate layer into contact with the mask and performing an exposure treatment, and then performing a development treatment after exposure to form a pattern. A step of forming a metal plating layer on the seed layer in an area where the above pattern is not present by a plating process, A step of forming a protective layer on the above metal plating layer, The process of removing the above pattern, The process includes the step of removing the exposed seed layer to obtain a conductive nanowire, The surface free energy of the surface on the temporary support side of the intermediate layer is 68.0 mJ / m 2 The following is a method for manufacturing a circuit wiring board.

[13] A transfer film having a temporary support, an intermediate layer, and a photosensitive layer, The surface free energy of the surface on the temporary support side of the intermediate layer is 68.0 mJ / m 2 The following: A transfer film in which the arithmetic mean roughness Ra of the surface on the temporary support side of the intermediate layer is 50 nm or less.

[14] The surface free energy on the intermediate layer side of the above-mentioned temporary support is 25.0 to 50.0 mJ / m 2 The transfer film described in

[13] .

[15] The transfer film according to

[13] or

[14] , wherein the intermediate layer contains polyvinyl alcohol.

[16] The transfer film according to

[15] , wherein the polyvinyl alcohol content is 5 to 95% by mass relative to the total mass of the intermediate layer.

[17] A transfer film according to any one of

[13] to

[16] , wherein the above intermediate layer further contains polyvinylpyrrolidone.

[18] The transfer film according to any one of

[13] to

[17] , wherein the intermediate layer contains one or more compounds X selected from the group consisting of water-soluble cellulose derivatives, polyethers, phenol derivatives, and glycerin.

[19] The transfer film according to

[18] , wherein the content of compound X is 0.1% by mass or more and less than 30% by mass with respect to the total mass of the intermediate layer.

[20] The transfer film according to

[18] or

[19] , wherein the compound X contains hydroxypropyl methylcellulose.

[21] A transfer film according to any of

[13] to

[20] , wherein the thickness of the above intermediate layer is 3.0 μm or less.

[22] A transfer film according to any one of

[13] to

[21] , wherein the thickness of the photosensitive layer is 2.0 to 20 μm. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a method for manufacturing a laminate that can suppress excessive adhesion between the photosensitive layer and the photomask after exposure, and can form a pattern with excellent resolution from the photosensitive layer. Furthermore, the present invention also provides a method for manufacturing a circuit wiring board. Furthermore, the present invention also provides a transfer film suitable for an exposure method in which a temporary support is peeled off before exposure, which can suppress excessive adhesion between the photosensitive layer and the photomask after exposure, and can form a pattern with excellent resolution. [Brief explanation of the drawing]

[0010] [Figure 1]This is a schematic diagram showing an example of a transfer film X1. [Figure 2] This is a schematic diagram showing an example of transfer film X2. [Modes for carrying out the invention]

[0011] The present invention will be described in detail below. In this specification, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. In this specification, in numerical ranges described in stages, the upper or lower limit stated in one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in numerical ranges described in this specification, the upper or lower limit stated in one numerical range may be replaced with the values ​​shown in the examples.

[0012] In this specification, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes, as long as their intended purpose is achieved.

[0013] In this specification, "transparent" means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more, and preferably 90% or more. In this specification, the average transmittance of visible light is a value measured using a spectrophotometer, which can be measured using, for example, a Hitachi U-3310 spectrophotometer manufactured by Hitachi, Ltd.

[0014] In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are calculated using polystyrene as the standard substance, measured by a gel permeation chromatography (GPC) analyzer using TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all product names of Tosoh Corporation) as the column, THF (tetrahydrofuran) as the eluent, a differential refractometer as the detector, and polystyrene as the standard substance. Furthermore, unless otherwise specified in this specification, the molecular weight of a compound with a molecular weight distribution is the weight-average molecular weight (Mw). In this specification, unless otherwise specified, the content of metallic elements is measured using an inductively coupled plasma (ICP) spectrometer. In this specification, unless otherwise specified, the refractive index is the value measured using an ellipsometer at a wavelength of 550 nm. In this specification, unless otherwise specified, hue values ​​are those measured using a colorimeter (CR-221, manufactured by Minolta, Inc.).

[0015] In this specification, "(meth)acrylic" is a concept that encompasses both acrylic and methacrylic, "(meth)acryloyloxy group" is a concept that encompasses both acryloyloxy group and methacryloyloxy group, "(meth)acrylamide group" is a concept that encompasses both acrylamide group and methacrylamide group, and "(meth)acrylate" is a concept that encompasses both acrylate and methacrylate.

[0016] In this specification, "alkali-soluble" means that the solubility in 100 g of a 1% by mass sodium carbonate aqueous solution at a liquid temperature of 22°C is 0.1 g or more. Therefore, for example, an alkali-soluble resin refers to a resin that satisfies the above solubility conditions.

[0017] In this specification, "water-soluble" means that the solubility in 100g of water at a pH of 7.0 at a liquid temperature of 22°C is 0.1g or more. Therefore, for example, a water-soluble resin refers to a resin that satisfies the above-mentioned solubility conditions.

[0018] In this specification, "solids" of a composition means the components that form the composition layer formed using the composition, and if the composition contains a solvent (organic solvent, water, etc.), it means all components excluding the solvent. Furthermore, any liquid components that form the composition layer are also considered to be solids.

[0019] [Method for manufacturing laminates] The method for manufacturing the laminate of the present invention is, A step of bonding the transfer film, which has a temporary support, an intermediate layer, and a photosensitive layer, to the substrate such that the surface of the photosensitive layer opposite to the intermediate layer side of the transfer film is in contact with the substrate (hereinafter also referred to as the "transfer film bonding step"), Between the above-mentioned temporary support and the above-mentioned intermediate layer, there is a step of peeling off the temporary support (hereinafter also referred to as the "temporary support peeling step"), The process includes bringing the exposed intermediate layer into contact with the mask and performing an exposure process, and further performing a development process after exposure to form a pattern (hereinafter also referred to as the "pattern formation process"). The surface free energy of the surface on the temporary support side of the intermediate layer is 68.0 mJ / m 2 The following applies:

[0020] The distinctive features of the present invention's method for manufacturing a laminate include the provision of an intermediate layer between the temporary support and the photosensitive layer, and the setting of the surface free energy of this intermediate layer on the temporary support side to be below a predetermined numerical range. According to the present invention's method for manufacturing a laminate, excessive adhesion between the photosensitive layer and the photomask after exposure can be suppressed, and resolution is also excellent.

[0021] The mechanism by which the present invention's method for manufacturing the laminate achieves the desired effect is not clear, but the inventors speculate as follows. First, the manufacturing method of the laminate of the present invention includes an intermediate layer between the temporary support and the photosensitive layer. As a result, in the pattern formation step after the temporary support peeling step, the mask and the photosensitive layer do not come into direct contact due to the presence of the intermediate layer. Consequently, excessive adhesion between the photosensitive layer and the mask after exposure is suppressed. The inventors conducted further investigations into the above-mentioned intermediate layer and found that the surface free energy of the surface of the intermediate layer on the temporary support side is 68.0 mJ / m 2We have found that if the value exceeds a certain limit, peeling becomes difficult at the interface between the intermediate layer and the temporary support during the temporary support peeling process, resulting in partial exposure of the photosensitive layer without peeling at the interface between the intermediate layer and the temporary support, and / or roughening of the surface of the intermediate layer after peeling off the temporary support (increase in the arithmetic mean roughness Ra of the intermediate layer surface). Specifically, we have clarified that if partial exposure of the photosensitive layer occurs without peeling at the interface between the intermediate layer and the temporary support, excessive adhesion between the exposed photosensitive layer and the mask occurs, making it difficult to peel off the mask after exposure. Furthermore, we have clarified that even if exposure and development can be performed after peeling off the temporary support, uniform exposure may be hindered due to the aforementioned exposure of the photosensitive layer and / or roughening of the surface of the intermediate layer (increase in the arithmetic mean roughness Ra of the intermediate layer surface), making it difficult to form a fine pattern with suppressed residue in the recessed areas of the pattern.

[0022] The method for manufacturing the laminate of the present invention will be described in detail below, step by step. While the descriptions of the constituent elements below may be based on a typical embodiment of the present invention, the present invention is not limited to such embodiments. Furthermore, in the following, the ability to further suppress excessive adhesion between the photosensitive layer and the photomask after exposure (hereinafter also referred to as "better mask non-adhesion") and / or to form a fine pattern with suppressed residue in the recessed areas of the pattern (hereinafter also referred to as "better resolution") is also referred to as "better effect of the present invention."

[0023] [First Embodiment] The first embodiment of the method for manufacturing the laminate comprises the following steps in this order: a transfer film lamination step, a temporary support peeling step, and a pattern formation step. Transfer film lamination process: A process of laminating a transfer film (hereinafter also referred to as "transfer film X") having a temporary support, an intermediate layer, and a photosensitive layer, such that the surface of the photosensitive layer opposite to the intermediate layer (the surface of the transfer film X opposite to the temporary support) is in contact with the substrate. Temporary support peeling step: A step of peeling the temporary support from between the temporary support and the intermediate layer. Pattern formation process: This process involves bringing the exposed intermediate layer into contact with a mask and performing an exposure treatment, followed by a development treatment to form a pattern (hereinafter also referred to as the "pattern formation process"). Furthermore, in the above-mentioned transfer film X, the surface free energy of the surface of the intermediate layer on the temporary support side is 68.0 mJ / m 2 The following applies:

[0024] <<Transfer film lamination process>> <Transfer Film X> Transfer film X will be explained later.

[0025] <Transfer film lamination process> The transfer film lamination process involves laminating the transfer film (transfer film X), which has a temporary support, an intermediate layer, and a photosensitive layer, to a substrate such that the surface of the photosensitive layer opposite to the intermediate layer is in contact with the substrate. If the transfer film X has a protective film, the protective film is removed before performing the lamination process.

[0026] During lamination, the substrate and the transfer film X are pressed together so that the surfaces opposite to the intermediate layer side of the photosensitive layer are in contact. There are no particular restrictions on the method of pressing as described above, and known transfer methods and lamination methods can be used. In particular, it is preferable to place the surface of the transfer film X opposite to the intermediate layer side of the photosensitive layer onto the substrate and apply pressure and heat using a roll or the like. For lamination, known laminators such as vacuum laminators and auto-cut laminators can be used. There are no particular restrictions on the lamination temperature, but it is preferably, for example, 70 to 130°C.

[0027] The substrate is preferably a conductive substrate having a support substrate and a conductive layer disposed on the support substrate. The conductive substrate may have any layer other than the conductive layer formed on the support substrate as needed. In other words, the substrate is preferably a conductive substrate having at least a support substrate and a conductive layer disposed on the support substrate.

[0028] Examples of support substrates include resin substrates, glass substrates, and semiconductor substrates. Preferred embodiments of the support substrate are described, for example, in paragraph

[0140] of International Publication No. 2018 / 155193, which are incorporated herein by reference. Furthermore, when the support substrate is a resin substrate, cycloolefin polymer and polyimide are preferred as the material of the resin substrate, and the thickness of the resin substrate is preferably 5 to 200 μm, and more preferably 10 to 100 μm.

[0029] 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, from the viewpoint of conductivity and fine wire formation. Furthermore, the support substrate may have only one conductive layer or two or more conductive layers. When two or more conductive layers are arranged, it is preferable that the conductive layers be made of different materials. Preferred embodiments of the conductive layer are described, for example, in paragraph

[0141] of International Publication No. 2018 / 155193, which are incorporated herein by reference.

[0030] A conductive substrate having at least one of transparent electrodes and routing wiring is preferred. A conductive substrate with such a configuration can be suitably used as a substrate for a touch panel. Transparent electrodes can function suitably as electrodes for touch panels. Preferably, transparent electrodes are composed of metal oxide films such as ITO (indium tin oxide) and IZO (indium zinc oxide), as well as metal fine wires such as metal mesh and metal nanowires. Examples of the fine metal wires include fine wires such as silver and copper. Among them, silver conductive materials such as silver mesh and silver nanowires are preferred.

[0031] The material of the routing wiring is preferably a metal. Examples of the metal as the material of the routing wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and alloys composed of two or more of these metal elements. As the material of the routing wiring, copper, molybdenum, aluminum, or titanium is preferable, and copper is particularly preferable.

[0032] In the method for manufacturing the laminate of the present invention, when the photosensitive layer in the transfer film X functions as an electrode protection film for a touch panel, for the purpose of protecting electrodes etc. (that is, at least one of the touch panel electrode and the touch panel wiring), it is preferable that the electrodes etc. are provided so as to cover directly or via another layer.

[0033] <<Temporary support peeling step>> The temporary support peeling step is a step of peeling the temporary support between the temporary support and the intermediate layer.

[0034] <Peeling treatment> The method for peeling the temporary support is not particularly limited and can be carried out based on known techniques. For example, a mechanism similar to the cover film peeling mechanism described in paragraphs

[0161] to

[0162] of JP-A-2010-072589 can be used.

[0035] <Surface free energy of the surface of the intermediate layer on the temporary support side> As described above, in the transfer film X, the surface free energy of the surface of the intermediate layer on the temporary support side is 68.0 mJ / m 2 or less. The surface free energy of the surface of the intermediate layer on the temporary support side (hereinafter, "surface free energy E IThis term is also called ). ) refers to the surface free energy at the surface of the intermediate layer on the temporary support side that is exposed when the temporary support is peeled off during the temporary support peeling process (the surface of the intermediate layer that is exposed after the temporary support is peeled off). Surface free energy E I The upper limit is 68.0 mJ / m 2 The following is the case, and the effect of the present invention is superior at 65.0 mJ / m 2 The following is preferable: 63.0 mJ / m 2 The following is more preferable: 60.0 mJ / m 2 The following is even more preferable. Furthermore, a lower limit of, for example, 45.0 mJ / m³ is also preferable. 2 The above is preferable, with a concentration of 50.0 mJ / m 2 The above is more preferable, 55.0 mJ / m 2 The above is even more preferable. In this specification, the surface free energy E of the surface on the temporary support side of the intermediate layer I It is calculated using the following method.

[0036] (Methods for measuring and calculating surface energy) The surface energy is measured at the contact angle θ between pure water H2O and methylene iodide CH2I2. H2O and θ CH2I2 The surface energy is determined using the following Owens equations (simultaneous equations (A) and (B)). Note that there are no particular restrictions on the support removal method or the type of substrate used in the following surface energy measurement.

[0037] (contact angle of water (θ) H2O )) First, the contact angle of water (θ H2O ) is measured by the following method. After laminating the transfer film onto the substrate, the temporary support is peeled off. Next, under conditions of 25°C room temperature and 50% relative humidity, 12 μL of pure water is dropped onto the temporary support side of the intermediate layer (the side exposed after the temporary support is removed). After 20 seconds, the contact angle is measured using a CA-D type contact angle meter (Kyowa Interface Science Co., Ltd.). The above measurement is performed a total of 5 times. Then, the arithmetic mean of the three measurements excluding the maximum and minimum values ​​out of the five measurements is used to determine the water contact angle (θ). H2O )

[0038] (Contact angle of diiodomethane (θ) CH2I2 )) Next, the contact angle (θ) of diiodomethane. CH2I2 ) is measured by the following method. After laminating the transfer film onto the substrate, the temporary support is peeled off. Next, under conditions of 25°C room temperature and 50% relative humidity, 12 μL of diiodomethane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) is dropped onto the temporary support side of the intermediate layer (the side exposed after the temporary support is removed). After 20 seconds, the contact angle is measured using a CA-D type contact angle meter (Kyowa Interface Science Co., Ltd.). The above measurement is performed a total of 5 times. Then, the arithmetic mean of the three measurements excluding the maximum and minimum values ​​out of the five measurements is used to determine the contact angle of diiodomethane (θ). CH2I2 )

[0039] (Calculation of surface energy based on Owens' equation) θ measured by the method described above H2O and θ CH2I2 The value of each of the following and the value of γ shown in Table 1 below are substituted into the following simultaneous equations (A) and (B) to obtain "γs d +γs h The value of "" is defined as the surface energy. Note that in the table below, if L is H2O, for example, γ L d is γ H2O d It is expressed as follows. Also, if L is CH2I2, for example, γ L d is γ CH2I2 d It is represented as follows.

[0040] [Table 1]

[0041] [Simultaneous equations] (A): 1 + cosθ H2O =2√γ S d (√γ H2O d / γ H2O,V ) + 2√γ S h (√γ H2O h / γ H2O,V ) (B): 1 + cosθ CH2I2 =2√γ S d (√γ CH2I2 d / γ CH2I2,V ) + 2√γ S h (√γ CH2I2 h / γ CH2I2,V )

[0042] <Arithmetic mean roughness Ra of the surface on the temporary support side of the intermediate layer> The arithmetic mean roughness Ra of the surface on the temporary support side of the intermediate layer refers to the arithmetic mean roughness Ra of the surface on the temporary support side of the intermediate layer that is exposed when the temporary support is peeled off during the temporary support peeling process (the surface in the intermediate layer that is exposed after the temporary support is peeled off). The upper limit of the arithmetic mean roughness Ra of the surface on the temporary support side of the intermediate layer is preferably 50 nm or less, more preferably 30 nm or less, and even more preferably 20 nm or less, in terms of achieving superior effects of the present invention. The lower limit is preferably, for example, 0 nm or more, and more preferably 1 nm or more. In this specification, the arithmetic mean roughness Ra of the surface on the temporary support side of the intermediate layer is a value measured by the following method.

[0043] The arithmetic mean roughness Ra of the surface on the temporary support side of the intermediate layer is measured by the following method. A 3D optical profiler (New View7300, Zygo) is used to obtain the surface profile of the object to be measured under the following conditions. The measurement and analysis software used is the Microscope Application of MetroPro ver8.3.2. Next, the Surface Map screen is displayed using the above software, and histogram data is obtained on the Surface Map screen. From the obtained histogram data, the arithmetic mean roughness Ra of the surface of the object to be measured is obtained.

[0044] <Thickness of the intermediate layer> The thickness of the intermediate layer is not particularly limited, but its upper limit is preferably 10 μm or less, more preferably 5.0 μm or less, even more preferably 4.0 μm or less, and particularly preferably 3.0 μm or less, in terms of achieving superior effects of the present invention. Its lower limit is preferably 50 nm or more, and more preferably 100 nm or more, in terms of achieving superior oxygen permeability. The thickness of the intermediate layer is calculated as the average value of five arbitrary points measured by cross-sectional observation using a Scanning Electron Microscope (SEM).

[0045] <Surface free energy on the intermediate layer side of the temporary support> Surface free energy of the intermediate layer side of the temporary support (hereinafter referred to as "surface free energy E") S This term is also called ). ) refers to the surface free energy of the intermediate layer side surface of the temporary support that is exposed when the temporary support is peeled off in the temporary support peeling process (the surface that is exposed in the temporary support after separation from the intermediate layer). Surface free energy E S For example, the upper limit could be 60.0 mJ / m 2 The following is preferable: 54.0 mJ / m 2 The following is more preferable: 50.0 mJ / m 2 The following is even more preferable. Furthermore, a lower limit of, for example, 20.0 mJ / m³ is also preferable. 2 The above is preferable, and the effect of the present invention is even better at 25.0 mJ / m2 The above is preferable. In this specification, the surface free energy E of the intermediate layer surface of the temporary support S This is the surface free energy E of the surface on the temporary support side of the intermediate layer mentioned above. I This value can be obtained using the same method as before.

[0046] Note that the surface free energy E I and surface free energy E S It is also preferable that the following relationships (1) and / or (2) are satisfied. (1) Surface free energy E I (mJ / m 2 )>Surface free energy E S (mJ / m 2 ) (2) Surface free energy E I (mJ / m 2 ) and surface free energy E S (mJ / m 2 The difference between ) is 3.0~40 mJ / m 2 (Preferably 3.0 to 30 mJ / m 2 )

[0047] <<Pattern Forming Process>> The pattern formation process involves bringing the exposed intermediate layer into contact with a mask, performing an exposure process, and then performing a development process to form a pattern.

[0048] <Exposure process> The exposure process involves peeling off the temporary support to expose the intermediate layer of a laminate, and then applying a pattern to the photosensitive layer. "Pattern exposure" refers to a form of exposure that involves exposure in a patterned manner, that is, an exposure method in which exposed and unexposed areas exist. The positional relationship between the exposed and unexposed areas in pattern exposure is not particularly restricted and can be adjusted as appropriate. In the exposure process, a mask having openings at predetermined positions is placed in close contact with the intermediate layer exposed by peeling off the temporary support, and the exposure process is carried out. For example, if the photosensitive layer is a negative-type photosensitive layer, performing the above exposure treatment may cause a hardening reaction of the components contained in the photosensitive layer in the exposed areas of the photosensitive layer (positions corresponding to the openings of the mask). After the exposure treatment, a development treatment (especially alkaline development treatment) is performed to remove the unexposed areas of the photosensitive layer and form a pattern.

[0049] Furthermore, if the photosensitive layer is a negative-type photosensitive layer, the light source for pattern exposure can be appropriately selected and used as long as it can irradiate light in a wavelength range that can cure the photosensitive layer (for example, 365 nm or 405 nm). In particular, the dominant wavelength of the exposure light for pattern exposure is preferably 365 nm. The dominant wavelength is the wavelength with the highest intensity. Examples of light sources include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps. The exposure dose is 5-200 mJ / cm². 2 Preferably, 10-200 mJ / cm² 2 This is preferable.

[0050] Preferred embodiments of the light source, exposure amount, and exposure method used for exposure are described, for example, in paragraphs

[0146] to

[0147] of International Publication No. 2018 / 155193, and these are incorporated herein by reference.

[0051] In the first embodiment of the method for manufacturing the laminate, it is preferable to remove the mask (photomask) used in the exposure treatment after the exposure treatment but before the development treatment.

[0052] <Development process> The developing process involves developing the photosensitive layer that has been exposed in a patterned manner, as obtained through the exposure process, to form a pattern. The above-mentioned photosensitive layer can be developed using a developing solution. For example, if the photosensitive layer is a negative-type photosensitive layer, developing with an alkaline developing solution removes the unexposed areas of the photosensitive layer, and as a result, a pattern can be formed in which the openings of the mask are convex.

[0053] In the developing process, an alkaline aqueous solution is preferred as the developer. Examples of alkaline compounds that may be included in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0054] Examples of development methods include paddle development, shower development, spin development, and dip development.

[0055] Examples of developers preferred in this specification include the developer described in paragraph

[0194] of International Publication No. 2015 / 093271, and examples of development methods preferred in this specification include the development method described in paragraph

[0195] of International Publication No. 2015 / 093271.

[0056] <<Post-exposure and post-bake processes>> The first embodiment of the method for manufacturing the laminate may include a step of exposing the pattern obtained by the development process (post-exposure step) and / or a step of heating it (post-bake step). If the process includes both a post-exposure step and a post-bake step, it is preferable to perform the post-bake step after the post-exposure step. The post-exposure exposure dose is 100-5000 mJ / cm². 2 Preferably, 200-3000 mJ / cm² 2 This is preferable. The post-bake temperature is preferably 80 to 250°C, and more preferably 90 to 160°C. The post-bake time is preferably 1 to 180 minutes, and more preferably 10 to 60 minutes.

[0057] The position and size of the pattern formed on the substrate by the procedure described above are not particularly limited. The pattern is preferably in the form of a fine line, and its width is preferably 20 μm or less, and more preferably 15 μm or less. There is no particular lower limit, but for example, it is preferably 1 μm or more, and 5 μm or more.

[0058] <Transfer Film X> Next, I will explain the transfer film X. The transfer film X comprises a temporary support, an intermediate layer, and a photosensitive layer, and the surface free energy of the surface of the intermediate layer on the temporary support side is 68.0 mJ / m². 2 Any transfer film that meets the following criteria is not particularly limited, and any known transfer film can be used. The following describes embodiments of the transfer film X.

[0059] The composition of the transfer film X is not particularly limited, and examples include the following: (1) "Temporary support / intermediate layer / photosensitive layer / protective film" (2) "Temporary support / intermediate layer / photosensitive layer / refractive index adjusting layer / protective film" In each of the above configurations, the photosensitive layer is preferably a negative-type photosensitive layer. It is also preferable that the photosensitive layer is a colored resin layer. Furthermore, the transfer film X described in (1) above may have two intermediate layers. Specifically, it may have the configuration of "temporary support / second intermediate layer / first intermediate layer / photosensitive layer / protective film". Furthermore, the patterns obtained by the manufacturing method of the laminate of the present invention can be applied to seed layer protection patterns in circuit wiring manufacturing methods and wiring protection film patterns in wiring protection film manufacturing methods, as described later. Therefore, the transfer film X may be an etching resist transfer film or a wiring protection film transfer film. When the transfer film X is an etching resist transfer film, the configuration of the transfer film X is preferably, for example, the configuration of (1) described above. When the transfer film X is a wiring protection film transfer film, the configuration of the transfer film X is preferably, for example, the configuration of (1) or (2) described above.

[0060] From the viewpoint of suppressing bubble generation in the lamination process in the above-described method for manufacturing the laminate, the maximum width of the waviness of the transfer film X 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 is 0 μm or more, preferably 0.1 μm or more, and more preferably 1 μm or more. The maximum width of the waviness of transfer film X is the value measured by the following procedure. First, a test sample is prepared by cutting the transfer film X to a size of 20 cm x 20 cm perpendicular to the main surface. If the transfer film X has a protective film, the protective film is removed. Next, the test sample is placed on a smooth and horizontal stage with the surface of the temporary support facing the stage. After placement, a 3D surface image is obtained by scanning the surface of the sample sample within a 10 cm square area in the center of the sample using a laser microscope (e.g., VK-9700SP manufactured by Keyence Corporation), and the minimum concave height is subtracted from the maximum convex height observed in the obtained 3D surface image. The above operation is performed for 10 test samples, and the arithmetic mean is defined as the "maximum waviness width of the transfer film X".

[0061] In the following, we will first describe the intermediate layer and the temporary support, and then describe the overall structure of the transfer film X with an example of a specific embodiment. Note that the transfer film X1 of the first embodiment described later as a specific embodiment of the transfer film X is a configuration that can be suitably used for a transfer film for an etching resist, and the transfer film X2 of the second embodiment is a configuration that can be suitably used for a transfer film for a wiring protective film.

[0062] (Intermediate layer) The intermediate layer of the transfer film X has a surface free energy (surface free energy E I ) of 68.0 mJ / m 2 or less. Note that the surface free energy E I intends the surface free energy on the surface of the intermediate layer on the temporary support side that is exposed by peeling off the temporary support from the transfer film X. The preferred embodiment and measurement method of the surface free energy E I are as described above.

[0063] In addition, as the upper limit value of the arithmetic mean roughness Ra of the surface of the intermediate layer of the transfer film X, 50 nm or less is preferable in terms of more excellent effects of the present invention. Note that the arithmetic mean roughness Ra of the surface of the intermediate layer on the temporary support side intends the arithmetic mean roughness Ra of the surface of the intermediate layer that is exposed by peeling off the temporary support from the transfer film X. The preferred embodiment and measurement method of the arithmetic mean roughness Ra of the surface of the intermediate layer are as described above.

[0064] In addition, as the upper limit value of the thickness of the intermediate layer of the transfer film X, 10 μm or less is preferable in terms of more excellent effects of the present invention. The preferred embodiment and measurement method of the thickness of the intermediate layer are as described above.

[0065] The intermediate layer is preferably a water-soluble resin layer containing a water-soluble resin. Furthermore, it is preferable that the intermediate layer has oxygen-blocking properties. Having oxygen-blocking properties in the intermediate layer improves sensitivity during exposure, reduces the time load on the exposure machine, and improves productivity, which is therefore preferable. In addition, if the photosensitive layer in the transfer film X is a negative-type photosensitive layer containing a radical polymerizable compound, there is the advantage that oxygen inhibition is less likely to occur in the polymerization reaction during exposure. The intermediate layer is preferably one 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).

[0066] The intermediate layer preferably contains a resin. The above resin preferably contains a water-soluble resin as part or all of it. Examples of resins that can be used as water-soluble resins include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins (e.g., water-soluble cellulose derivatives such as hydroxypropyl cellulose and hydroxypropyl methylcellulose), acrylamide-based resins, polyether-based resins (e.g., polyalkylene oxide-based resins such as polyethylene glycol and polypropylene glycol), gelatin, vinyl ether-based resins, polyamide resins, and copolymers thereof. Furthermore, as the water-soluble resin, copolymers of (meth)acrylic acid / vinyl compounds can also be used. As the copolymer of (meth)acrylic acid / vinyl compounds, copolymers of (meth)acrylic acid / (meth)acrylate are preferred, and copolymers of methacrylic acid / methacrylate are more preferred. When the water-soluble resin is a copolymer of (meth)acrylic acid / vinyl compounds, the composition ratio (mol%) is preferably, for example, 90 / 10~20 / 80, and more preferably 80 / 20~30 / 70.

[0067] The lower limit of the weight-average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and even more preferably 10,000 or more. The upper limit is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less. The dispersion degree (Mw / Mn) of the water-soluble resin is preferably 1 to 10, and more preferably 1 to 5.

[0068] As for the water-soluble resin, it is preferable to include one or more of polyvinyl alcohol and polyvinylpyrrolidone, more preferably polyvinyl alcohol, and even more preferably both polyvinyl alcohol and polyvinylpyrrolidone, in terms of having superior effects and / or superior oxygen barrier ability. Furthermore, it is preferable to use one or more of polyvinyl alcohol and polyvinylpyrrolidone in combination with one or more of water-soluble cellulose derivatives and polyethers, and it is even more preferable to use one or more of polyvinyl alcohol and polyvinylpyrrolidone in combination with water-soluble cellulose derivatives.

[0069] The water-soluble cellulose derivative is not particularly limited, but examples include hydroxyethylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, methylcellulose, and ethylcellulose. Examples of polyethers include polyethylene glycol and polypropylene glycol.

[0070] Water-soluble resins may be used individually or in combination of two or more types. The content of the water-soluble resin is not particularly limited, but in terms of achieving superior effects of the present invention and / or superior oxygen barrier ability, it is preferably 50% by mass or more, and more preferably 70% by mass or more, relative to the total mass of the intermediate layer. There is no particular upper limit, but for example, it is 100% by mass or less, preferably 99.9% by mass or less, more preferably 99.8% by mass or less, and even more preferably 99% by mass or less.

[0071] Furthermore, the intermediate layer may contain components other than the resin mentioned above. The molecular weight of the other components mentioned above is not particularly limited, but is preferably less than 5,000, more preferably 4,000 or less, even more preferably 3,000 or less, even more preferably 2,000 or less, and particularly preferably 1,500 or less. The lower limit is, for example, 60 or more.

[0072] Among the other components mentioned above, in particular, the surface free energy E on the temporary support side of the intermediate layer. I Polyhydric alcohols, alkylene oxide adducts of polyhydric alcohols, phenol derivatives, or amide compounds are preferred because they are easy to adjust, and polyhydric alcohols or phenol derivatives are more preferred. The number of hydroxyl groups contained in the polyhydric alcohols is not particularly limited; for example, 2 to 10 groups are preferred. Examples of polyhydric alcohols include glycerin, diglycerin, and diethylene glycol. Examples of alkylene oxide adducts of polyhydric alcohols include compounds obtained by adding ethylene oxide and propylene oxide to the aforementioned polyhydric alcohols. The average number of additions is not particularly limited, for example, 1 to 100, preferably 2 to 50, and more preferably 2 to 20. Examples of phenol derivatives include bisphenol A and bisphenol S. Examples of amide compounds include N-methylpyrrolidone.

[0073] If the intermediate layer contains the above-mentioned other components, these other components may be used individually or in combination of two or more types. The content of the other components mentioned above is not particularly limited, but in terms of achieving superior effects of the present invention, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, relative to the total mass of the intermediate layer. There is no particular upper limit, but for example, it is preferably less than 30% by mass, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0074] As for the intermediate layer, it is preferable that it contains one or more of polyvinyl alcohol and polyvinylpyrrolidone, and compound X selected from the group consisting of water-soluble cellulose derivatives, polyethers, phenol derivatives, and glycerin, in terms of having superior effects of the present invention and / or superior oxygen barrier ability. When the intermediate layer has the above composition, compound X tends to be more unevenly distributed on the surface of the intermediate layer on the temporary support side, and / or a weak boundary layer (WBL) is less likely to be formed by mixing the intermediate layer and the photosensitive layer, and the surface free energy E on the temporary support side of the intermediate layer I Furthermore, the arithmetic mean roughness Ra on the same surface can be more easily adjusted to a more appropriate value. Surface free energy E on the temporary support side of the intermediate layer I Furthermore, when the arithmetic mean roughness Ra on the surface is adjusted to a more appropriate value, delamination at the interface between the temporary support and the intermediate layer becomes easier during the delamination of the temporary support without causing cohesive failure of the intermediate layer, and a pattern with excellent resolution is more easily formed. The composition of the intermediate layer is more preferably to include one or more of polyvinyl alcohol and polyvinylpyrrolidone, and one or more of water-soluble cellulose derivatives and polyethers as compound X. It is even more preferably to include one or more of polyvinyl alcohol and polyvinylpyrrolidone, and a water-soluble cellulose derivative as compound X, as it is easier to suppress plasticization of the intermediate layer. It is particularly preferably to include one or more of polyvinyl alcohol and polyvinylpyrrolidone, and hydroxypropyl methylcellulose as compound X, as it is easier to peel off the temporary support. Furthermore, it is preferable to use polyvinyl alcohol and polyvinylpyrrolidone in combination. When the intermediate layer has the above composition, the total content of polyvinyl alcohol and polyvinylpyrrolidone is preferably 50% by mass or more, and more preferably 70% by mass or more, relative to the total mass of the intermediate layer, in terms of achieving superior effects of the present invention. There is no particular upper limit, but for example, it is 100% by mass or less, preferably 99.9% by mass or less, more preferably 99.8% by mass or less, and even more preferably 99% by mass or less. Furthermore, when the intermediate layer has the above composition, the polyvinyl alcohol content is preferably 5 to 95% by mass relative to the total mass of the intermediate layer. Furthermore, when the intermediate layer has the above composition, the mixing ratio (mass ratio) of polyvinyl alcohol to polyvinylpyrrolidone is preferably 5 / 95 to 95 / 5, more preferably 20 / 80 to 80 / 20, even more preferably 25 / 75 to 70 / 25, and particularly preferably 60 / 40 to 75 / 25. Furthermore, when the intermediate layer has the above composition, the content of compound X is not particularly limited, but in terms of achieving superior effects of the present invention, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, relative to the total mass of the intermediate layer. As an upper limit, it is preferably less than 30% by mass, and more preferably 15% by mass or less. When the content of compound X is less than 30% by mass relative to the total mass of the intermediate layer, phase separation of the intermediate layer forming components is easily suppressed, and surface roughening of the intermediate layer caused by this is less likely to occur, resulting in superior resolution.

[0075] (Temporary support) The transfer film X has a temporary support. The temporary support is a component that supports the photosensitive layer and is ultimately removed by a peeling process.

[0076] The temporary support structure may be single-layered or multi-layered. The temporary support is preferably a film, and more preferably a resin film. The temporary support is preferably a film that is flexible and does not undergo significant deformation, shrinkage, or elongation under pressure, or under pressure and heat. Examples of the above-mentioned films include polyethylene terephthalate film (e.g., biaxially oriented polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film. Among these, polyethylene terephthalate film is preferred as a temporary support. In addition, the film used as the temporary support preferably has no deformation such as wrinkles and no scratches or the like.

[0077] From the viewpoint that the pattern can be exposed by pattern exposure through the temporary support, the temporary support preferably has high transparency. The transmittance at 365 nm is preferably 60% or more, more preferably 70% or more. From the viewpoints of pattern formation properties during pattern exposure through the temporary support and the transparency of the temporary support, the haze of the temporary support is preferably small. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and still more preferably 0.1% or less. From the viewpoints of pattern formation properties during pattern exposure through the temporary support and the transparency of the temporary support, the number of fine particles, foreign matters, and defects contained in the temporary support is preferably small. The number of fine particles, foreign matters, and defects having a diameter of 1 μm or more in the temporary support is preferably 50 pieces / 10 mm 2 or less, more preferably 10 pieces / 10 mm 2 or less, still more preferably 3 pieces / 10 mm 2 or less, and particularly preferably 0 pieces / 10 mm 2 is particularly preferred.

[0078] The thickness of the temporary support is not particularly limited, but is preferably 5 to 200 μm, more preferably 5 to 150 μm, still more preferably 5 to 50 μm, and most preferably 5 to 25 μm, from the viewpoints of ease of handling and versatility. The thickness of the temporary support is calculated as the average value of any five points measured by cross-sectional observation using a SEM (Scanning Electron Microscope).

[0079] Examples of the temporary support include a biaxially stretched polyethylene terephthalate film with a film thickness of 16 μm, a biaxially stretched polyethylene terephthalate film with a film thickness of 12 μm, and a biaxially stretched polyethylene terephthalate film with a film thickness of 9 μm.

[0080] Preferred forms of the temporary support are described, for example, in paragraphs

[0017] to

[0018] of Japanese Patent Publication No. 2014-085643, paragraphs

[0019] to

[0026] of Japanese Patent Publication No. 2016-027363, paragraphs

[0041] to

[0057] of International Publication No. 2012 / 081680, and paragraphs

[0029] to

[0040] of International Publication No. 2018 / 179370, the contents of which are incorporated herein by reference.

[0081] To improve handling, a layer containing fine particles (a lubricant layer) may be provided on the surface of the temporary support. The lubricant layer may be provided on one side of the temporary support or on both sides. The diameter of the particles contained in the lubricant layer is preferably 0.05 to 0.8 μm. Furthermore, the thickness of the lubricant layer is preferably 0.05 to 1.0 μm.

[0082] Surface free energy (Surface free energy E) of the intermediate layer surface of the temporary support S ) is 60.0 mJ / m 2 The following are preferable. Note that the surface free energy E S This refers to the surface free energy at the surface of the intermediate layer side of the temporary support that is exposed when the temporary support is peeled off from the transfer film X. Surface free energy E S Preferred embodiments and measurement methods are as previously described.

[0083] Commercially available temporary supports include Lumirror 16KS40 and Lumirror 16FB40 (both manufactured by Toray Industries, Inc.), and Cosmoshine A4100, Cosmoshine A4300, and Cosmoshine A8300 (all manufactured by Toyobo Co., Ltd.).

[0084] (Overall composition of transfer film X) Next, the overall configuration of the transfer film X will be described with reference to an example of a specific embodiment. As mentioned above, the transfer film X1 of the first embodiment has a configuration that is suitably usable as a transfer film for etching resist, and the transfer film X2 of the second embodiment has a configuration that is suitably usable as a transfer film for wiring protection film. The thickness of the photosensitive layer is not particularly limited, but is often 30 μm or less. However, in terms of achieving superior effects of the present invention, a thickness of 20 μm or less is preferred, 15 μm or less is more preferred, 10 μm or less is even more preferred, and 5.0 μm or less is particularly preferred. As a lower limit, in terms of achieving superior strength in the film obtained by curing the photosensitive layer, a thickness of 0.60 μm or more is preferred, 1.5 μm or more is more preferred, and 2.0 μm or more is even more preferred. The thickness of the photosensitive layer is calculated as the average value of five arbitrary points measured by cross-sectional observation using a Scanning Electron Microscope (SEM).

[0085] • Transfer film X1 of the first embodiment An example of an embodiment of the transfer film X1 of the first embodiment will be described below. The transfer film 10 shown in Figure 1 comprises, in this order, a temporary support 1, a composition layer 7 including an intermediate layer 3 and a photosensitive layer 5, and a protective film 9. Although the transfer film 10 shown in Figure 1 has a protective film 9 placed on it, the protective film 9 does not necessarily have to be placed on it. In Figure 1, each layer except for the protective film 9 that can be placed on the temporary support 1 is referred to as a composition layer 7. The following describes each element that constitutes the transfer film X1. The components of the intermediate layer and temporary support that make up the transfer film X1 are as previously described.

[0086] ·Photosensitive layer After transferring the photosensitive layer onto the transfer target, a pattern can be formed on the transfer target by exposure and development. The photosensitive layer is preferably a negative-type photosensitive layer. A negative-type photosensitive layer is a photosensitive layer in which the exposed area becomes less soluble in the developer solution upon exposure. When the photosensitive layer is a negative-type photosensitive layer, the pattern formed corresponds to the cured layer.

[0087] When the photosensitive layer is a negative-type photosensitive layer, it is preferable that the negative-type photosensitive layer contains a resin, a polymerizable compound, and a polymerization initiator. Furthermore, when the photosensitive layer is a negative-type photosensitive layer, it is also preferable that part or all of the resin contains an alkali-soluble resin (such as polymer A, which is an alkali-soluble resin), as described below. In other words, in one embodiment, it is preferable that the photosensitive layer contains a resin including an alkali-soluble resin, a polymerizable compound, and a polymerization initiator. Such a photosensitive layer (negative-type photosensitive layer) preferably contains, based on the total mass of the photosensitive layer, 10-90% by mass of resin; 5-70% by mass of polymerizable compound; and 0.01-20% by mass of polymerization initiator. The following will explain each component in order.

[0088] ...Polymer A (resin) When the photosensitive layer is a negative-type photosensitive layer, the resin contained in the photosensitive layer is also specifically called polymer A. Polymer A is preferably an alkali-soluble resin. From the viewpoint of achieving superior resolution by suppressing swelling of the negative-type photosensitive layer due to the developer, the acid value of polymer A is preferably 220 mg KOH / g or less, more preferably less than 200 mg KOH / g, and even more preferably less than 190 mg KOH / g. The lower limit of the acid value of polymer A is not particularly limited, but from the viewpoint of superior developability, it is preferably 60 mg KOH / g or higher, more preferably 120 mg KOH / g or higher, even more preferably 150 mg KOH / g or higher, and particularly preferably 170 mg KOH / g or higher.

[0089] The acid value (mgKOH / g) is the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample. The acid value can be determined, for example, according to the method described in JIS K0070:1992. The acid value of polymer A can be adjusted by the types of constituent units that make up polymer A and the content of constituent units that contain acid groups.

[0090] 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 from the viewpoint of improving resolution and developability. A weight-average molecular weight of 100,000 or less is more preferred, and 60,000 or less is even more preferred. On the other hand, a weight-average molecular weight of 5,000 or more is preferred from the viewpoint of controlling the properties of the developed aggregates and the properties of the unexposed film, such as edge fusing and cut-tip properties, when used as a negative-type photosensitive resin laminate. A weight-average molecular weight of 10,000 or more is more preferred, 20,000 or more is even more preferred, and 30,000 or more is particularly preferred. Edge fusing refers to the degree to which the negative-type photosensitive layer tends to protrude from the end face of the roll when the negative-type photosensitive resin laminate is wound into a roll. Cut-tip properties refer to the degree to which the chip tends to fly off when the unexposed film is cut with a cutter. If this chip adheres to the upper surface of a negative-type photosensitive resin laminate, it will be transferred to the mask during subsequent exposure processes, causing defective products. The degree of dispersion of polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0. In this disclosure, the degree of dispersion is the ratio of the weight-average molecular weight to the number-average molecular weight (weight-average molecular weight / number-average molecular weight). In this disclosure, the weight-average molecular weight and the number-average molecular weight are values ​​measured using gel permeation chromatography.

[0091] In the negative-type photosensitive layer, from the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position shifts during exposure, it is preferable that polymer A contains structural units based on monomers having aromatic hydrocarbon groups. Examples of such aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The content of structural units based on monomers having aromatic hydrocarbon groups in polymer A is preferably 20% by mass or more, and more preferably 30% by mass or more, based on the total mass of polymer A. There is no particular upper limit, but it is preferably 95% by mass or less, and more preferably 85% by mass or less. When polymer A contains multiple types, it is preferable that the average value of the content of structural units based on monomers having aromatic hydrocarbon groups is within the above range.

[0092] Examples of monomers having aromatic hydrocarbon groups include monomers having aralkyl groups, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer). Among these, monomers having aralkyl groups or styrene are preferred. In one embodiment, when the monomer component having aromatic hydrocarbon groups in polymer A is styrene, the content of styrene-based structural units is preferably 20 to 70% by mass, more preferably 25 to 65% by mass, even more preferably 30 to 60% by mass, and particularly preferably 30 to 55% by mass, based on the total mass of polymer A. When the photosensitive layer contains multiple types of polymer A, the content of structural units having aromatic hydrocarbon groups is determined as a weight average.

[0093] Examples of aralkyl groups include substituted or unsubstituted phenylalkyl groups (excluding benzyl groups) and substituted or unsubstituted benzyl groups, with substituted or unsubstituted benzyl groups being preferred.

[0094] Examples of monomers having a phenylalkyl group include phenylethyl (meth)acrylate.

[0095] Examples of monomers having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; and vinyl monomers having a benzyl group, such as vinylbenzyl chloride and vinylbenzyl alcohol. Among these, benzyl (meth)acrylate is preferred. In one embodiment, when the monomer component having an aromatic hydrocarbon group in polymer A is benzyl (meth)acrylate, the content of the constituent units based on benzyl (meth)acrylate is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, even more preferably 70 to 90% by mass, and particularly preferably 75 to 90% by mass, based on the total mass of polymer A.

[0096] Polymer A, which includes a constituent unit based on a monomer having an aromatic hydrocarbon group, is preferably obtained by polymerizing the monomer having an aromatic hydrocarbon group with at least one of the first monomers described later and / or at least one of the second monomers described later.

[0097] Polymer A, which does not contain constituent units based on monomers having aromatic hydrocarbon groups, is preferably obtained by polymerizing at least one of the first monomers described later, and more preferably by copolymerizing at least one of the first monomers with at least one of the second monomers described later.

[0098] The first monomer is a monomer having a carboxyl group in its molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid semi-ester. Among these, (meth)acrylic acid is preferred. The content of the constituent units based on the first monomer in polymer A is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 30% by mass, relative to the total mass of polymer A. Setting the above content to 5% by mass or more is preferable from the viewpoint of achieving good developability and controlling edge fusing. Setting the above content to 50% by mass or less is preferable from the viewpoint of high resolution and tail shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern.

[0099] The second monomer is non-acidic and has at least one polymerizable unsaturated group in its molecule. Examples of the second monomer include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; esters of vinyl alcohols such as vinyl acetate; and (meth)acrylonitrile. Among these, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or n-butyl (meth)acrylate are preferred, and methyl (meth)acrylate is more preferred. The content of the constituent units based on the second monomer in polymer A is preferably 5 to 60% by mass, more preferably 15 to 50% by mass, and even more preferably 17 to 45% by mass, relative to the total mass of polymer A.

[0100] When polymer A contains constituent units based on monomers having aralkyl groups and / or constituent units based on styrene monomers, it is preferable from the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position shifts during exposure. For example, copolymers containing constituent units based on methacrylic acid, benzyl methacrylate, and styrene, and copolymers containing constituent units based on methacrylic acid, methyl methacrylate, benzyl methacrylate, and styrene are preferred. In one embodiment, polymer A is preferably a polymer containing 25-55% by mass of constituent units based on monomers having aromatic hydrocarbon groups, 20-35% by mass of constituent units based on a first monomer, and 15-45% by mass of constituent units based on a second monomer. In another embodiment, polymer is preferably a polymer containing 70-90% by mass of constituent units based on monomers having aromatic hydrocarbon groups and 10-25% by mass of constituent units based on a first monomer.

[0101] Polymer A may have a linear, branched, or alicyclic structure in its side chains. Branched or alicyclic structures can be introduced into the side chains of polymer A by using monomers containing a group with a branched structure in the side chain, or monomers containing a group with an alicyclic structure in the side chain. The group with the alicyclic structure may be monocyclic or polycyclic. Specific examples of monomers containing a group having a branched structure in its side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, tert-amyl (meth)acrylate, sec-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and tert-octyl (meth)acrylate. Among these, isopropyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl methacrylate are preferred, and isopropyl methacrylate or tert-butyl methacrylate are more preferred. Specific examples of monomers containing a group with an alicyclic structure in its side chain include monomers having a monocyclic aliphatic hydrocarbon group and monomers having a polycyclic aliphatic hydrocarbon group. Also, (meth)acrylates having an alicyclic hydrocarbon group with 5 to 20 carbon atoms are examples. More specific examples include (meth)acrylic acid (bicyclo[2.2.1]heptyl-2), (meth)acrylic acid-1-adamantyl, (meth)acrylic acid-2-adamantyl, (meth)acrylic acid-3-methyl-1-adamantyl, (meth)acrylic acid-3,5-dimethyl-1-adamantyl, (meth)acrylic acid-3-ethyladamantyl, (meth)acrylic acid-3-methyl-5-ethyl-1-adamantyl, (meth)acrylic acid-3,5,8-triethyl-1-adamantyl, (meth)acrylic acid-3,5-dimethyl-8-ethyl-1-adamantyl, (meth)acrylic acid-2-methyl-2-adamantyl, (meth)acrylic acid-2-ethyl-2-adamantyl, (meth)acrylic acid-3-hydroxy Examples include C-1-adamantyl, octahydro-4,7-menthanoinden-5-yl (meth)acrylate, octahydro-4,7-menthanoinden-1-ylmethyl (meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl (meth)acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fentyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, and cyclohexyl (meth)acrylate.Among these (meth)acrylic acid esters, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fentyl (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecane (meth)acrylate are preferred, and cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate are more preferred.

[0102] Polymer A may be used alone or in combination of two or more types. When using two or more types, it is preferable to use a mixture of two types of polymer A containing constituent units based on monomers having aromatic hydrocarbon groups, or to use a mixture of polymer A containing constituent units based on monomers having aromatic hydrocarbon groups and polymer A not containing constituent units based on monomers having aromatic hydrocarbon groups. In the latter case, the proportion of polymer A containing constituent units based on monomers having aromatic hydrocarbon groups used is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, and more preferably 90% by mass or more, based on the total mass of polymer A.

[0103] The synthesis of polymer A is preferably carried out by adding appropriate amounts of benzoyl peroxide and a radical polymerization initiator such as azoisobutyronitrile to a solution obtained by diluting one or more of the above-mentioned monomers with a solvent such as acetone, methyl ethyl ketone, and isopropanol, and then heating and stirring. In some cases, the synthesis may be carried out by adding a portion of the mixture dropwise to the reaction solution. After the reaction is complete, the solvent may be further added to adjust the concentration to the desired level. In addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may also be used as synthesis methods.

[0104] The glass transition temperature (Tg) of polymer A is preferably 30 to 135°C. By using polymer A having a Tg of 135°C or lower, line width thickening and deterioration of resolution when the focal position shifts during exposure can be suppressed. From this viewpoint, the Tg of polymer A is more preferably 130°C or lower, even more preferably 120°C or lower, and particularly preferably 110°C or lower. Furthermore, using polymer A having a Tg of 30°C or higher is preferable from the viewpoint of improving edge fusing resistance. From this viewpoint, the Tg of polymer A is more preferably 40°C or higher, even more preferably 50°C or higher, particularly preferably 60°C or higher, and most preferably 70°C or higher.

[0105] The negative-type photosensitive layer may also contain other resins as polymer A, in addition to those mentioned above. Other resins include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0106] As polymer A, an alkali-soluble resin, as described in the later section on thermoplastic resin layers, may be used.

[0107] The content of polymer A is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, even more preferably 30 to 70% by mass, and particularly preferably 40 to 60% by mass, based on the total mass of the negative-type photosensitive layer. A polymer A content of 90% by mass or less is preferable from the viewpoint of controlling the development time. On the other hand, a polymer A content of 10% by mass or more is preferable from the viewpoint of improving edge fusing resistance.

[0108] ...polymerizable compound If the photosensitive layer is a negative-type photosensitive layer, it is preferable that the negative-type photosensitive layer contains a polymerizable compound having polymerizable groups. In this specification, "polymerizable compound" means a compound that polymerizes under the action of a polymerization initiator described later, and is a compound different from polymer A described above.

[0109] The polymerizable groups in polymerizable compounds are not particularly limited as long as they are groups that participate in polymerization reactions. Examples include groups having ethylenically unsaturated groups such as vinyl groups, acryloyl groups, methacryloyl groups, styryl groups, and maleimide groups; and groups having cationic polymerizable groups such as epoxy groups and oxetane groups. The polymerizable group is preferably a group having an ethylenically unsaturated group, and more preferably an acryloyl group or a methacryloyl group.

[0110] As polymerizable compounds, compounds having one or more ethylenically unsaturated groups (ethylenically unsaturated compounds) are preferred in that they provide superior photosensitivity to the negative-type photosensitive layer, and compounds having two or more ethylenically unsaturated groups in one molecule (polyfunctional ethylenically unsaturated compounds) are more preferred. Furthermore, in terms of superior resolution and exfoliation properties, the number of ethylenically unsaturated groups in one molecule of an ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and even more preferably 2 or less.

[0111] In terms of achieving a better balance between the photosensitivity, resolution, and peelability of the negative-type photosensitive layer, it is preferable to include a difunctional or trifunctional ethylenically unsaturated compound having two or three ethylenically unsaturated groups in one molecule, and more preferably a difunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule. The content of the difunctional ethylenically unsaturated compound relative to the total mass of the polymerizable compound is preferably 20% by mass or more, more preferably over 40% by mass, and even more preferably 55% by mass or more, relative to the total mass of the negative-type photosensitive layer, from the viewpoint of excellent peelability. There is no particular upper limit, and it may be 100% by mass. That is, all of the polymerizable compounds may be difunctional ethylenically unsaturated compounds. Furthermore, as an ethylenically unsaturated compound, a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group is preferred.

[0112] ...Polymerizable compound B1 The negative-type photosensitive layer may also preferably contain polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups. Polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule, selected from the polymerizable compound B described above.

[0113] In the negative-type photosensitive layer, the mass ratio of polymerizable compound B1 to the total mass of polymerizable compounds is preferably 40% or more, more preferably 50% or more, even more preferably 55% or more, and particularly preferably 60% or more, from the viewpoint of superior resolution. There is no particular upper limit, but from the viewpoint of peelability, for example, it is 100% or less, preferably 99% or less, more preferably 95% or less, even more preferably 90% or less, and particularly preferably 85% or less.

[0114] Examples of aromatic rings in polymerizable compound B1 include aromatic hydrocarbon rings such as benzene rings, naphthalene rings, and anthracene rings; aromatic heterocycles such as thiophene rings, furan rings, pyrrole rings, imidazole rings, triazole rings, and pyridine rings; and fused rings thereof. Aromatic hydrocarbon rings are preferred, and benzene rings are more preferred. The above aromatic rings may have substituents. Polymerizable compound B1 may have only one aromatic ring, or it may have two or more aromatic rings.

[0115] Polymerizable compound B1 is preferably a bisphenol structure, as this improves resolution by suppressing swelling of the photosensitive layer due to the developing solution. Examples of bisphenol structures include the bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), the bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and the bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), with the bisphenol A structure being preferred.

[0116] Examples of polymerizable compounds B1 having a bisphenol structure include compounds having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. The two polymerizable groups at both ends of the bisphenol structure may be directly bonded, or they may be bonded via one or more alkylene oxy groups. The alkylene oxy groups added to both ends of the bisphenol structure are preferably ethylene oxy groups or propylene oxy groups, with ethylene oxy groups being more preferred. The number of alkylene oxy groups added to the bisphenol structure is not particularly limited, but 4 to 16 per molecule is preferred, and 6 to 14 are more preferred. Polymerizable compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of Japanese Patent Publication No. 2016-224162, and the contents described in this publication are incorporated herein by reference.

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

[0118] As polymerizable compound B1, compounds represented by the following general formula (B1) are also preferred.

[0119] [ka]

[0120] In general formula B1, R1 and R2 each independently represent a hydrogen atom or a methyl group. A represents C2H4. B represents C3H6. n1 and n3 are each independently integers from 1 to 39, and n1+n3 is an integer from 2 to 40. n2 and n4 are each independently integers from 0 to 29, and n2+n4 is an integer from 0 to 30. The arrangement of the constituent units of -(AO)- and -(BO)- may be random or in a block. In the case of a block, either -(AO)- or -(BO)- may be on the bisphenyl group side. In one embodiment, n1+n2+n3+n4 is preferably 2 to 20, more preferably 2 to 16, and even more preferably 4 to 12. Also, n2+n4 is preferably 0 to 10, more preferably 0 to 4, even more preferably 0 to 2, and particularly preferably 0.

[0121] Polymerizable compound B1 may be used alone or in combination of two or more types. From the viewpoint of achieving superior resolution, the content of polymerizable compound B1 is preferably 10% by mass or more, and more preferably 20% by mass or more, relative to the total mass of the negative-type photosensitive layer. There is no particular upper limit, but from the viewpoint of transferability and edge fusion (the phenomenon of photosensitive resin seeping out from the edges of the transfer material), it is preferably 70% by mass or less, and more preferably 60% by mass or less.

[0122] The negative-type photosensitive layer may contain polymerizable compounds other than the polymerizable compound B1 described above. Polymerizable compounds other than polymerizable compound B1 are not particularly limited and can be appropriately selected from known compounds. Examples include compounds having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compounds), difunctional ethylenically unsaturated compounds without aromatic rings, and trifunctional or more ethylenically unsaturated compounds.

[0123] 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.

[0124] Examples of bifunctional ethylenically unsaturated compounds that do not have an aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate. Examples of alkylene glycol di(meth)acrylates include tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), tricyclodecanedimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate. 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. Examples of urethane di(meth)acrylates include propylene oxide-modified urethane di(meth)acrylates and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates. Examples of commercially available products include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., Ltd.).

[0125] Examples of ethylenically unsaturated compounds with three or more functions include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide modified products thereof. Here, "(tri / tetra / penta / hexa)(meth)acrylate" is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, while "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate. In one embodiment, the negative photosensitive layer may also contain the polymerizable compound B1 described above and a trifunctional or greater ethylenically unsaturated compound, and more preferably, the polymerizable compound B1 described above and two or more trifunctional or greater ethylenically unsaturated compounds. In this case, the mass ratio of polymerizable compound B1 to trifunctional or greater ethylenically unsaturated compounds is preferably (total mass of polymerizable compound B1):(total mass of trifunctional or greater ethylenically unsaturated compounds) = 1:1 to 5:1, more preferably 1.2:1 to 4:1, and even more preferably 1.5:1 to 3:1. In one embodiment, the negative photosensitive layer preferably contains the polymerizable compound B1 described above and two or more trifunctional ethylenically unsaturated compounds.

[0126] Examples of alkylene oxide modified products of ethylenically unsaturated compounds with three or more functions include caprolactone-modified (meth)acrylate compounds (such as KAYARAD® DPCA-20 manufactured by Nippon Kayaku Co., Ltd. and A-9300-1CL manufactured by Shin Nakamura Chemical Industry Co., Ltd.), alkylene oxide-modified (meth)acrylate compounds (such as KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin Nakamura Chemical Industry Co., Ltd., and EBECRYL® 135 manufactured by Daicel Ornex Co., Ltd.), ethoxylated glycerin triacrylate (such as A-GLY-9E manufactured by Shin Nakamura Chemical Industry Co., Ltd.), Arronix® TO-2349 (manufactured by Toagosei Co., Ltd.), Arronix M-520 (manufactured by Toagosei Co., Ltd.), and Arronix M-510 (manufactured by Toagosei Co., Ltd.).

[0127] Furthermore, polymerizable compounds having an acidic group (such as a carboxyl group) may be used as the polymerizable compound. The above acidic group may form an acid anhydride group. Examples of polymerizable compounds having an acidic group include Arronix® TO-2349 (manufactured by Toagosei Co., Ltd.), Arronix® M-520 (manufactured by Toagosei Co., Ltd.), and Arronix® M-510 (manufactured by Toagosei Co., Ltd.). As a polymerizable compound having an acid group, for example, a polymerizable compound having an acid group described in paragraphs 0025 to 0030 of Japanese Patent Application Publication No. 2004-239942 may be used.

[0128] Polymerizable compounds may be used individually or in combination of two or more. The polymerizable compound content is preferably 10 to 70% by mass, more preferably 15 to 70% by mass, and even more preferably 20 to 70% by mass, relative to the total mass of the negative photosensitive layer.

[0129] The molecular weight (or weight-average molecular weight if a molecular weight distribution exists) of the polymerizable compound (including polymerizable compound B1) is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.

[0130] ...polymerization initiator If the photosensitive layer is a negative-type photosensitive layer, it is also preferable that the negative-type photosensitive layer contains a polymerization initiator. Polymerization initiators are selected according to the type of polymerization reaction, and examples include thermal polymerization initiators and photopolymerization initiators. The polymerization initiator may be either a radical polymerization initiator or a cationic polymerization initiator.

[0131] The negative-type photosensitive layer preferably contains a photopolymerization initiator. A photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound upon exposure to active light such as ultraviolet light, visible light, and X-rays. There are no particular limitations on the photopolymerization initiator; known photopolymerization initiators can be used. Examples of photopolymerization initiators include photoradical polymerization initiators and photocationic polymerization initiators, with photoradical polymerization initiators being preferred.

[0132] Examples of photo-radical polymerization initiators include photopolymerization initiators having an oxime ester structure, photopolymerization initiators having an α-aminoalkylphenone structure, photopolymerization initiators having an α-hydroxyalkylphenone structure, photopolymerization initiators having an acylphosphine oxide structure, and photopolymerization initiators having an N-phenylglycine structure.

[0133] Furthermore, the negative-type photosensitive layer preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and their derivatives as a photoradical polymerization initiator, from the viewpoint of photosensitivity, visibility of exposed and unexposed areas, and resolution. The two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different. Examples of derivatives of the 2,4,5-triarylimidazole dimer include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0134] As photoradical polymerization initiators, for example, polymerization initiators described in paragraphs 0031 to 0042 of Japanese Patent Publication No. 2011-95716 and paragraphs 0064 to 0081 of Japanese Patent Publication No. 2015-14783 may be used.

[0135] Examples of photoradical polymerization initiators include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (trade name: manufactured by Midori Chemical Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (trade name: manufactured by Midori Chemical Co., Ltd.), Irgacure OXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad 651 and 369 (trade name: manufactured by IGM Resins BV), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0136] Examples of commercially available photoradical polymerization initiators include 1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyl oxime) (trade name: IRGACURE® OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyl oxime) (trade name: IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), IRGACURE OXE-04 (manufactured by BASF), and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, IGM Resins). (Manufactured by 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), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (Trade name: Omnirad 369, manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropan-1-one (Trade name: Omnirad 1173, manufactured by IGM Resins BV), 1-hydroxycyclohexylphenyl ketone (Trade name: Omnirad 184, manufactured by IGM Resins BV) (Manufactured by BV), 2,2-dimethoxy-1,2-diphenylethane-1-one (Trade name: Omnirad 651, manufactured by IGM Resins BV), 2,4,6-trimethylbenzolyl-diphenylphosphine oxide (Trade name: Omnirad TPO H, manufactured by IGM Resins BV), bis(2,4,6-trimethylbenzolyl)phenylphosphine oxide (Trade name: Omnirad 819, manufactured by IGM Resins BV)(manufactured by DKSH Japan), oxime ester-based photopolymerization initiator (product name: Lunar 6, manufactured by DKSH Japan), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (product name: Omnirad 907FF, manufactured by IGM Resins BV), 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-butan-1-one (product name: Omnirad 379, manufactured by IGM Resins (Manufactured by BV), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (Trade name: B-CIM, manufactured by Hampford), and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (Trade name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (Trade name: TR-PBG-305, manufactured by Changzhou Strong Electronics Co., Ltd.) Examples include 1,2-propanedione,3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazole-3-yl]-,2-(O-acetyloxime) (trade name: TR-PBG-326, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazole-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.).

[0137] A photocationic polymerization initiator (photoacid generator) is a compound that generates acid upon receiving active light. While compounds that are sensitive to active light with a wavelength of 300 nm or higher, preferably 300-450 nm, and generate acid are preferred as photocationic polymerization initiators, their chemical structure is not limited. Furthermore, photocationic polymerization initiators that are not directly sensitive to active light with a wavelength of 300 nm or higher can also be preferably used in combination with a sensitizer, provided they become sensitive to active light with a wavelength of 300 nm or higher and generate acid. As the photocationic polymerization initiator, a photocationic polymerization initiator that generates an acid with a pKa of 4 or less is preferred, a photocationic polymerization initiator that generates an acid with a pKa of 3 or less is more preferred, and a photocationic polymerization initiator that generates an acid with a pKa of 2 or less is particularly preferred. There is no specific lower limit for the pKa, but for example, -10.0 or higher is preferred.

[0138] Examples of photocationic polymerization initiators include ionic photocationic polymerization initiators and nonionic photocationic polymerization initiators. Examples of ionic photocationic polymerization initiators include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, as well as quaternary ammonium salts. As the ionic photocationic polymerization initiator, the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of Japanese Patent Application Publication No. 2014-085643 may be used.

[0139] Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triazines, diazomethane compounds, imidosulfonate compounds, and oximesulfonate compounds. For trichloromethyl-s-triazines, diazomethane compounds, and imidosulfonate compounds, compounds described in paragraphs 0083 to 0088 of Japanese Patent Publication No. 2011-221494 may be used. For oximesulfonate compounds, compounds described in paragraphs 0084 to 0088 of International Publication No. 2018 / 179640 may be used.

[0140] The negative photosensitive layer preferably contains a photoradical polymerization initiator, and more preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and their derivatives.

[0141] Polymerization initiators may be used individually or in combination of two or more types. The content of the polymerization initiator (preferably a 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, based on the total mass of the negative photosensitive layer. The upper limit is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, based on the total mass of the negative photosensitive layer.

[0142] ···Pigment From the viewpoint of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, the photosensitive layer preferably contains a dye (also called "dye N") whose maximum absorption wavelength in the wavelength range of 400-780 nm during color development is 450 nm or higher, and whose maximum absorption wavelength changes with the presence of an acid, base, or radical. Although the detailed mechanism is unknown, the inclusion of dye N improves adhesion to adjacent layers (e.g., water-soluble resin layers) and results in superior resolution.

[0143] In this specification, the phrase "the maximum absorption wavelength of a dye changes due to an acid, base, or radical" may mean any of the following: a dye in a colored state is decolorized by an acid, base, or radical; a dye in a decolorized state is colored by an acid, base, or radical; or a dye in a colored state changes to a colored state of another hue. Specifically, the dye N may be a compound that changes from a decolorized state to a colored state upon exposure, or a compound that changes from a colored state to a decolorized state upon exposure. In this case, the dye may change its colored or decolorized state due to the generation and action of acids, bases, or radicals within the photosensitive layer upon exposure, or it may be a dye that changes its colored or decolorized state due to a change in the state (e.g., pH) within the photosensitive layer caused by acids, bases, or radicals. Furthermore, the dye may change its colored or decolorized state upon direct stimulation by acids, bases, or radicals without the need for exposure.

[0144] In particular, from the viewpoint of visibility and resolution of the exposed and unexposed areas, the dye N is preferably a dye whose maximum absorption wavelength changes with acid or radicals, and more preferably a dye whose maximum absorption wavelength changes with radicals. If the photosensitive layer is a negative-type photosensitive layer, it is preferable that the negative-type photosensitive layer contains both a dye N whose maximum absorption wavelength changes due to radicals, and a photoradical polymerization initiator, from the viewpoint of visibility and resolution of the exposed and unexposed areas. Furthermore, from the viewpoint of visibility between the exposed and unexposed areas, it is preferable that the dye N is a dye that develops color in response to an acid, base, or radical.

[0145] An example of the color development mechanism of dye N is a configuration in which a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator), or a photobase generator is added to the photosensitive layer, and after exposure, radicals, acids, or bases generated from the photoradical polymerization initiator, photocationic polymerization initiator, or photobase generator cause a radical-reactive dye, an acid-reactive dye, or a base-reactive dye (e.g., a leuco dye) to develop color.

[0146] From the viewpoint of visibility of the exposed and unexposed areas, the maximum absorption wavelength of dye N in the wavelength range of 400 to 780 nm during color development is preferably 550 nm or higher, more preferably 550 to 700 nm, and even more preferably 550 to 650 nm. Furthermore, the dye N may have only one maximum absorption wavelength in the wavelength range of 400-780 nm during color development, or it may have two or more. If the dye N has two or more maximum absorption wavelengths in the wavelength range of 400-780 nm during color development, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths should be 450 nm or higher.

[0147] The maximum absorption wavelength of dye N is obtained by measuring the transmission spectrum of a solution containing dye N (at a temperature of 25°C) in the range of 400 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 (maximum absorption wavelength).

[0148] Examples of dyes that develop or decolorize upon exposure include leuco compounds. Examples of the dye that decolorizes upon exposure include leuco compounds, diarylmethane-based dyes, oxazine-based dyes, xanthene-based dyes, iminonaphthoquinone-based dyes, azomethine-based dyes, and anthraquinone-based dyes. As the dye N, a leuco compound is preferable from the viewpoint of the visibility of the exposed portion and the unexposed portion.

[0149] Examples of the leuco compound include a leuco compound having a triarylmethane skeleton (triarylmethane-based dye), a leuco compound having a spiropyran skeleton (spiropyran-based dye), a leuco compound having a fluoran skeleton (fluoran-based dye), a leuco compound having a diarylmethane skeleton (diarylmethane-based dye), a leuco compound having a rhodamine lactam skeleton (rhodamine lactam-based dye), a leuco compound having an indolyl phthalide skeleton (indolyl phthalide-based dye), and a leuco compound having a leuco auramine skeleton (leuco auramine-based dye). Among them, a triarylmethane-based dye or a fluoran-based dye is preferable, and a leuco compound having a triphenylmethane skeleton (triphenylmethane-based dye) or a fluoran-based dye is more preferable.

[0150] From the viewpoint of the visibility of the exposed portion and the unexposed portion, the leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring. Thereby, the lactone ring, the sultine ring, or the sultone ring of the leuco compound can be reacted with a radical generated from a photo radical polymerization initiator or an acid generated from a photo cationic polymerization initiator to change the leuco compound to a closed ring state for decolorization or change the leuco compound to an open ring state for color development. As the leuco compound, a compound having a lactone ring, a sultine ring, or a sultone ring and in which the lactone ring, the sultine ring, or the sultone ring is opened by a radical or an acid to develop color is preferable, and a compound having a lactone ring and in which the lactone ring is opened by a radical or an acid to develop color is more preferable.

[0151] Examples of the dye N include the following dyes and leuco compounds. Specific examples of dyes among pigment N include Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuchsine, Methyl Violet 2B, Quinaldine Red, Rose Bengal, Methanyl Yellow, Thymol Sulfophthalein, Xylenol Blue, Methyl Orange, Paramethyl Red, Congofred, Benzopulpurine 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Parafuchsine, Victoria Pure Blue - Naphthalene Sulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Co., Ltd.), Oil Pink #312 (manufactured by Orient Chemical Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Co., Ltd.), Oil Scarlet #308 (manufactured by Orient Chemical Co., Ltd.) Examples include Orient Chemical Industries Co., Ltd.'s Oil Red OG, Orient Chemical Industries Co., Ltd.'s Oil Red RR, Orient Chemical Industries Co., Ltd.'s Oil Green #502, Orient Chemical Industries Co., Ltd.'s Spiron Red BEH Special, Hodogaya Chemical Co., Ltd.'s m-Cresol Purple, Cresol Red, Rhodamine B, Rhodamine 6G, Sulforhodamine B, Auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-pN,N-bis(hydroxyethyl)aminophenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0152] Specific examples of leuco compounds among the pigment N include p,p',p''-hexamethyltriaminotriphenylmethane (leucocrystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoylleucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(Np-tolyl-N-ethyl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluorane, 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, 3-(N-cyclohexyl-N-methylamino)- 6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-xylidinofluorane, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorane, 3-(N,N-diethylamino)-6-methoxy-7-aminofluorane, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluorane, 3-(N,N-diethylamino)-7-chlorofluorane, 3-(N,N-di Ethylamino)-7-benzylaminofluorane, 3-(N,N-diethylamino)-7,8-benzofluorane, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluorane, 3-(N,N-dibutylamino)-6-methyl-7-xylidinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3,3-bis(1-ethyl-2-methylindole-3-yl)phthalide, 3,3-bis(1-n-butyl-2- Examples include methylindole-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-zaphthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)phthalide, and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthene-3-one.

[0153] From the viewpoints of the visibility of the exposed and unexposed areas, the pattern visibility after development, and the resolution, the dye N is preferably a dye whose maximum absorption wavelength changes due to radicals, and more preferably a dye that develops color due to radicals. As the dye N, leuco crystal violet, crystal violet lactone, brilliant green, or victoria pure blue - naphthalene sulfonate is preferable.

[0154] The dye N may be used alone or in combination of two or more. From the viewpoints of the visibility of the exposed and unexposed areas, the pattern visibility after development, and the resolution, the content of the dye N is preferably 0.1% by mass or more, more preferably 0.1 - 10% by mass, still more preferably 0.1 - 5% by mass, and particularly preferably 0.1 - 1% by mass based on the total mass of the photosensitive layer.

[0155] The content of the dye N means the content of the dye when all the dye N contained in the total mass of the photosensitive layer is in the colored state. Hereinafter, taking the dye that develops color due to radicals as an example, the method for quantifying the content of the dye N will be described. Prepare a solution by dissolving 0.001 g and 0.01 g of the dye in 100 mL of methyl ethyl ketone. Add the photo - radical polymerization initiator Irgacure OXE01 (trade name, BASF Japan Ltd.) to each of the obtained solutions, and irradiate with light of 365 nm to generate radicals and make all the dyes in the colored state. Then, in an air atmosphere, using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), measure the absorbance of each solution at a liquid temperature of 25 °C and create a calibration curve. Next, measure the absorbance of the solution in which all the dyes are colored in the same manner as above except that 3 g of the photosensitive layer is dissolved in methyl ethyl ketone instead of the dye. Calculate the content of the dye contained in the photosensitive layer based on the calibration curve from the absorbance of the solution containing the obtained photosensitive layer. Note that 3 g of the photosensitive layer is the same as 3 g of the total solid content in the photosensitive composition.

[0156] ···Thermally cross - linkable compound When the photosensitive layer is a negative-type photosensitive layer, it is preferable to include a thermally crosslinkable compound from the viewpoint of the strength of the resulting cured film and the tackiness of the resulting uncured film. In this specification, thermally crosslinkable compounds having ethylenically unsaturated groups, as described later, will not be treated as polymerizable compounds, but as thermally crosslinkable compounds. Examples of thermally crosslinkable compounds include methylol compounds and blocked isocyanate compounds. Among these, blocked isocyanate compounds are preferred from the viewpoint of the strength of the resulting cured film and the tackiness of the resulting uncured film. Since blocked isocyanate compounds react with hydroxyl and carboxyl groups, for example, if the resin and / or polymerizable compound has at least one of a hydroxyl and a carboxyl group, the hydrophilicity of the formed film tends to decrease, and the function of the film when the cured negative-type photosensitive layer is used as a protective film tends to be enhanced. Blocked isocyanate compounds refer to "compounds having a structure in which the isocyanate group of an isocyanate is protected (so-called masked) with a blocking agent."

[0157] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160°C, and more preferably 130 to 150°C. The dissociation temperature of blocked isocyanates refers to "the temperature of the endothermic peak associated with the deprotection reaction of blocked isocyanates, as measured by differential scanning calorimetry (DSC) analysis using a differential scanning calorimeter." As a differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Corporation can be suitably used. However, the differential scanning calorimeter is not limited to this.

[0158] Examples of blocking agents with a dissociation temperature of 100-160°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 formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime). Among these, as a blocking agent with a dissociation temperature of 100 to 160°C, at least one selected from oxime compounds is preferred, for example, from the viewpoint of storage stability.

[0159] Blocked isocyanate compounds are preferably configured to have an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the film and enhancing adhesion to the transfer target. Blocked isocyanate compounds having an isocyanurate structure can be obtained, for example, by isocyanurating and protecting hexamethylene diisocyanate. Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure using an oxime compound as a blocking agent are preferred from the viewpoint of making it easier to set the dissociation temperature within a favorable range and reducing development residue compared to compounds without an oxime structure.

[0160] The blocked isocyanate compound may have polymerizable groups. There are no particular restrictions on the polymerizable group; known polymerizable groups can be used, and radical polymerizable groups are preferred. Polymerizable groups include ethylenically unsaturated groups such as (meth)acryloxy groups, (meth)acrylamide groups, and styryl groups, as well as epoxy groups such as glycidyl groups. Among the polymerizable groups, ethylenically unsaturated groups are preferred, (meth)acryloxy groups are more preferred, and acryloxy groups are even more preferred.

[0161] Commercially available blocked isocyanate compounds can be used. Examples of commercially available block isocyanate compounds include Karens (registered trademark) AOI-BM, Karens (registered trademark) MOI-BM, Karens (registered trademark) MOI-BP, etc. (manufactured by Showa Denko K.K.), and the block-type Duranate series (e.g., Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation). In addition, as the block isocyanate compound, a compound having the following structure can also be used.

[0162]

Chemical formula

[0163] The thermally crosslinkable compound may be used alone or in combination of two or more. When the photosensitive layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the photosensitive layer.

[0164] ···Other additives The photosensitive layer may contain known additives as required in addition to the above components. Examples of the additives include radical polymerization inhibitors, sensitizers, plasticizers, heterocyclic compounds (such as triazole), benzotriazoles, carboxybenzotriazoles, pyridines (such as isonicotinamide), purine bases (such as adenine), and surfactants. [[ID=..]] Each additive may be used alone or in combination of two or more.

[0165] The photosensitive layer may contain a radical polymerization inhibitor. Examples of radical polymerization inhibitors include the thermal polymerization inhibitors described in paragraph 0018 of Japanese Patent No. 4502784. Among these, phenothiazine, phenoxazine, or 4-methoxyphenol are preferred. Other radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. In order not to impair the sensitivity of the photosensitive layer, it is preferable to use nitrosophenylhydroxyamine aluminum salt as a radical polymerization inhibitor. The preferred content of the radical polymerization inhibitor is the same as the content of the same component in the photosensitive layer of the transfer film X2 in the second embodiment.

[0166] 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.

[0167] Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole. Commercially available carboxybenzotriazoles such as CBT-1 (Johoku Chemical Industry Co., Ltd., trade name) can be used.

[0168] The total content of benzotriazoles and carboxybenzotriazoles is preferably 0.01 to 3% by mass, and more preferably 0.05 to 1% by mass, relative to the total mass of the photosensitive layer. When the content is 0.01% by mass or more, the storage stability of the photosensitive layer is better. On the other hand, when the content is 3% by mass or less, the maintenance of sensitivity and suppression of dye decolorization are better.

[0169] Furthermore, the radical polymerization inhibitor is preferably a hindered phenol compound, for example. Examples of hindered phenol compounds include bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, and pentaerythritol tetrakiss-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

[0170] The photosensitive layer may contain a sensitizer. The sensitizer is not particularly limited, and known sensitizers, dyes, and pigments can be used. Examples of sensitizers include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds. Examples of commercially available sensitizers include "SB-PI 701" (4,4′-bis(diethylamino)benzophenone) manufactured by Sanyo Trading Co., Ltd.

[0171] The sensitizer may be used alone or in combination of two or more types. When the photosensitive layer contains a sensitizer, the amount of sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving sensitivity to light sources and improving curing speed by balancing polymerization rate and chain transfer, 0.01 to 5% by mass and more preferably 0.05 to 1% by mass are preferred based on the total mass of the photosensitive layer.

[0172] The photosensitive layer may contain at least one selected from the group consisting of plasticizers and heterocyclic compounds. Examples of plasticizers and heterocyclic compounds include those described in paragraphs 0097-0103 and 0111-0118 of International Publication No. 2018 / 179640.

[0173] The photosensitive layer preferably contains a surfactant. Examples of surfactants include the same surfactants that may be included in the photosensitive layer of the second embodiment transfer film X2 described later, and the preferred embodiments are also the same.

[0174] Furthermore, the photosensitive layer may further contain known additives such as metal oxide particles, antioxidants, rust inhibitors, dispersants, acid builders, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic precipitation inhibitors. Furthermore, it is also preferable to include N-phenylcarbamoylmethyl-N-carboxymethylaniline and / or N,N-tetraethyl-4,4-diaminobenzophenone as a chain transfer agent. The additives contained in the photosensitive layer are described in paragraphs 0165 to 0184 of Japanese Patent Publication No. 2014-085643, and the contents of this publication are incorporated herein by reference.

[0175] From the viewpoint of improving reliability and lamination, the water content in the photosensitive layer is preferably 0.01 to 1.0% by mass, and more preferably 0.05 to 0.5% by mass.

[0176] Furthermore, from the viewpoint of superior adhesion, the transmittance of light at a wavelength of 365 nm in the photosensitive layer is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more. There is no particular upper limit, but 99.9% or less is preferred.

[0177] ...Impurities etc. The photosensitive layer may contain a predetermined amount of impurities. Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and their ions. Among these, halide ions, sodium ions, and potassium ions are particularly prone to contamination as impurities, so it is preferable to have the following content levels.

[0178] The impurity content in the photosensitive layer is preferably 80 ppm or less by mass, more preferably 10 ppm or less, and even more preferably 2 ppm or less. The impurity content can be 1 ppb or more by mass, and may also be 0.1 ppm or more.

[0179] Methods to keep impurities within the above range include selecting raw materials for the composition that have a low impurity content, preventing the inclusion of impurities during the preparation of the photosensitive layer, and removing them by washing. By such methods, the amount of impurities can be kept within the above range.

[0180] Impurities can be quantified using known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0181] The photosensitive layer preferably contains low amounts of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane. The content of these compounds relative to the total mass of the photosensitive layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less, based on mass. The lower limit, based on mass, can be 10 ppb or more, or 100 ppb or more, relative to the total mass of the photosensitive layer. The content of these compounds can be suppressed in the same way as the metal impurities mentioned above. Furthermore, they can be quantified using known measurement methods.

[0182] From the viewpoint of improving reliability and lamination, the water content in the photosensitive layer is preferably 0.01 to 1.0% by mass, and more preferably 0.05 to 0.5% by mass.

[0183] Pigments The photosensitive layer may be a colored resin layer containing a pigment. In recent electronic devices, liquid crystal display windows may have a cover glass attached to the back edge of a transparent glass substrate or similar material to protect the liquid crystal display window. This cover glass has a black, frame-shaped light-shielding layer formed on the back edge. A colored resin layer may be used to form such a light-shielding layer. The pigment can be selected appropriately according to the desired hue, and can be chosen from black pigment, white pigment, or pigments of other chromatic colors besides black and white. In particular, when forming black patterns, black pigment is preferably selected as the pigment.

[0184] As the black pigment, any known black pigment (organic pigment or inorganic pigment, etc.) can be appropriately selected, as long as it does not impair the effects of the present invention. Among these, from the viewpoint of optical density, suitable black pigments include, for example, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, and graphite, with carbon black being particularly preferred. As for carbon black, from the viewpoint of surface resistance, carbon black in which at least a part of the surface is coated with resin is preferred.

[0185] From the viewpoint of dispersion stability, the particle size of the black pigment is preferably 0.001 to 0.1 μm in number-average particle size, and more preferably 0.01 to 0.08 μm. Here, particle size refers to the diameter of a circle with the same area as the pigment particle, calculated from the area of ​​the pigment particle taken with an electron microscope. Number-average particle size is the average value obtained by calculating the above particle size for any 100 particles and averaging the calculated particle sizes of those 100 particles.

[0186] As for pigments other than black pigments, white pigments can be used, specifically those described in paragraphs 0015 and 0114 of Japanese Patent Publication No. 2005-007765. Specifically, among the white pigments, titanium dioxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate are preferred as inorganic pigments, titanium dioxide or zinc oxide are more preferred, and titanium dioxide is even more preferred. Among the inorganic pigments, rutile-type or anatase-type titanium dioxide is even more preferred, and rutile-type titanium dioxide is particularly preferred. Furthermore, the surface of titanium dioxide may be treated with silica, alumina, titania, zirconia, or organic substances, and may be treated with two or more of these treatments. This suppresses the catalytic activity of titanium dioxide and improves its heat resistance and fading properties. From the viewpoint of reducing the thickness of the photosensitive layer after heating, at least one of alumina treatment and zirconia treatment is preferred as the surface treatment for the titanium oxide surface, and both alumina treatment and zirconia treatment are particularly preferred.

[0187] Furthermore, if the photosensitive layer is a colored resin layer, from the viewpoint of transferability, it is also preferable that the photosensitive layer further contains chromatic pigments other than black and white pigments. When chromatic pigments are included, the particle size of the chromatic pigments is preferably 0.1 μm or less, and more preferably 0.08 μm or less, in terms of superior dispersibility. Examples of chromatic pigments include Victoria Pure Blue BO (Color Index (CI) 42595), 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), and Monastral First Blue (CI Pigment Examples include CI Pigment Blue 15), Monolight First Black B (CI Pigment Black 1), Carbon, CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red 215, CI Pigment Green 7, CI Pigment Blue 15:1, CI Pigment Blue 15:4, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64, and CI Pigment Violet 23. Among these, CI Pigment Red 177 is preferred.

[0188] If the photosensitive layer contains a pigment, the pigment content is preferably more than 3% by mass and 40% by mass or less, more preferably more than 3% by mass and 35% by mass or less, even more preferably more than 5% by mass and 35% by mass or less, and particularly preferably 10% by mass or more and 35% by mass or less, based on the total mass of the photosensitive layer.

[0189] When the photosensitive layer contains pigments other than black pigment (white pigment and chromatic pigment), the content of pigments other than black pigment is preferably 30% by mass or less, more preferably 1 to 20% by mass, and even more preferably 3 to 15% by mass, relative to the black pigment.

[0190] Furthermore, if the photosensitive layer contains a black pigment and is formed from a photosensitive composition, it is preferable that the black pigment (preferably carbon black) is introduced into the photosensitive composition in the form of a pigment dispersion. The dispersion may also be prepared by pre-mixing a mixture of black pigment and a pigment dispersant, adding the mixture to an organic solvent (or vehicle), and dispersing it in a disperser. The pigment dispersant can be selected according to the pigment and solvent; for example, commercially available dispersants can be used. The vehicle refers to the medium that disperses the pigment in the pigment dispersion, and is liquid in form, containing 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.

[0191] There are no particular restrictions on the disperser, and examples of known dispersers include kneaders, roll mills, attritors, super mills, dissolvers, homomixers, and sand mills. Furthermore, fine grinding may be performed using frictional force through mechanical grinding. For information on dispersers and fine grinding, refer to the "Dictionary of Pigments" (by Kunizo Asakura, 1st edition, Asakura Shoten, 2000, pp. 438, 310).

[0192] The thickness of the photosensitive layer is not particularly limited, but is often 30 μm or less. However, in terms of achieving superior effects of the present invention, a thickness of 20 μm or less is preferred, 15 μm or less is more preferred, 10 μm or less is even more preferred, and 5.0 μm or less is particularly preferred. As a lower limit, in terms of achieving superior strength in the film obtained by curing the photosensitive layer, a thickness of 0.60 μm or more is preferred, 1.5 μm or more is more preferred, and 2.0 μm or more is even more preferred. The thickness of the photosensitive layer is calculated as the average value of five arbitrary points measured by cross-sectional observation using a Scanning Electron Microscope (SEM).

[0193] ·· Protective film The transfer film X1 may have a protective film. As protective films, resin films having heat resistance and solvent resistance can be used. Examples include polyolefin films such as polypropylene film and polyethylene film, polyester films such as polyethylene terephthalate film, polycarbonate film, and polystyrene film. Alternatively, a resin film made of the same material as the temporary support described above may be used as the protective film. Among these, polyolefin film is preferred as the protective film, polypropylene film or polyethylene film is more preferred, and polyethylene film is even more preferred.

[0194] The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, even more preferably 5 to 40 μm, and particularly preferably 15 to 30 μm. The thickness of the protective film is preferably 1 μm or more for superior mechanical strength, and 100 μm or less for relatively low cost.

[0195] Furthermore, in the case of protective films, the number of fisheyes with a diameter of 80 μm or more contained in the protective film is 5 per square meter. 2 The following is preferable: "Fish eyes" refer to foreign matter, undissolved material, and oxidatively degraded materials that are incorporated into the film during the manufacturing process, such as by heat melting, kneading, extrusion, biaxial stretching, and casting.

[0196] The number of particles with a diameter of 3 μm or larger contained in the protective film is 30 particles / mm². 2 The following is preferable: 10 pieces / mm 2The following is more preferable: 5 pieces / mm 2 The following is even more preferable. This makes it possible to suppress defects caused by the transfer of irregularities resulting from particles contained in the protective film to the photosensitive or conductive layer.

[0197] From the standpoint of providing windability, the arithmetic mean roughness Ra of the surface opposite to the surface in contact with the composition layer of the protective film is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less. From the viewpoint of suppressing defects during transfer, the surface roughness Ra of the protective film in contact with the composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less. The arithmetic mean roughness Ra of each surface of the protective film is measured in the same manner as the measurement method for the "arithmetic mean roughness Ra of the intermediate layer side of the temporary support" described above.

[0198] The optimal relationship between the physical properties of the temporary support, photosensitive layer, and protective film. In the following, it is preferable that the physical properties of the temporary support, photosensitive layer, and protective film of the transfer film X1 exhibit the following characteristics. The transfer film X1 preferably satisfies one or more of Preferred Embodiment 1, Preferred Embodiment 2, Preferred Embodiment 3, Preferred Embodiment 4, and Preferred Embodiment 5, and more preferably satisfies all of them.

[0199] "The elongation at break of the cured film with a photosensitive layer cured" was measured by curing a 20 μm thick photosensitive layer with an ultra-high pressure mercury lamp at 120 mJ / cm². 2 After exposure and curing, use a high-pressure mercury lamp at 400 mJ / cm². 2 The cured film is then subjected to further exposure and heated at 145°C for 30 minutes, after which it is measured by a tensile test. The method for measuring the "arithmetic mean roughness Ra on the intermediate layer side of the temporary support" is as previously described. The method for measuring the "arithmetic mean roughness Ra of the photosensitive layer surface of the protective film" is the same as the method for measuring the "arithmetic mean roughness Ra of the intermediate layer side of the temporary support" described above.

[0200] ...Preferred embodiment 1 The transfer film X1 preferably satisfies all of the following conditions (P1) to (P3) in terms of the physical properties of the temporary support, photosensitive layer, and protective film. (P1) The elongation at break of the cured film with the photosensitive layer cured is 15% or more at 120°C. (P2) The arithmetic mean roughness Ra of the intermediate layer surface of the temporary support is 50 nm or less. (P3) The arithmetic mean roughness Ra of the photosensitive layer surface of the protective film is 150 nm or less.

[0201] ...Preferred Mode 2 The physical properties of the temporary support and photosensitive layer of the transfer film X1 preferably satisfy the following formula (1). X×Y<1500 Formula (1) Here, in equation (1), X represents the value (%) of the elongation at break of the cured film with the photosensitive layer cured at 120°C, and Y represents the value (nm) of the arithmetic mean roughness Ra of the surface on the intermediate layer side of the temporary support. In the above formula (1), the value expressed as X × Y is preferably 750 or less.

[0202] ...Preferred Mode 3 The physical properties of the photosensitive layer of the transfer film X1 preferably satisfy the following condition (P4). (P4) The elongation at break of the cured film with the photosensitive layer cured at 120°C is more than twice as large as the elongation at break at 23°C.

[0203] ...Preferred Mode 4 The physical properties of the temporary support and photosensitive layer of the transfer film X1 preferably satisfy the following formula (2). Y ≤ Z Equation (2) Here, in equation (2), Y represents the arithmetic mean roughness Ra value (nm) of the intermediate layer side surface of the temporary support, and Z represents the arithmetic mean roughness Ra value (nm) of the photosensitive layer side surface of the protective film.

[0204] • Method for manufacturing the transfer film X1 of the first embodiment The method for manufacturing the transfer film X1 of the first embodiment is not particularly limited, and known methods can be used. Examples of methods for manufacturing the transfer film 10 include the steps of: applying an intermediate layer forming composition to the surface of a temporary support 1 to form a coating film, and further drying this coating film to form an intermediate layer 3; and applying a photosensitive composition to the surface of the intermediate layer 3 to form a coating film, and further drying this coating film to form a photosensitive layer 5. In this specification, "drying" means removing at least a portion of the solvent contained in the composition. Examples of drying methods include natural drying, heat drying, and vacuum drying. These methods can be applied individually or in combination.

[0205] A transfer film 10 is manufactured by pressing a protective film 9 onto the photosensitive layer 5 of the laminate manufactured by the above manufacturing method. In the method for manufacturing the transfer film of the first embodiment, it is preferable to manufacture a transfer film 10 comprising a temporary support 1, an intermediate layer 3, a photosensitive layer 5, and a protective film 9 by including a step of providing a protective film 9 so as to be in contact with the side of the photosensitive layer 5 opposite to the side having the temporary support 1. After manufacturing the transfer film 10 using the above manufacturing method, the transfer film 10 may be wound up to produce and store a roll of transfer film. The roll of transfer film can be provided in its original form for the lamination process with the substrate using the roll-to-roll method described later.

[0206] Intermediate layer forming composition and method for forming an intermediate layer The intermediate layer forming composition preferably contains the various components that form the intermediate layer as described above, as well as a solvent. In the intermediate layer forming composition, the preferred range of content of each component relative to the total solid content of the composition is the same as the preferred range of content of each component relative to the total mass of the intermediate layer as described above. The solvent is not particularly limited as long as it can dissolve or disperse the water-soluble resin, but 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 C1-C3 alcohols, acetone, ethylene glycol, and glycerin, with C1-C3 alcohols being preferred, and methanol or ethanol being more preferred. The solvent may be used individually or in combination of two or more types. The solvent content 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, per 100 parts by mass of the total solids content of the composition.

[0207] The method for forming the intermediate layer is not particularly limited as long as it is a method capable of forming a layer containing the above components, and examples include known coating methods (slit coating, spin coating, curtain coating, and inkjet coating, etc.).

[0208] For drying the coating film of the intermediate layer forming composition, heat drying and vacuum drying are preferred. The drying temperature is preferably 80°C or higher, and more preferably 90°C or higher. Furthermore, the upper limit is preferably 130°C or lower, and more preferably 120°C or lower. Drying can also be performed by continuously changing the temperature. Furthermore, the drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. There is no particular upper limit to the drying time, but it is preferably 600 seconds or less, and more preferably 300 seconds or less.

[0209] • Photosensitive composition and method for forming a photosensitive layer In terms of superior productivity, it is preferable to form the photosensitive layer by a coating method using a photosensitive composition containing the components that constitute the photosensitive layer as described above (e.g., binder polymer, polymerizable compound, polymerization initiator, etc.) and a solvent.

[0210] The photosensitive composition preferably contains the various components that form the photosensitive layer described above, and a solvent. In the photosensitive composition, 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 photosensitive layer described above. The solvent is not particularly limited as long as it can dissolve or disperse each component other than the solvent, and any known solvent can be used. Specifically, examples include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol and ethanol, etc.), ketone solvents (acetone and methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aprotic polar solvents (N,N-dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents (n-propyl acetate, etc.), amide solvents, lactone solvents, and mixed solvents containing two or more of these.

[0211] The solvent preferably includes at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. More preferably, a mixed solvent containing at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one selected from the group consisting of ketone solvents and cyclic ether solvents is preferred, and even more preferably, a mixed solvent containing at least three types: at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, a ketone solvent, and a cyclic ether solvent.

[0212] Examples of alkylene glycol ether solvents include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether (such as propylene glycol monomethyl ether acetate), propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether. Examples of alkylene glycol ether acetate solvents include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate. As solvents, those described in paragraphs 0092-0094 of International Publication No. 2018 / 179640 and those described in paragraph 0014 of Japanese Patent Application Publication No. 2018-177889 may be used, and these contents are incorporated herein by reference. The solvent may be used individually or in combination of two or more types. The solvent content is preferably 50 to 1,900 parts by mass, more preferably 100 to 1,200 parts by mass, and even more preferably 100 to 900 parts by mass, per 100 parts by mass of the total solids content of the composition.

[0213] Methods for applying the photosensitive composition include, for example, printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (i.e., slit coating).

[0214] For drying the photosensitive composition coating, heat drying and reduced-pressure drying are preferred methods. The drying temperature is preferably 80°C or higher, and more preferably 90°C or higher. Furthermore, the upper limit is preferably 130°C or lower, and more preferably 120°C or lower. Drying can also be performed by continuously changing the temperature. Furthermore, the drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. There is no particular upper limit to the drying time, but it is preferably 600 seconds or less, and more preferably 300 seconds or less.

[0215] Furthermore, the transfer film X1 of the first embodiment can be manufactured by laminating the protective film onto the photosensitive layer. The method for laminating the protective film onto the photosensitive layer is not particularly limited and includes known methods. Examples of devices for laminating a protective film onto a photosensitive layer include vacuum laminators and known laminators such as auto-cut laminators. The laminator is preferably equipped with a heat-sensitive roller, such as a rubber roller, and capable of applying pressure and heating.

[0216] The transfer film X1 of the first embodiment is preferably used, for example, in the formation of circuit wiring that is placed on a support substrate such as a sheet, metal substrate, ceramic substrate, and glass in the manufacturing process film of semiconductor packages, printed circuit boards, and interposer redistribution layers.

[0217] • Transfer film X2 of the second embodiment Below, an example of an embodiment of the transfer film X2 of the second embodiment will be described. The transfer film 20 shown in Figure 2 comprises, in this order, a temporary support 11, a composition layer 19 including an intermediate layer 13, a photosensitive layer 15, and a refractive index adjusting layer 17, and a protective film 21. Although the transfer film 20 shown in Figure 2 has a protective film 21 placed on it, the protective film 21 does not necessarily have to be placed on it. Furthermore, although the transfer film 20 shown in Figure 2 has a refractive index adjustment layer 17, the refractive index adjustment layer 17 does not necessarily have to be included. In Figure 2, each layer except for the protective film 21 that can be placed on the temporary support 11 is referred to as a composition layer 17. The following describes each element constituting the transfer film X2. The intermediate layer and temporary support constituting the transfer film X2 are as previously described. Furthermore, the structure of the protective film is the same as that of the transfer film X1.

[0218] ·Photosensitive layer The transfer film X2 of the second embodiment has a photosensitive layer. After transferring the photosensitive layer onto the transfer target, a pattern can be formed on the transfer target by exposure and development. The photosensitive layer is preferably a negative-type photosensitive layer. A negative-type photosensitive layer is a photosensitive layer in which the exposed area becomes less soluble in the developer solution upon exposure. When the photosensitive layer is a negative-type photosensitive layer, the pattern formed corresponds to the cured layer.

[0219] The following details the components that may be included in the photosensitive layer.

[0220] ...Binder polymer The photosensitive layer may contain a binder polymer. Examples of binder polymers 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 the reaction of epoxy resin with (meth)acrylic acid, and acid-modified epoxy acrylate resins obtained by the reaction of epoxy acrylate resin with acid anhydrides.

[0221] One preferred embodiment of the binder polymer is (meth)acrylic resin, which exhibits excellent alkali developability and film-forming properties. In this specification, (meth)acrylic resin means a resin having constituent units derived from (meth)acrylic compounds. The content of constituent 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, relative to the total constituent units of the (meth)acrylic resin. (Meth)acrylic resin may consist solely of constituent units derived from (meth)acrylic compounds, or it may contain constituent units derived from polymerizable monomers other than (meth)acrylic compounds. That is, the upper limit of the content of constituent units derived from (meth)acrylic compounds is 100% by mass or less of the total constituent units of the (meth)acrylic resin.

[0222] Examples of (meth)acrylic compounds include (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylamide, and (meth)acrylonitrile. Examples of (meth)acrylic acid esters include alkyl (meth)acrylates, tetrahydrofurfuryl (meth)acrylates, dimethylaminoethyl (meth)acrylates, diethylaminoethyl (meth)acrylates, glycidyl (meth)acrylates, benzyl (meth)acrylates, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, with alkyl (meth)acrylates being preferred. Examples of (meth)acrylamides include acrylamides such as diacetone acrylamide.

[0223] The alkyl group of the alkyl (meth)acrylate may be linear or branched. Specific examples include alkyl (meth)acrylates having an alkyl group with 1 to 12 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, and dodecyl (meth)acrylate. As the (meth)acrylic acid ester, alkyl (meth)acrylic acid ester having an alkyl group with 1 to 4 carbon atoms is preferred, and methyl (meth)acrylic acid or ethyl (meth)acrylic acid is more preferred.

[0224] (Meth)acrylic resin may have constituent units other than those derived from (meth)acrylic compounds. The polymerizable monomers that form the above structural units are not particularly limited as long as they are compounds other than (meth)acrylic compounds that can copolymerize with (meth)acrylic compounds. For example, styrene, vinyltoluene, and α-methylstyrene may have substituents at the α-position or on the aromatic ring. Examples include styrene compounds, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid, maleic anhydride, monomethyl maleic acid, monoethyl maleic acid, and monoisopropyl maleic acid, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, and crotonic acid. These polymerizable monomers may be used individually or in combination of two or more.

[0225] Furthermore, (meth)acrylic resins are preferably made of constituent units having acidic groups in order to improve alkali developability. Examples of acidic groups include carboxyl groups, sulfo groups, phosphoric acid groups, and phosphonic acid groups. In particular, the (meth)acrylic resin is more preferably having a constituent unit having a carboxyl group, and even more preferably having a constituent unit derived from the above-mentioned (meth)acrylic acid.

[0226] The content of constituent units having acid groups in the (meth)acrylic resin (preferably constituent 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. There is no particular upper limit, but in terms of excellent alkali resistance, it is preferably 50% by mass or less, and more preferably 40% by mass or less.

[0227] Furthermore, it is more preferable that the (meth)acrylic resin has constituent units derived from the alkyl (meth)acrylate ester described above. The content of constituent units derived from alkyl methacrylate in the (meth)acrylic resin is preferably 50 to 90% by mass, more preferably 60 to 90% by mass, and even more preferably 65 to 90% by mass, relative to the total constituent units of the (meth)acrylic resin.

[0228] As the (meth)acrylic resin, a resin having both constituent units derived from (meth)acrylic acid and constituent units derived from alkyl (meth)acrylate is preferred, and a resin composed only of constituent units derived from (meth)acrylic acid and alkyl (meth)acrylate is more preferred. Furthermore, as the (meth)acrylic resin, acrylic resins having constituent units derived from methacrylic acid, constituent units derived from methyl methacrylate, and constituent units derived from ethyl acrylate are also preferred.

[0229] Furthermore, the (meth)acrylic resin preferably has at least one selected from the group consisting of constituent units derived from methacrylic acid and constituent units derived from alkyl methacrylate, in order to achieve superior effects of the present invention, and preferably has both constituent units derived from methacrylic acid and constituent units derived from alkyl methacrylate. The total content of constituent units derived from methacrylic acid and alkyl methacrylate in the (meth)acrylic resin is preferably 40% by mass or more, and more preferably 60% by mass or more, relative to the total constituent units of the (meth)acrylic resin, in order to achieve superior effects of the present invention. There is no particular upper limit, and it may be 100% by mass or less, and preferably 80% by mass or less.

[0230] Furthermore, the (meth)acrylic resin may also preferably have at least one selected from the group consisting of constituent units derived from methacrylic acid and constituent units derived from alkyl methacrylate, and at least one selected from the group consisting of constituent units derived from acrylic acid and constituent units derived from alkyl acrylate, in order to further enhance the effects of the present invention. From the viewpoint of superior effects of the present invention, the total content of constituent units derived from methacrylic acid and constituent units derived from alkyl methacrylate is preferably 60 / 40 to 80 / 20 by mass ratio with respect to the total content of constituent units derived from acrylic acid and constituent units derived from alkyl acrylate.

[0231] (Meth)acrylic resin is preferably end-typed ester groups because it exhibits excellent developability of the photosensitive layer after transfer. Furthermore, the terminal portion of the (meth)acrylic resin is composed of a part derived from the polymerization initiator used in its synthesis. (Meth)acrylic resin having an ester group at its terminal can be synthesized by using a polymerization initiator that generates radicals having an ester group.

[0232] Another preferred embodiment of the binder polymer is an alkali-soluble resin. The binder polymer is preferably one with an acid value of 60 mg KOH / g or higher, for example, from the viewpoint of developability. Furthermore, the binder polymer is more preferably a resin having carboxyl groups with an acid value of 60 mgKOH / g or more (a so-called carboxyl group-containing resin), and even more preferably a (meth)acrylic resin having carboxyl groups with an acid value of 60 mgKOH / g or more (a so-called carboxyl group-containing (meth)acrylic resin), since it readily forms a strong film by thermal crosslinking with the crosslinking component upon heating. If the binder polymer is a resin containing carboxyl groups, the three-dimensional crosslinking density can be increased by adding a thermally crosslinkable compound, such as a blocked isocyanate compound, and performing thermal crosslinking. Furthermore, if the carboxyl groups of a resin containing carboxyl groups are dehydrated and made hydrophobic, the resistance to moist heat can be improved.

[0233] As long as the acid value of the carboxyl group-containing (meth)acrylic resin is 60 mgKOH / g or higher, there are no particular restrictions, and it can be appropriately selected from known (meth)acrylic resins, as long as the above acid value condition is met. For example, among the polymers described in paragraph

[0025] of Japanese Patent Publication No. 2011-095716, a carboxyl group-containing acrylic resin with an acid value of 60 mgKOH / g or more, and among the polymers described in paragraphs

[0033] to

[0052] of Japanese Patent Publication No. 2010-237589, a carboxyl group-containing acrylic resin with an acid value of 60 mgKOH / g or more can be preferably used.

[0234] Other preferred embodiments of the binder polymer include styrene-acrylic copolymers. In this specification, 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 structural units derived from the styrene compound and structural units derived from the (meth)acrylic compound is preferably 30% by mass or more, and more preferably 50% by mass or more, relative to the total structural units of the copolymer. Furthermore, the content of structural units derived from styrene compounds is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 5 to 80% by mass, relative to the total structural units of the copolymer. Furthermore, the content of constituent 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, relative to the total constituent units of the copolymer.

[0235] The binder polymer preferably has an aromatic ring structure, and more preferably has a constituent unit having an aromatic ring structure, in order to achieve superior effects of the present invention. Monomers that form structural units having an aromatic ring structure 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, monomers having an aralkyl group or styrene are preferred. Examples of aralkyl groups include substituted or unsubstituted phenylalkyl groups (excluding benzyl groups) and substituted or unsubstituted benzyl groups, with substituted or unsubstituted benzyl groups being preferred.

[0236] Examples of monomers having a phenylalkyl group include phenylethyl (meth)acrylate.

[0237] Examples of monomers having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; and vinyl monomers having a benzyl group, such as vinylbenzyl chloride and vinylbenzyl alcohol. Among these, benzyl (meth)acrylate is preferred.

[0238] Furthermore, the binder polymer is more preferably composed of constituent units represented by the following formula (S) (constituent units derived from styrene) in order to achieve superior effects of the present invention.

[0239] [ka]

[0240] When the binder polymer has constituent units having an aromatic ring structure, the content of constituent units having an aromatic ring structure is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, and even more preferably 20 to 60% by mass, relative to the total constituent units of the binder polymer, from the viewpoint of achieving superior effects of the present invention. Furthermore, the content of constituent units having an aromatic ring structure in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and even more preferably 20 to 60 mol%, relative to the total constituent units of the binder polymer, in order to achieve superior effects of the present invention. Furthermore, the content of the constituent unit represented by the above formula (S) in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, even more preferably 20 to 60 mol%, and particularly preferably 20 to 50 mol%, relative to the total constituent units of the binder polymer, in order to achieve superior effects of the present invention. In this specification, when the content of "constituent units" is specified by molar ratio, the above-mentioned "constituent units" shall be considered synonymous with "monomer units." Furthermore, in this specification, the above-mentioned "monomer units" may be modified after polymerization by polymer reactions, etc. The same applies hereafter.

[0241] The binder polymer preferably has an aliphatic hydrocarbon ring structure, as this enhances the effects of the present invention. In other words, the binder polymer preferably has a constituent unit having an aliphatic hydrocarbon ring structure. The aliphatic hydrocarbon ring structure may be monocyclic or polycyclic. In particular, the binder polymer is more preferably a ring structure in which two or more aliphatic hydrocarbon rings are fused together.

[0242] Examples of rings constituting the aliphatic hydrocarbon ring structure in a constituent unit having an aliphatic hydrocarbon ring structure include the tricyclodecane ring, cyclohexane ring, cyclopentane ring, norbornane ring, and isoborone ring. In particular, a ring formed by the fusion of two or more aliphatic hydrocarbon rings is preferred in terms of the superior effects of the present invention, and a tetrahydrodicyclopentadiene ring (tricyclo[5.2.1.0 2,6 A decane ring is more preferable. Monomers that form structural units having an aliphatic hydrocarbon ring structure include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate. Furthermore, the binder polymer is more preferably having a structural unit represented by the following formula (Cy) in order to achieve superior effects of the present invention, and is even more preferably having a structural unit represented by the above formula (S) and a structural unit represented by the following formula (Cy).

[0243] [ka]

[0244] In the formula (Cy), R M R represents a hydrogen atom or a methyl group. Cy This represents a monovalent group having an aliphatic hydrocarbon ring structure.

[0245] R in equation (Cy) M It is preferable that it be a methyl group. R in equation (Cy) Cy From the viewpoint of achieving superior effects of the present invention, it is preferable that the group is a monovalent group having an aliphatic hydrocarbon ring structure with 5 to 20 carbon atoms, more preferably a monovalent group having an aliphatic hydrocarbon ring structure with 6 to 16 carbon atoms, and even more preferably a monovalent group having an aliphatic hydrocarbon ring structure with 8 to 14 carbon atoms. Also, R in equation (Cy) Cy The aliphatic hydrocarbon ring structure in is preferably a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure, or an isoborone ring structure, from the viewpoint of achieving superior effects of the present invention, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, and even more preferably a tetrahydrodicyclopentadiene ring structure. Furthermore, R in equation (Cy) Cy The aliphatic hydrocarbon ring structure in the present invention is preferably a ring structure in which two or more aliphatic hydrocarbon rings are fused, and more preferably a ring in which two to four aliphatic hydrocarbon rings are fused, from the viewpoint of achieving superior effects of the present invention. Furthermore, R in equation (Cy) CyFrom the viewpoint of achieving superior effects of the present invention, it is preferable that the group is one in which the oxygen atom of -C(=O)O- in formula (Cy) is directly bonded to the 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.

[0246] The binder polymer may have one or more constituent units having an aliphatic hydrocarbon ring structure. When the binder polymer has constituent units having an aliphatic hydrocarbon ring structure, the content of constituent units having an aliphatic hydrocarbon ring structure is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and even more preferably 20 to 70% by mass, relative to the total constituent units of the binder polymer, in order to achieve superior effects of the present invention. Furthermore, the content of constituent units having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and even more preferably 20 to 50 mol%, relative to the total constituent units of the binder polymer, in order to achieve superior effects of the present invention. Furthermore, the content of the constituent unit represented by the above formula (Cy) in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and even more preferably 20 to 50 mol%, relative to the total constituent units of the binder polymer, in order to achieve superior effects of the present invention.

[0247] When the binder polymer has constituent units having an aromatic ring structure and constituent units having an aliphatic hydrocarbon ring structure, the total content of constituent units having an aromatic ring structure and constituent units having an aliphatic hydrocarbon ring structure is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 40 to 75% by mass, relative to the total constituent units of the binder polymer, in order to achieve superior effects of the present invention. Furthermore, the total content of constituent units having an aromatic ring structure and constituent units having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and even more preferably 40 to 60 mol%, relative to the total constituent units of the binder polymer, in order to achieve superior effects of the present invention. Furthermore, the total content of the constituent units represented by formula (S) and formula (Cy) in the binder polymer is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and even more preferably 40 to 60 mol%, relative to the total constituent units of the binder polymer, in order to achieve superior effects of the present invention. Furthermore, in the binder polymer, the molar amounts nS of the constituent units represented by the above formula (S) and nCy of the constituent units represented by the above formula (Cy) preferably satisfy the relationship shown in the following formula (SCy), more preferably satisfy the following formula (SCy-1), and even more preferably satisfy the following formula (SCy-2), in order to achieve superior effects of the present invention. 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)

[0248] The binder polymer preferably has constituent units having acidic groups, as this provides superior effects for the present invention. Examples of the above-mentioned acidic groups include carboxyl groups, sulfol groups, phosphonic acid groups, and phosphate groups, with carboxyl groups being preferred. As for the constituent units having the above acid group, the constituent units derived from (meth)acrylic acid shown below are preferred, and the constituent units derived from methacrylic acid are more preferred.

[0249] [ka]

[0250] The binder polymer may have one or more constituent units having acidic groups. When the binder polymer has constituent units having acidic groups, the content of constituent units having acidic groups is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 10 to 30% by mass, relative to the total constituent units of the binder polymer, in order to achieve superior effects of the present invention. Furthermore, the content of constituent units having acid groups in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, and even more preferably 20 to 40 mol%, relative to the total constituent units of the binder polymer, in order to achieve superior effects of the present invention. Furthermore, the content of (meth)acrylic acid-derived structural units in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, and even more preferably 20 to 40 mol%, relative to the total structural units of the binder polymer, in order to achieve superior effects of the present invention.

[0251] The binder polymer is preferably having a reactive group, and more preferably having a constituent unit having a reactive group, from the viewpoint of achieving superior effects of the present invention. As the reactive group, a radical polymerizable group is preferred, and an ethylenically unsaturated group is more preferred. Furthermore, if the binder polymer has an ethylenically unsaturated group, it is preferable that the binder polymer has a structural unit having an ethylenically unsaturated group in its side chain. In this specification, "main chain" refers to the relatively longest bonding chain in the polymer compound molecule constituting the resin, and "side chain" refers to an atomic group branching off from the main chain. As the ethylenically unsaturated group, an allyl group or a (meth)acryloxy group is more preferred. Examples of constituent units having reactive groups are listed below, but are not limited to these.

[0252] [ka]

[0253] The binder polymer may have one or more reactive structural units. When the binder polymer has constituent units having reactive groups, the content of constituent units having reactive groups is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and even more preferably 20 to 40% by mass, relative to the total constituent units of the binder polymer, in order to achieve superior effects of the present invention. Furthermore, the content of the constituent units having reactive groups in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and even more preferably 20 to 50 mol%, relative to the total constituent units of the binder polymer, in order to achieve superior effects of the present invention.

[0254] Methods for introducing reactive groups into a binder polymer include reacting functional groups such as hydroxyl groups, carboxyl groups, primary amino groups, secondary amino groups, acetoacetyl groups, and sulfo groups with compounds such as epoxy compounds, blocked isocyanate compounds, isocyanate compounds, vinyl sulfone compounds, aldehyde compounds, methylol compounds, and carboxylic acid anhydrides. A preferred method for introducing reactive groups into a binder polymer is to synthesize a polymer having carboxyl groups by polymerization, and then, by polymer reaction, react some of the carboxyl groups of the resulting polymer with glycidyl (meth)acrylate to introduce (meth)acryloxy groups into the polymer. This method makes it possible to obtain a binder polymer having (meth)acryloxy groups in its side chains. The above polymerization reaction is preferably carried out at a temperature of 70 to 100°C, and more preferably at 80 to 90°C. As the polymerization initiator used in the above polymerization reaction, an azo-based initiator is preferred, and for example, V-601 (trade name) or V-65 (trade name) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. is more preferred. The above polymer reaction is preferably carried out at a temperature of 80 to 110°C. In the above polymer reaction, it is preferable to use a catalyst such as an ammonium salt.

[0255] As binder polymers, polymers X1 to X4 shown below are preferred in terms of their superior effects according to the present invention. The content ratios (a to d) and weight-average molecular weight Mw of each constituent unit shown below can be appropriately changed depending on the purpose, but the following configuration is particularly preferred in terms of its superior effects according to the present invention. (Polymer X1) a: 20-60% by mass, b: 10-50% by mass, c: 5.0-25% by mass, d: 10-50% by mass. (Polymer X2) a: 20-60% by mass, b: 10-50% by mass, c: 5.0-25% by mass, d: 10-50% by mass. (Polymer X3) a: 30-65% by mass, b: 1.0-20% by mass, c: 5.0-25% by mass, d: 10-50% by mass. (Polymer X4) a: 1.0-20% by mass, b: 20-60% by mass, c: 5.0-25% by mass, d: 10-50% by mass.

[0256] [ka] JPEG0007871481000009.jpg47106JPEG0007871481000010.jpg47103JPEG0007871481000011.jpg50108

[0257] Furthermore, the binder polymer may also contain a polymer having a constituent unit having a carboxylic acid anhydride structure (hereinafter also referred to as "polymer X"). The carboxylic acid anhydride structure may be either a linear carboxylic acid anhydride structure or a cyclic carboxylic acid anhydride structure, but a cyclic carboxylic acid anhydride structure is preferred. The ring in the cyclic carboxylic acid anhydride structure is preferably a 5- to 7-membered ring, more preferably a 5-membered or 6-membered ring, and even more preferably a 5-membered ring.

[0258] The constituent unit having a carboxylic acid anhydride structure is preferably a constituent unit that contains a divalent group in the main chain obtained by removing two hydrogen atoms from the compound represented by the following formula P-1, or a constituent unit in which a monovalent group obtained by removing one hydrogen atom from the compound represented by the following formula P-1 is directly bonded to the main chain or via a divalent linking group.

[0259] [ka]

[0260] In formula P-1, R A1a represents a substituent, n 1a Individual R A1a They may be the same or different, Z 1a represents a divalent group that forms a ring containing -C(=O)-OC(=O)-, and n 1a This represents a non-negative integer.

[0261] R A1a Examples of substituents represented by this formula include alkyl groups. Z 1a Preferably, the alkylene group has 2 to 4 carbon atoms, more preferably an alkylene group has 2 or 3 carbon atoms, and even more preferably an alkylene group has 2 carbon atoms. n 1a This represents a non-negative integer. 1a When n represents an alkylene group with 2 to 4 carbon atoms, 1a It is preferably an integer between 0 and 4, more preferably an integer between 0 and 2, and even more preferably 0. n 1a If R represents an integer greater than or equal to 2, there are multiple R A1a These may be the same or different. Also, there may be multiple Rs. A1a These elements may be joined to form a ring, but it is preferable that they are not joined to form a ring.

[0262] As for the constituent units having a carboxylic acid anhydride structure, constituent units derived from unsaturated carboxylic acid anhydrides are preferred, constituent units derived from unsaturated cyclic carboxylic acid anhydrides are more preferred, constituent units derived from unsaturated aliphatic cyclic carboxylic acid anhydrides are even more preferred, constituent units derived from maleic anhydride or itaconic anhydride are particularly preferred, and constituent units derived from maleic anhydride are most preferred.

[0263] The following are specific examples of constituent units having a carboxylic acid anhydride structure, but constituent units having a carboxylic acid anhydride structure are not limited to these examples. In the constituent units below, Rx represents a hydrogen atom, a methyl group, a CH2OH group, or a CF3 group, and Me represents a methyl group.

[0264] [ka]

[0265] [ka]

[0266] The constituent units having a carboxylic acid anhydride structure in polymer X may be a single unit or two or more units.

[0267] The total content of constituent units having a carboxylic acid anhydride structure is preferably 0 to 60 mol%, more preferably 5 to 40 mol%, and even more preferably 10 to 35 mol%, relative to the total constituent units of polymer X.

[0268] The photosensitive layer may contain only one type of polymer X, or it may contain two or more types. When the photosensitive layer contains polymer X, the effects of the present invention are more superior, so the content of polymer X is preferably 0.1 to 30% by mass, more preferably 0.2 to 20% by mass, even more preferably 0.5 to 20% by mass, and still more preferably 1 to 20% by mass, based on the total mass of the photosensitive layer.

[0269] The weight-average molecular weight (Mw) of the binder polymer is preferably 5,000 or more, more preferably 10,000 or more, even more preferably 10,000 to 50,000, and particularly preferably 20,000 to 30,000, from the viewpoint of achieving superior effects of the present invention.

[0270] The acid value of the binder polymer is preferably 10 to 200 mg KOH / g, more preferably 60 to 200 mg KOH / g, even more preferably 60 to 150 mg KOH / g, and particularly preferably 70 to 125 mg KOH / g. The acid value of the binder polymer can be measured, for example, according to the method described in JIS K0070:1992. From the viewpoint of developability, the degree of dispersion of the binder polymer 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.

[0271] The photosensitive layer may contain only one type of binder polymer, or it may contain two or more types. The binder polymer content is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass, relative to the total mass of the photosensitive layer, in order to achieve superior effects of the present invention.

[0272] ...polymerizable compound The photosensitive layer may contain polymerizable compounds. Polymerizable compounds are compounds that have polymerizable groups. Examples of polymerizable groups include radical polymerizable groups and cationic polymerizable groups, with radical polymerizable groups being preferred.

[0273] The polymerizable compound preferably contains a radical polymerizable compound having an ethylenically unsaturated group (hereinafter also simply referred to as "ethylenically unsaturated compound"). A (meth)acryloxy group is preferred as the ethylenically unsaturated group. In this specification, the ethylenically unsaturated compound is a compound other than the binder polymer described above, and preferably has a molecular weight of less than 5,000.

[0274] One preferred embodiment of a polymerizable 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 of these independently represents a (meth)acryloyloxy group, and R 1 This represents a divalent linking group having a chain-like structure.

[0275] Q in equation (M) 1 and Q 2 From the standpoint of ease of synthesis, Q 1 and Q 2 It is preferable that they are the same group. Also, Q in equation (M) 1 and Q 2 From the viewpoint of reactivity, it is preferable that it be an acryloyloxy group. R in equation (M) 1 As for the advantages of the present invention, alkylene group, alkylene oxyalkylene group (-L 1 -OL 1 -), or polyalkylene oxyalkylene group (-(L 1 -O) p -L 1 -) is preferred, a hydrocarbon group having 2 to 20 carbon atoms is more preferred, a polyalkylene oxyalkylene group is more preferred, an alkylene group having 4 to 20 carbon atoms is even more preferred, and a linear alkylene group having 6 to 18 carbon atoms is particularly preferred. The hydrocarbon group described above only needs to have a chain-like structure in at least part of it. The portion other than the chain-like structure is not particularly limited and may be, for example, a branched chain, a cyclic, or a 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 formed by 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. Note that the above L 1Each of these independently represents an alkylene group, preferably an ethylene group, a propylene group, or a butylene group, and more preferably an ethylene group or a 1,2-propylene group. p represents an integer of 2 or more, preferably an integer between 2 and 10.

[0276] Furthermore, Q in compound M 1 and Q 2 The number of atoms in the shortest connecting chain between these elements is preferably 3 to 50, more preferably 4 to 40, even more preferably 6 to 20, and particularly preferably 8 to 12, from the viewpoint of achieving superior effects of the present invention. In this specification, "Q 1 and Q 2 "The number of atoms in the shortest linking chain connecting the two points" is Q 1 R connected to 1 From the atom to Q 2 R connected to 1 This is the shortest number of atoms required to connect up to the first atom in a given structure.

[0277] 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, hydrogenated bisphenol A di(meth)acrylate, hydrogenated bisphenol F di(meth)acrylate, 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 mixtures. Among the above compounds, it is preferable that the present invention exhibits superior effects, and therefore, 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, more preferably at least one compound selected from the group consisting of 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate is preferred, and even more preferably at least one compound selected from the group consisting of 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate is preferred.

[0278] Furthermore, one preferred embodiment of a polymerizable compound is a difunctional or ethylenically unsaturated compound. In this specification, "bifunctional or more ethylenically unsaturated compounds" means compounds having two or more ethylenically unsaturated groups in one molecule. In ethylenically unsaturated compounds, the (meth)acryloyl group is preferred as the ethylenically unsaturated group. As the ethylenically unsaturated compound, (meth)acrylate compounds are preferred.

[0279] There are no particular restrictions on the bifunctional ethylenically unsaturated compound, and it can be appropriately selected from known compounds. Examples of bifunctional ethylenically unsaturated compounds other than compound M mentioned above include tricyclodecanedimethanol di(meth)acrylate and 1,4-cyclohexanediol di(meth)acrylate.

[0280] Commercially available bifunctional ethylenically unsaturated compounds include tricyclodecanedimethanol diacrylate (trade name: NK ester A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecanedimenanol 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.).

[0281] There are no particular restrictions on the ethylenically unsaturated compound with three or more functions; it can be appropriately selected from known compounds. Examples of ethylenically unsaturated compounds with three or more functions include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds with a glycerin tri(meth)acrylate skeleton.

[0282] 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, while "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate.

[0283] Polymerizable compounds include caprolactone-modified (meth)acrylate compounds (such as KAYARAD® DPCA-20 manufactured by Nippon Kayaku Co., Ltd. and A-9300-1CL manufactured by Shin Nakamura Chemical Industry Co., Ltd.), alkylene oxide-modified (meth)acrylate compounds (such as KAYARAD® RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin Nakamura Chemical Industry Co., Ltd., and EBECRYL® 135 manufactured by Daicel Ornex Co., Ltd.), and ethoxylated glycerin triacrylate (such as NK ester A-GLY-9E manufactured by Shin Nakamura Chemical Industry Co., Ltd.).

[0284] Examples of polymerizable compounds include urethane (meth)acrylate compounds. 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. Furthermore, urethane (meth)acrylates with three or more functionalities can also be mentioned. The lower limit of the number of functional groups is more preferably six or more, and even more preferably eight or more. The upper limit of the number of functional groups is preferably 20 or less. Examples of urethane (meth)acrylates with three or more functionalities include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), U-15HA (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), UA-1100H (manufactured by Shin Nakamura Chemical Industry 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.).

[0285] One preferred embodiment of a polymerizable compound is an ethylenically unsaturated compound having an acidic group. Examples of acidic groups include phosphate groups, sulfo groups, and carboxyl groups. Among these, the carboxyl group is preferred as the acid group. Examples of ethylenically unsaturated compounds containing acidic groups include 3-4 functional ethylenically unsaturated compounds containing acidic groups (pentaerythritol tri-tetraacrylate (PETA) skeleton with carboxyl groups introduced (acid value: 80-120 mg KOH / g)) and 5-6 functional ethylenically unsaturated compounds containing acidic groups (dipentaerythritol penta-hexaacrylate (DPHA) skeleton with carboxyl groups introduced (acid value: 25-70 mg KOH / g)). These trifunctional or more ethylenically unsaturated compounds having acidic groups may be used in combination with bifunctional ethylenically unsaturated compounds having acidic groups, if necessary.

[0286] As the ethylenically unsaturated compound having an acidic group, at least one selected from the group consisting of bifunctional or more ethylenically unsaturated compounds having a carboxyl group and their carboxylic acid anhydrides is preferred. If the ethylenically unsaturated compound having an acidic group is at least one selected from the group consisting of bifunctional or more ethylenically unsaturated compounds having a carboxyl group and their carboxylic acid anhydrides, the developability and film strength are further improved. The ethylenically unsaturated compound having a carboxyl group and possessing two or more functionalities is not particularly limited and can be appropriately selected from known compounds. Examples of ethylenically unsaturated compounds with two or more functionalities containing a carboxyl group include Arronix® TO-2349 (manufactured by Toagosei Co., Ltd.), Arronix® M-520 (manufactured by Toagosei Co., Ltd.), and Arronix® M-510 (manufactured by Toagosei Co., Ltd.).

[0287] As an ethylenically unsaturated compound having an acidic group, the polymerizable compound having an acidic group described in paragraphs

[0025] to

[0030] of Japanese Patent Application Publication No. 2004-239942 is preferred, and the contents described in this publication are incorporated herein.

[0288] Examples of polymerizable compounds 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)acrylate esters. These are used individually or in combination of two or more types.

[0289] Compounds obtained by reacting polyhydric alcohols with α,β-unsaturated carboxylic acids include, for example, bisphenol A-based (meth)acrylate compounds such as 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane, polyethylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups, polypropylene glycol di(meth)acrylate having 2 to 14 propylene oxide groups, polyethylene polypropylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups and 2 to 14 propylene oxide groups, and Examples include methylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxytri(meth)acrylate, trimethylolpropane diethoxytri(meth)acrylate, trimethylolpropane triethoxytri(meth)acrylate, trimethylolpropane tetraethoxytri(meth)acrylate, trimethylolpropane pentaethoxytri(meth)acrylate, di(trimethylolpropane)tetraacrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Among these, ethylene 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 are more preferred.

[0290] Polymerizable compounds include caprolactone-modified ethylenically unsaturated compounds (e.g., KAYARAD® DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin Nakamura Chemical Industry 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 Industry Co., Ltd., EBECRYL® 135 manufactured by Daicel Ornex Co., Ltd.), and ethoxylated glycerin triacrylates (e.g., A-GLY-9E manufactured by Shin Nakamura Chemical Industry Co., Ltd.).

[0291] Among polymerizable compounds (especially ethylenically unsaturated compounds), those containing ester bonds are particularly preferred due to their excellent developability of the photosensitive layer after transfer. The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in its molecule. However, in terms of superior effects of the present invention, ethylene 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 are more preferred. From the standpoint of providing reliability, it is preferable that the ethylenically unsaturated compound includes an ethylenically unsaturated compound having an aliphatic group with 6 to 20 carbon atoms and an ethylene unsaturated compound having the above-mentioned tetramethylolmethane structure or 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 tricyclodecanedimethanol di(meth)acrylate.

[0292] One preferred embodiment of a polymerizable compound is a polymerizable compound having an aliphatic hydrocarbon ring structure (preferably a difunctional ethylenically unsaturated compound). The polymerizable compounds described above are preferably polymerizable compounds having a ring structure in which two or more aliphatic hydrocarbon rings are fused (preferably a structure selected from the group consisting of tricyclodecane and tricyclodecene structures), more preferably bifunctional ethylenically unsaturated compounds 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 above 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 in terms of superior effects of the present invention.

[0293] The molecular weight of the polymerizable compound is preferably 200 to 3,000, more preferably 250 to 2,600, even more preferably 280 to 2,200, and particularly preferably 300 to 2,200. Of the polymerizable compounds contained in the photosensitive layer, the proportion of polymerizable compounds with a molecular weight of 300 or less is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less, relative to the total amount of polymerizable compounds contained in the photosensitive layer.

[0294] As one preferred embodiment of the photosensitive layer, it is preferable that the photosensitive layer contains a bifunctional or more ethylenically unsaturated compound, more preferably a trifunctional or more ethylenically unsaturated compound, and even more preferably a trifunctional or tetrafunctional ethylenically unsaturated compound.

[0295] Furthermore, as one preferred embodiment of the photosensitive layer, it is preferable that the photosensitive layer comprises a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and a binder polymer having a constituent unit having an aliphatic hydrocarbon ring.

[0296] Furthermore, as one preferred embodiment of the photosensitive layer, it is preferable that the photosensitive layer contains a compound represented by formula (M) and an ethylenically unsaturated compound having an acid group, more preferably 1,9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, and even more preferably 1,9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate and a succinic acid modified form of dipentaerythritol pentaacrylate.

[0297] Furthermore, as one preferred embodiment of the photosensitive layer, it is preferable that the photosensitive layer 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.

[0298] Furthermore, as one preferred embodiment of the photosensitive layer, it is preferable that the photosensitive layer contains a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth)acrylate compound) and a trifunctional or more ethylenically unsaturated compound (preferably a trifunctional or more (meth)acrylate compound), from the viewpoint of suppressing development residue and rust prevention. The mass ratio of the content of a bifunctional ethylenically unsaturated compound to that of a trifunctional or more functional ethylenically unsaturated compound is preferably 10:90 to 90:10, and more preferably 30:70 to 70:30. The content of difunctional ethylenically unsaturated compounds relative to the total amount of all ethylenically unsaturated compounds is preferably 20 to 80% by mass, and more preferably 30 to 70% by mass. The amount of the bifunctional ethylenically unsaturated compound in the photosensitive layer is preferably 10 to 60% by mass, and more preferably 15 to 40% by mass.

[0299] Furthermore, as one preferred embodiment of the photosensitive layer, it is preferable that the photosensitive layer contains 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 layer, the photosensitive layer preferably contains compound M and an ethylenically unsaturated compound having an acid group, from the viewpoint of substrate adhesion, development residue suppression, and rust prevention; 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; even more preferably contains compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a trifunctional or more 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 trifunctional or more functional ethylenically unsaturated compound, an ethylenically unsaturated compound having an acid group, and a urethane (meth)acrylate compound. Furthermore, as one preferred embodiment of the photosensitive layer, the photosensitive layer preferably contains 1,9-nonanediol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, from the viewpoint of substrate adhesion, development residue suppression, and rust prevention, more preferably contains 1,9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, more preferably contains 1,9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate, dipentaerythritol hexaacrylate, and an ethylenically unsaturated compound having a carboxylic acid group, and particularly preferably contains 1,9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate, an ethylenically unsaturated compound having a carboxylic acid group, and a urethane acrylate compound.

[0300] The photosensitive layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound. The content of the ethylenically unsaturated compound with two or more functions in the above-mentioned ethylenically unsaturated compound is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass, based on the total content of all ethylenically unsaturated compounds contained in the photosensitive layer.

[0301] Polymerizable compounds (especially ethylenically unsaturated compounds) may be used individually or in combination of two or more. The content of polymerizable compounds (especially ethylenically unsaturated compounds) in the photosensitive layer is preferably 1 to 70% by mass, more preferably 5 to 70% by mass, even more preferably 5 to 60% by mass, and particularly preferably 5 to 50% by mass, based on the total mass of the photosensitive layer.

[0302] ...polymerization initiator The photosensitive layer may contain a polymerization initiator. As the polymerization initiator, a photopolymerization initiator is preferred. There are no particular restrictions on the photopolymerization initiator; known photopolymerization initiators can be used. Examples of photopolymerization initiators include photopolymerization initiators having an oxime ester structure (hereinafter also referred to as "oxime-based photopolymerization initiators"), photopolymerization initiators having an α-aminoalkylphenone structure (hereinafter also referred to as "α-aminoalkylphenone-based photopolymerization initiators"), photopolymerization initiators having an α-hydroxyalkylphenone structure (hereinafter also referred to as "α-hydroxyalkylphenone-based polymerization initiators"), photopolymerization initiators having an acylphosphine oxide structure (hereinafter also referred to as "acylphosphine oxide-based photopolymerization initiators"), and photopolymerization initiators having an N-phenylglycine structure (hereinafter also referred to as "N-phenylglycine-based photopolymerization initiators").

[0303] The photopolymerization initiator preferably includes at least one selected from the group consisting of oxime-based photopolymerization initiators, α-aminoalkylphenone-based photopolymerization initiators, α-hydroxyalkylphenone-based polymerization initiators, and N-phenylglycine-based photopolymerization initiators, and more preferably includes at least one selected from the group consisting of oxime-based photopolymerization initiators, α-aminoalkylphenone-based photopolymerization initiators, and N-phenylglycine-based photopolymerization initiators.

[0304] Furthermore, as photopolymerization initiators, for example, those described in paragraphs

[0031] to

[0042] of Japanese Patent Application Publication No. 2011-95716 and paragraphs

[0064] to

[0081] of Japanese Patent Application Publication No. 2015-014783 may be used.

[0305] Commercially available photopolymerization initiators include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyl oxime) [trade name: IRGACURE® OXE-01, manufactured by BASF], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyl oxime) [trade name: IRGACURE® OXE-02, manufactured by BASF], IRGACURE® OXE03 (manufactured by BASF), IRGACURE® OXE04 (manufactured by BASF), and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [trade name: Omnirad® 379EG, IGM Resins]. [Manufactured by 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], 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 [Trade name: Omnirad® 369, manufactured by IGM Resins BV], 2-hydroxy-2-methyl-1-phenylpropan-1-one [Trade name: Omnirad® 1173, manufactured by IGM Resins BV], 1-hydroxycyclohexylphenyl ketone [Trade name: Omnirad® 184, manufactured by IGM Resins [Manufactured by BV Corporation], 2,2-dimethoxy-1,2-diphenylethane-1-one [Trade name: Omnirad (registered trademark) 651, IGM Resins B.Oxime ester-based products such as [Product name: Lunar(registered trademark) 6, manufactured by DKSH Japan Co., Ltd.], 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyl oxime) (Product name: TR-PBG-305, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), 1,2-propanedione,3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazole-3-yl]-,2-(O-acetyloxime) (Product name: TR-PBG Examples include -326 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazole-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), APi-307 (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, manufactured by Shenzhen UV-ChemTech Ltd.), etc.

[0306] The photopolymerization initiator may be used alone or in combination of two or more types. When using two or more types in combination, it is preferable to use an oxime-based photopolymerization initiator and at least one selected from α-aminoalkylphenone-based photopolymerization initiators and α-hydroxyalkylphenone-based polymerization initiators. If the photosensitive layer contains a photopolymerization initiator, the content of the photopolymerization 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 layer. Furthermore, the upper limit is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the photosensitive layer.

[0307] ...heterocyclic compounds The photosensitive layer may contain a heterocyclic compound. The heterocyclic compound may have either a monocyclic or polycyclic heterocyclic ring. Examples of heteroatoms present in heterocyclic compounds include nitrogen atoms, oxygen atoms, and sulfur atoms. It is preferable that heterocyclic compounds have at least one atom selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms, and more preferably a nitrogen atom.

[0308] 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, as heterocyclic compounds, at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzimidazole compounds, and benzoxazole compounds is preferred, and at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, and benzoxazole compounds is more preferred.

[0309] Preferred examples of heterocyclic compounds are shown below. Examples of triazole and benzotriazole compounds include the following compounds.

[0310] [ka]

[0311] [ka]

[0312] Examples of tetrazole compounds include the following compounds:

[0313] [ka]

[0314] [ka]

[0315] Examples of thiadiazole compounds include the following compounds:

[0316] [ka]

[0317] Examples of triazine compounds include the following:

[0318] [ka]

[0319] Examples of rhodanine compounds include the following compounds:

[0320] [ka]

[0321] Examples of thiazole compounds include the following compounds:

[0322] [ka]

[0323] Examples of benzothiazole compounds include the following compounds:

[0324] [ka]

[0325] Examples of benzimidazole compounds include the following:

[0326] [ka]

[0327] [ka]

[0328] Examples of benzoxazole compounds include the following compounds:

[0329] [ka]

[0330] Heterocyclic compounds can be used individually or in combination of two or more. When the photosensitive layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01 to 20.0% by mass, more preferably 0.10 to 10.0% by mass, even more preferably 0.30 to 8.0% by mass, and particularly preferably 0.50 to 5.0% by mass, relative to the total mass of the photosensitive layer.

[0331] ...Aliphatic thiol compounds The photosensitive layer may contain an aliphatic thiol compound. The inclusion of an aliphatic thiol compound in the photosensitive layer suppresses curing shrinkage of the formed film and relieves stress through an ene-thiol reaction between the aliphatic thiol compound and a radical polymerizable compound having an ethylenically unsaturated group.

[0332] As the aliphatic thiol compound, monofunctional aliphatic thiol compounds or polyfunctional aliphatic thiol compounds (i.e., aliphatic thiol compounds with two or more functions) are preferred.

[0333] Among the above, polyfunctional aliphatic thiol compounds are preferred as aliphatic thiol compounds in terms of the adhesion of the formed pattern (especially the adhesion after exposure).

[0334] In this specification, "polyfunctional aliphatic thiol compound" means an aliphatic compound having two or more thiol groups (also called "mercapto groups") in its molecule.

[0335] As the polyfunctional aliphatic thiol compound, low molecular weight compounds with a molecular weight of 100 or more are preferred. 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.

[0336] As for the number of functional groups in polyfunctional aliphatic thiol compounds, for example, 2 to 10 functional groups are preferred, 2 to 8 functional groups are more preferred, and 2 to 6 functional groups are even more preferred, from the viewpoint of the adhesion of the formed pattern.

[0337] 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-mercaptopropionyloxyethyl) Examples include di(3-mercaptopropyl) ether, 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.

[0338] Among the above, as polyfunctional aliphatic thiol compounds, at least one compound selected from the group consisting of trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione is preferred.

[0339] Examples of monofunctional aliphatic thiol compounds include 1-octanthiol, 1-dodecanethiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.

[0340] The photosensitive layer may contain one aliphatic thiol compound or two or more aliphatic thiol compounds.

[0341] When the photosensitive layer contains an aliphatic thiol compound, the content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5 to 50% by mass, even more preferably 5 to 30% by mass, and particularly preferably 8 to 20% by mass, based on the total mass of the photosensitive layer.

[0342] ...thermally crosslinkable compound The photosensitive layer preferably contains a thermally crosslinkable compound, from the viewpoint of the strength of the resulting cured film and the tackiness of the resulting uncured film. In this specification, thermally crosslinkable compounds having ethylenically unsaturated groups, as described later, will not be treated as ethylenically unsaturated compounds, but as thermally crosslinkable compounds. Examples of thermally crosslinkable compounds include epoxy compounds, oxetane compounds, methylol compounds, and blocked isocyanate compounds. Among these, blocked isocyanate compounds are preferred in terms of the strength of the resulting cured film and the tackiness of the resulting uncured film. Since blocked isocyanate compounds react with hydroxyl and carboxyl groups, for example, if at least one of the binder polymer and the radical polymerizable compound having an ethylenically unsaturated group has at least one of a hydroxyl group and a carboxyl group, the hydrophilicity of the formed film tends to decrease, and its function as a protective film is enhanced. Blocked isocyanate compounds refer to "compounds having a structure in which the isocyanate group of an isocyanate is protected (so-called masked) with a blocking agent."

[0343] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160°C, and more preferably 130 to 150°C. The dissociation temperature of blocked isocyanates refers to "the temperature of the endothermic peak associated with the deprotection reaction of blocked isocyanates, as measured by differential scanning calorimetry (DSC) analysis using a differential scanning calorimeter." As a 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.

[0344] Examples of blocking agents with a dissociation temperature of 100-160°C include active methylene compounds [malonate diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)] and oxime compounds (formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime, etc., which have a structure represented by -C(=N-OH)- in the molecule). Among these, as a blocking agent with a dissociation temperature of 100 to 160°C, at least one selected from oxime compounds is preferred, for example, from the viewpoint of storage stability.

[0345] Blocked isocyanate compounds are preferably configured to have an isocyanurate structure, for example, to improve the brittleness of the film and enhance adhesion to the substrate. Blocked isocyanate compounds having an isocyanurate structure can be obtained, for example, by isocyanurating and protecting hexamethylene diisocyanate. Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure using an oxime compound as a blocking agent are preferred because they make it easier to set the dissociation temperature within a favorable range and reduce development residue compared to compounds without an oxime structure.

[0346] The blocked isocyanate compound may have polymerizable groups. There are no particular restrictions on the polymerizable group; known polymerizable groups can be used, and radical polymerizable groups are preferred. Polymerizable groups include ethylenically unsaturated groups such as (meth)acryloxy groups, (meth)acrylamide groups, and styryl groups, as well as epoxy groups such as glycidyl groups. Among the polymerizable groups, ethylenically unsaturated groups are preferred, (meth)acryloxy groups are more preferred, and acryloxy groups are even more preferred.

[0347] Commercially available blocked isocyanate compounds can be used. Examples of commercially available blocked isocyanate compounds include Karenz® AOI-BM, Karenz® MOI-BM, Karenz® MOI-BP, etc. (all manufactured by Showa Denko K.K.), and the block-type Duranate series (for example, Duranate® TPA-B80E, Duranate® WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation).

[0348] The thermally crosslinkable compound may be used alone or in combination of two or more types. If the photosensitive layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass, relative to the total mass of the photosensitive layer.

[0349] ...surfactants The photosensitive layer may contain a surfactant. Examples of surfactants include those described in paragraph

[0017] of Japanese Patent No. 4502784 and paragraphs

[0060] to

[0071] of Japanese Unexamined Patent Publication No. 2009-237362.

[0350] As the surfactant, nonionic surfactants, fluorinated surfactants, or silicone surfactants are preferred. Furthermore, as the surfactant, nonionic surfactants are preferred. Examples of commercially available fluorine-based surfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, and MFS-33. 0, EXP.MFS-578, EXP.MFS-578-2, EXP.MFS-579, EXP.MFS-586, EXP.MFS-587, EXP.MFS-628, EXP.MFS-631, EXP.MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (all manufactured by DIC Corporation), Florard FC430, FC431, FC171 (all manufactured by Sumitomo 3M Co., Ltd.), Surflon 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 PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA), Futegent Examples include 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 U-120E (Unichem Corporation). Furthermore, acrylic compounds having a molecular structure with a functional group containing a fluorine atom, in which the fluorine atom-containing functional group is cleaved and the fluorine atom volatilizes when heat is applied, can also be suitably used as fluorine-based surfactants. Examples of such fluorine-based surfactants include the Megafac DS series manufactured by DIC Corporation (Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), such as Megafac DS-21. Furthermore, as a 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. In addition, block polymers can also be used as fluorine-based surfactants. Furthermore, as a fluorine-based surfactant, a fluorine-containing polymer compound can also be preferably used, which includes a structural unit derived from a (meth)acrylate compound having a fluorine atom and a structural unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkylene oxy groups (preferably ethylene oxy groups, propylene oxy groups). Furthermore, fluorine-containing polymers having ethylenically unsaturated bond-containing groups in their side chains can also be used as fluorine-based surfactants. Examples include Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation). For compounds having a linear perfluoroalkyl group with 7 or more carbon atoms, it is preferable to use alternative materials for PFOA or PFOS as the fluorine-based surfactant, from the viewpoint of improving environmental suitability.

[0351] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters. Specific examples include Pluronic® L10, L31, L61, L62, 10R5, 17R2, 25R2 (all manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1, HYDROPALAT WE 3323 (all manufactured by BASF), Solspers 20000 (all manufactured by Lubrizol Nippon Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), Paionin D-1105, D-6112, D-6112-W, D-6315 (all manufactured by Takemoto Oil & Fat Co., Ltd.), Orfin E1010, Surfinol 104, 400, 440 (all manufactured by Nisshin Chemical Industry Co., Ltd.), and others.

[0352] Examples of silicone-based surfactants include linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

[0353] Specific examples of surfactants include EXP.S-309-2, EXP.S-315, EXP.S-503-2, EXP.S-505-2 (all manufactured by DIC Corporation), DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (all manufactured by Toray Dow Corning Co., Ltd.), as well as X-22-4952, X-22-4272, X-22-626. 6, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF -6001, KF-6002, KP-101KP-103, KP-104, KP-105, KP-106, KP-109, KP-109, KP-112, KP-120, KP-121, KP-124 , KP-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, KP-652 (all manufactured by Shin-Etsu Silicone Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Pa Examples include BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, and BYK323 (all manufactured by Bic Chemie).

[0354] Surfactants can be used individually or in combination of two or more types. If the photosensitive layer contains a surfactant, the surfactant content is preferably 0.01 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, and even more preferably 0.05 to 0.80% by mass, relative to the total mass of the photosensitive layer.

[0355] ...polymerization inhibitors The photosensitive layer may contain a polymerization inhibitor. A polymerization inhibitor is a compound that has the function of delaying or inhibiting a polymerization reaction. For example, known compounds used as polymerization inhibitors can be used.

[0356] Polymerization inhibitors include, for example, phenothiazine compounds such as phenothiazine, bis-(1-dimethylbenzyl)phenothiazine, and 3,7-dioctylphenothiazine; bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, and pentaerythritol tetrakis3-(3,5-di-te Examples include hindered phenol compounds such as rt-butyl-4-hydroxyphenyl)propionate; nitroso compounds or their salts such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, and N-nitrosophenylhydroxylamine; quinone compounds such as methylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, and 4-benzoquinone; phenol compounds such as 4-methoxyphenol, 4-methoxy-1-naphthol, and t-butylcatechol; and metal salt compounds such as copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, and manganese diphenyldithiocarbamate. In particular, in terms of superior effects of the present invention, at least one selected from the group consisting of phenothiazine compounds, nitroso compounds or their salts, and hindered phenol compounds is preferred as the polymerization inhibitor, with phenothiazine, bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid], [ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), p-methoxyphenol, and N-nitrosophenylhydroxylamine aluminum salt being more preferred.

[0357] Polymerization inhibitors may be used individually or in combination of two or more types. If the photosensitive layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and even more preferably 0.02 to 2.0% by mass, relative to the total mass of the photosensitive layer. The content of the polymerization inhibitor is preferably 0.005 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and even more preferably 0.01 to 1.0% by mass, relative to the total mass of the polymerizable compound.

[0358] ...Hydrogen-donating compounds The photosensitive layer may contain a hydrogen-donating compound. Hydrogen-donating compounds have effects such as further improving the sensitivity of photopolymerization initiators to active light and suppressing polymerization inhibition of polymerizable compounds by oxygen.

[0359] Examples of hydrogen-donating compounds include amines and amino acid compounds.

[0360] Examples of amines include compounds described in "Journal of Polymer Society" Vol. 10, p. 3173 (1972) by Mrs. Sander et al., Japanese Patent Publication No. 44-020189, Japanese Unexamined Patent Publication No. 51-082102, Japanese Unexamined Patent Publication No. 52-134692, Japanese Unexamined Patent Publication No. 59-138205, Japanese Unexamined Patent Publication No. 60-084305, Japanese Unexamined Patent Publication No. 62-018537, Japanese Unexamined Patent Publication No. 64-033104, and Research Disclosure No. 33825, etc. More specifically, examples include 4,4'-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (also known as leucocrystal violet), triethanolamine, p-dimethylaminobenzoate ethyl ester, p-formyldimethylaniline, and p-methylthiodimethylaniline. In particular, in terms of exhibiting superior effects of the present invention, at least one amine selected from the group consisting of 4,4'-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane is preferred.

[0361] Examples of amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. In particular, N-phenylglycine is preferred as the amino acid compound because it exhibits superior effects compared to the present invention.

[0362] Examples of hydrogen-donating compounds include organometallic compounds (such as tributyltin acetate) described in Japanese Patent Publication No. 48-042965, hydrogen donors described in Japanese Patent Publication No. 55-034414, and sulfur compounds (such as trithiane) described in Japanese Patent Application Publication No. 6-308727.

[0363] Hydrogen-donating compounds may be used individually or in combination of two or more. When the photosensitive layer contains a hydrogen-donating compound, the hydrogen-donating compound content is preferably 0.01 to 10.0% by mass, more preferably 0.01 to 8.0% by mass, and even more preferably 0.03 to 5.0% by mass, relative to the total mass of the photosensitive layer, in terms of improving the curing rate by balancing the polymerization growth rate and chain transfer.

[0364] ...Impurities etc. The photosensitive layer may contain a predetermined amount of impurities. Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and their ions. Among these, halide ions, sodium ions, and potassium ions are particularly prone to contamination as impurities, so it is preferable to have the following content levels.

[0365] The impurity content in the photosensitive layer is preferably 80 ppm or less by mass, more preferably 10 ppm or less, and even more preferably 2 ppm or less. The impurity content in the photosensitive layer can be 1 ppb or more or 0.1 ppm or more by mass.

[0366] Methods to keep impurities within the above range include selecting raw materials for the photosensitive layer that have a low impurity content, preventing the inclusion of impurities during the formation of the photosensitive layer, and removing them by washing. By such methods, the amount of impurities can be kept within the above range.

[0367] Impurities can be quantified using known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0368] The photosensitive layer preferably contains low amounts of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane. The content of these compounds in the photosensitive layer is preferably 100 ppm or less by mass, more preferably 20 ppm or less, and even more preferably 4 ppm or less. The lower limit can be 10 ppb or more by mass, and can also be 100 ppb or more. The content of these compounds can be suppressed in the same way as the metal impurities mentioned above. Furthermore, they can be quantified by known measurement methods.

[0369] The water content in the photosensitive layer is preferably 0.01 to 1.0% by mass, and more preferably 0.05 to 0.5% by mass, from the viewpoint of improving reliability and lamination.

[0370] ...Remaining monomers The photosensitive layer may contain residual monomers of each constituent unit of the alkali-soluble resin described above. From the viewpoint of patternability and reliability, the residual monomer content is preferably 5,000 ppm by mass or less, more preferably 2,000 ppm by mass or less, and even more preferably 500 ppm by mass or less, relative to the total mass of the alkali-soluble resin. There is no particular lower limit, but it is preferably 1 ppm by mass or more, and more preferably 10 ppm by mass or more. The residual monomers of each constituent unit of the alkali-soluble resin are preferably 3,000 ppm by mass or less, more preferably 600 ppm by mass or less, and even more preferably 100 ppm by mass or less, relative to the total mass of the photosensitive layer, from the viewpoint of patternability and reliability. There is no particular lower limit, but it is preferably 0.1 ppm by mass or more, and more preferably 1 ppm by mass or more.

[0371] It is preferable that the amount of residual monomers when synthesizing alkali-soluble resins by polymer reactions be within the above range. For example, when synthesizing alkali-soluble resins by reacting glycidyl acrylate with a carboxylic acid side chain, it is preferable that the content of glycidyl acrylate be within the above range. The amount of residual monomer can be measured by known methods such as liquid chromatography and gas chromatography.

[0372] ...other ingredients The photosensitive layer may contain components other than those described above (hereinafter also referred to as "other components"). Examples of other components include colorants, antioxidants, and particles (e.g., metal oxide particles). Other additives described in paragraphs

[0058] to

[0071] of Japanese Patent Application Publication No. 2000-310706 may also be considered as other components.

[0373] -particle- Metal oxide particles are preferred as the particles. The metals in metal oxide particles include metalloids such as B, Si, Ge, As, Sb, and Te. The average primary particle diameter of the particles is preferably 1 to 200 nm, and more preferably 3 to 80 nm, from the viewpoint of the transparency of the cured film. The average primary particle diameter of a particle is calculated by measuring the particle diameters of 200 arbitrary particles using an electron microscope and taking the arithmetic mean of the measurement results. If the particle is not spherical, the longest side is used as the particle diameter.

[0374] If the photosensitive layer contains particles, it may contain only one type of particle with different metal types and sizes, or it may contain two or more types. The photosensitive layer is preferably free of particles, or if the photosensitive layer contains particles, the particle content is preferably greater than 0% by mass and 35% by mass or less relative to the total mass of the photosensitive layer; more preferably free of particles, or the particle content is preferably greater than 0% by mass and 10% by mass or less relative to the total mass of the photosensitive composition; even more preferably free of particles, or the particle content is preferably greater than 0% by mass and 5% by mass or less relative to the total mass of the photosensitive layer; even more preferably free of particles, or the particle content is preferably greater than 0% by mass and 1% by mass or less relative to the total mass of the photosensitive layer; and particularly preferably free of particles.

[0375] -Coloring agent- The photosensitive layer may contain trace amounts of colorants (pigments, dyes, etc.), but from the viewpoint of transparency, it is preferable that it is substantially free of colorants. If the photosensitive layer contains a coloring agent, the coloring agent content is preferably less than 1% by mass, and more preferably less than 0.1% by mass, relative to the total mass of the photosensitive layer.

[0376] -Antioxidant- 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 chlorhydroquinone; and paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, and paraphenylenediamine. In particular, 3-pyrazolidones are preferred as antioxidants, and 1-phenyl-3-pyrazolidone is more preferred, as they exhibit superior effects compared to the present invention.

[0377] If the photosensitive layer contains an antioxidant, the antioxidant content 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 layer. There is no particular upper limit, but 1% by mass or less is preferred.

[0378] Thickness of the photosensitive layer The thickness of the photosensitive layer is not particularly limited, but is often 30 μm or less. However, in terms of achieving superior effects of the present invention, a thickness of 20 μm or less is preferred, 15 μm or less is more preferred, 10 μm or less is even more preferred, and 5.0 μm or less is particularly preferred. As a lower limit, in terms of achieving superior strength in the film obtained by curing the photosensitive layer, a thickness of 0.60 μm or more is preferred, 1.5 μm or more is more preferred, and 2.0 μm or more is even more preferred. The thickness of the photosensitive layer is calculated as the average value of five arbitrary points measured by cross-sectional observation using a Scanning Electron Microscope (SEM).

[0379] Refractive index of the photosensitive layer The refractive index of the photosensitive layer is preferably 1.47 to 1.56, and more preferably 1.49 to 1.54.

[0380] • Color of the photosensitive layer The photosensitive layer is preferably achromatic. Specifically, the total internal reflection (incident angle 8°, light source: D-65 (2° field of view)) is L in the CIE1976 (L*, a*, b*) color space. * The value is preferably between 10 and 90, a * The value is preferably -1.0 to 1.0, b * The value is preferably between -1.0 and 1.0.

[0381] Furthermore, it is preferable that the pattern obtained by curing the photosensitive layer (cured film of the photosensitive layer) is achromatic. Specifically, total internal reflection (incident angle 8°, light source: D-65 (2° field of view)) in the CIE1976 (L*, a*, b*) color space results in the L of the pattern. * The value is preferably between 10 and 90, and pattern a * The value is preferably between -1.0 and 1.0, and pattern b * The value is preferably between -1.0 and 1.0.

[0382] • Moisture permeability of the photosensitive layer The moisture permeability of the pattern obtained by curing the photosensitive layer (cured photosensitive layer film) at a thickness of 40 μm is 500 g / m² from the viewpoint of corrosion prevention. 2 Preferably, it should be less than 24 hours, and 300 g / m². 2 It is more preferable that the value be less than 24 hours, and 100 g / m². 2 It is even more preferable that it be less than 24 hours. Furthermore, the moisture permeability was measured by exposing the photosensitive layer to i-line radiation at an exposure dose of 300 mJ / cm². 2After exposure, the photosensitive layer is cured by post-baking at 145°C for 30 minutes, and the measurement is performed on the cured film.

[0383] • Refractive index adjusting layer In the second embodiment, the transfer film X2 preferably has a refractive index adjusting layer. Known refractive index adjusting layers can be used as the refractive index adjusting layer. Examples of materials included in the refractive index adjusting layer include binder polymers, polymerizable compounds, metal salts, and particles. The method for controlling the refractive index of the refractive index adjustment layer is not particularly limited and includes, for example, a method using a resin with a predetermined refractive index alone, a method using a resin and particles, and a method using a composite of a metal salt and a resin.

[0384] Examples of binder polymers and polymerizable compounds include the binder polymers and polymerizable compounds described in the "Photosensitive Layer" section above.

[0385] Examples of particles include metal oxide particles and metal particles. There are no particular restrictions on the type of metal oxide particles, and known metal oxide particles can be used. The metals in the metal oxide particles include metalloids such as B, Si, Ge, As, Sb, and Te.

[0386] The average primary particle diameter of the particles is preferably 1 to 200 nm, and more preferably 3 to 80 nm, from the viewpoint of the transparency of the cured film. The average primary particle diameter of a particle is calculated by measuring the particle diameters of 200 arbitrary particles using an electron microscope and taking the arithmetic mean of the measurement results. If the particle is not spherical, the longest side is used as the particle diameter.

[0387] 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, as metal oxide particles, at least one selected from the group consisting of zirconium oxide particles and titanium oxide particles is more preferred, for example, because it is easy to adjust the refractive index.

[0388] 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), calcined 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 (NanoYouth OZ-S30M, manufactured by Nissan Chemical Industries, Ltd.), and zirconium oxide particles (NanoYouth OZ-S30K, manufactured by Nissan Chemical Industries, Ltd.).

[0389] The particles may be used individually or in combination of two or more types. The particle content in the refractive index adjustment layer is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 40 to 85% by mass, relative to the total mass of the refractive index adjustment layer. When titanium oxide is used as the metal oxide particles, the titanium oxide particle content is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 40 to 85% by mass, relative to the total mass of the refractive index adjustment layer.

[0390] The refractive index of the refractive index adjustment layer is preferably higher than that of the photosensitive layer. The refractive index of the refractive index adjustment layer is preferably 1.50 or higher, more preferably 1.55 or higher, even more preferably 1.60 or higher, and particularly preferably 1.65 or higher. The upper limit of the refractive index of the refractive index adjustment layer is preferably 2.10 or lower, more preferably 1.85 or lower, and even more preferably 1.78 or lower.

[0391] The thickness of the refractive index adjustment layer is preferably 50 to 500 nm, more preferably 55 to 110 nm, and even more preferably 60 to 100 nm. The thickness of the refractive index adjustment layer is calculated as the average value of five arbitrary points measured by cross-sectional observation using a scanning electron microscope (SEM).

[0392] • Method for manufacturing a transfer film according to the second embodiment The method for manufacturing the transfer film of the second embodiment is not particularly limited, and known methods can be used. Examples of methods for manufacturing the transfer film 20 include the steps of: applying an intermediate layer forming composition to the surface of a temporary support 11 to form a coating film, and further drying this coating film to form an intermediate layer 13; applying a photosensitive composition to the surface of the intermediate layer 13 to form a coating film, and further drying this coating film to form a photosensitive layer 15; and applying a refractive index adjusting layer forming composition to the surface of the photosensitive layer 15 to form a coating film, and further drying this coating film to form a refractive index adjusting layer 17.

[0393] A transfer film 20 is manufactured by pressing a protective film 21 onto the refractive index adjustment layer 17 of the laminate manufactured by the above manufacturing method. In the second embodiment, the method for manufacturing the transfer film preferably includes a step of providing a protective film 21 so as to contact the side of the refractive index adjustment layer 17 opposite to the side having the temporary support 11, thereby manufacturing a transfer film 20 comprising a temporary support 11, an intermediate layer 13, a photosensitive layer 15, a refractive index adjustment layer 17, and a protective film 21. After manufacturing the transfer film 20 using the above manufacturing method, the transfer film 20 may be wound up to produce and store a roll of transfer film. The roll of transfer film can be provided in its original form for the lamination process with the substrate using the roll-to-roll method described later.

[0394] Alternatively, the transfer film 20 may be manufactured by forming an intermediate layer 13 and a photosensitive layer 15 on a temporary support 11, separately forming a refractive index adjustment layer 17 on a protective film 21, and then laminating the refractive index adjustment layer 17 to the photosensitive layer 15.

[0395] Intermediate layer forming composition and method for forming an intermediate layer The composition for forming the intermediate layer and the method for forming the intermediate layer are the same as those for the transfer film X1 of the first embodiment.

[0396] • Photosensitive composition and method for forming a photosensitive layer In terms of superior productivity, it is preferable that the photosensitive layer in the transfer film X2 be formed by a coating method using a photosensitive composition containing the components constituting the photosensitive layer described above (e.g., binder polymer, polymerizable compound, polymerization initiator, etc.) and a solvent. Specifically, the method for manufacturing the transfer film of the second embodiment is to apply the photosensitive composition onto a temporary support to form a coating film, and then dry this coating film at a predetermined temperature to form a photosensitive layer.

[0397] Organic solvents are preferred as solvents that may be included in the photosensitive composition. Examples of organic solvents include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam, n-propanol, and 2-propanol.

[0398] Furthermore, if necessary, organic solvents with a boiling point of 180-250°C (high-boiling point solvents) can also be used as solvents.

[0399] The solvent may be used alone, or two or more solvents may be used in combination. The total solid content of the photosensitive composition is preferably 5 to 80% by mass, more preferably 5 to 40% by mass, and even more preferably 5 to 30% by mass, based on the total mass of the photosensitive composition. In other words, the solvent content in the photosensitive composition is preferably 20 to 95% by mass, more preferably 60 to 95% by mass, and even more preferably 70 to 95% by mass, based on the total mass of the photosensitive composition.

[0400] The viscosity of the photosensitive composition at 25°C is preferably 1 to 50 mPa·s, more preferably 2 to 40 mPa·s, and even more preferably 3 to 30 mPa·s, from the viewpoint of coatability. The viscosity is measured using a viscometer. As a viscometer, for example, a viscometer manufactured by Toki Sangyo Co., Ltd. (product name: VISCOMETER TV-22) can be suitably used. However, the viscometer is not limited to the above-mentioned viscometer.

[0401] The surface tension of the photosensitive composition at 25°C is preferably 5 to 100 mN / m, more preferably 10 to 80 mN / m, and even more preferably 15 to 40 mN / m, from the viewpoint of coatability. The surface tension is measured using a surface tensiometer. As a surface tensiometer, for example, a surface tensiometer manufactured by Kyowa Interface Science Co., Ltd. (product name: Automatic Surface Tensiometer CBVP-Z) can be suitably used. However, the surface tensiometer is not limited to the above-mentioned surface tensiometer.

[0402] Methods for applying the photosensitive composition include, for example, printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (i.e., slit coating).

[0403] For drying the photosensitive composition coating, heat drying and reduced-pressure drying are preferred methods. The drying temperature is preferably 80°C or higher, and more preferably 90°C or higher. Furthermore, the upper limit is preferably 130°C or lower, and more preferably 120°C or lower. Drying can also be performed by continuously changing the temperature. Furthermore, the drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. There is no particular upper limit to the drying time, but it is preferably 600 seconds or less, and more preferably 300 seconds or less.

[0404] • Composition for forming a refractive index adjusting layer and method for forming a refractive index adjusting layer The refractive index adjusting layer forming composition preferably contains the various components for forming the refractive index adjusting layer described above and a solvent. In the refractive index adjusting layer forming composition, the preferred range of content of each component relative to the total solid content of the composition is the same as the preferred range of 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 adjustment layer. Preferably, it is at least one selected from the group consisting of water and water-miscible organic solvents, and more preferably water or a mixed solvent of water and a water-miscible organic solvent. Examples of water-miscible organic solvents include C1-C3 alcohols, acetone, ethylene glycol, and glycerin, with C1-C3 alcohols being preferred, and methanol or ethanol being more preferred. The solvent may be used alone or in combination of two or more types. The solvent content 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, per 100 parts by mass of the total solids content of the composition.

[0405] The method for forming the refractive index adjustment layer is not particularly limited as long as it is a method capable of forming a layer containing the above components, and examples include known coating methods (slit coating, spin coating, curtain coating, and inkjet coating, etc.).

[0406] For drying the coating film, heat drying and vacuum drying are preferred. The drying temperature is preferably 80°C or higher, and more preferably 90°C or higher. Furthermore, the upper limit is preferably 130°C or lower, and more preferably 120°C or lower. Drying can also be performed by continuously changing the temperature. Furthermore, the drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. There is no particular upper limit to the drying time, but it is preferably 600 seconds or less, and more preferably 300 seconds or less.

[0407] Furthermore, the transfer film of the second embodiment can be manufactured by laminating the protective film onto the refractive index adjustment layer. The method for laminating the protective film onto the refractive index adjustment layer is not particularly limited and includes known methods. Examples of devices used to laminate a protective film onto a refractive index adjustment layer include vacuum laminators and known laminators such as auto-cut laminators. The laminator is preferably equipped with a heat-sensitive roller, such as a rubber roller, and capable of applying pressure and heating.

[0408] The optimal relationship between the physical properties of the temporary support, photosensitive layer, and protective film. Similarly to the transfer film X2 of the second embodiment described above, it is preferable that the physical properties of the temporary support, photosensitive layer, and protective film satisfy one or more of Preferred Embodiment 1, Preferred Embodiment 2, Preferred Embodiment 3, Preferred Embodiment 4, and Preferred Embodiment 5, and it is more preferable that they satisfy all of them. Each of Preferred Embodiment 1, Preferred Embodiment 2, Preferred Embodiment 3, Preferred Embodiment 4, and Preferred Embodiment 5 is as previously described.

[0409] [Manufacturing method for circuit wiring (Manufacturing method for circuit wiring 1)] The present invention also relates to a method for manufacturing circuit wiring. The pattern formed by the manufacturing method of the laminate of the present invention described above can be used as a protective pattern for the seed layer during plating in the manufacturing of circuit wiring using the semi-additive method (SAP).

[0410] The method for manufacturing circuit wiring according to the present invention is: A method for manufacturing circuit wiring, including the method for manufacturing a laminate according to the present invention as described above, The process of forming a seed layer on a substrate to form a substrate with a seed layer (hereinafter also referred to as the "seed layer formation process"), A step (transfer film lamination step) is to laminate the transfer film and the substrate with the seed layer such that the side of the transfer film having a temporary support, an intermediate layer, and a photosensitive layer is in contact with the substrate with the seed layer, thereby obtaining a substrate with a photosensitive layer having the substrate, the seed layer, the photosensitive layer, the intermediate layer, and the temporary support in this order. Between the above-mentioned temporary support and the above-mentioned intermediate layer, there is a step of peeling off the temporary support (temporary support peeling step), The process involves bringing the exposed intermediate layer into contact with the mask and performing an exposure process, and then performing a development process after exposure to form a pattern (pattern formation process), The process involves forming a metal plating layer on the seed layer in the area where the above pattern is not present by a plating process (hereinafter also referred to as the "metal plating layer formation process"), The process of forming a protective layer on the above metal plating layer (hereinafter also referred to as the "protective layer formation process"), The process of removing the above pattern (hereinafter also referred to as the "pattern removal process"), The process includes removing the exposed seed layer to obtain a conductive nanowire (hereinafter also referred to as the "conductive nanowire formation process"), The surface free energy of the surface on the temporary support side of the intermediate layer is 68.0 mJ / m 2 The following applies:

[0411] The method for manufacturing circuit wiring according to the present invention will be described in detail step by step below. While the descriptions of the constituent elements below may be based on a typical embodiment of the present invention, the present invention is not limited to such embodiments.

[0412] [First Embodiment] The first embodiment of the method for manufacturing circuit wiring comprises, in this order, a seed layer formation step, a transfer film lamination step, a temporary support peeling step, a pattern formation step, a metal plating layer formation step, a protective layer formation step, a pattern removal step, and a conductive nanowire formation step, wherein the surface free energy of the surface of the intermediate layer on the temporary support side is 68.0 mJ / m 2 The following applies: Furthermore, the transfer film lamination step, the temporary support peeling step, and the pattern formation step are the same as in the first embodiment of the method for manufacturing the laminate described above, except that the substrate is a substrate with a seed layer, and the preferred embodiment is also the same.

[0413] <<Seed layer formation process>> The seed layer formation process is the process of forming a seed layer on a substrate. Examples of substrates used in this process include the substrate described in the transfer film lamination step in the first embodiment of the method for manufacturing the laminate described above.

[0414] <Seed layer> There are no particular restrictions on the metal included in the seed layer; known metals can be used. Examples of the main components (so-called primary metals) contained in the seed layer include copper, chromium, lead, nickel, gold, silver, tin, and zinc. The term "primary component" refers to the metal present in the largest quantity among the metals contained in the seed layer.

[0415] The thickness of the seed layer is not particularly limited, but is preferably 50 nm or more, and more preferably 100 nm or more. There is no particular upper limit, but is preferably 2 μm or less.

[0416] The method for forming the seed layer is not particularly limited, and known methods include, for example, a method of applying a dispersion of metal nanoparticles and sintering the coating film, sputtering, and vapor deposition.

[0417] <<Metal Plating Layer Formation Process>> The metal plating layer formation process is a process in which a metal plating layer is formed on a seed layer in an area where no pattern is placed, by a plating treatment. Plating methods include electrolytic plating and electroless plating, and electrolytic plating is preferred from the viewpoint of productivity.

[0418] The metal included in the metal plating layer is not particularly limited, and any known metal can be used. The metal plating layer may contain, for example, metals such as copper, chromium, lead, nickel, gold, silver, tin, and zinc, as well as alloys of these metals. In particular, the metal plating layer preferably contains copper or an alloy thereof, as this provides superior conductivity for the conductive nanowire. Furthermore, the main component of the metal plating layer is preferably copper, as this provides superior conductivity for the conductive nanowire.

[0419] There are no particular restrictions on the lower limit of the thickness of the metal plating layer, but it is preferably 0.1 μm or more, and more preferably 1 μm. There are no particular restrictions on the upper limit, but it is preferably 20 μm or less.

[0420] <<Protective layer formation process>> The protective layer lamination process is a process of forming a protective layer on top of the metal plating layer. The protective layer material is preferably one that has resistance to the removal solution or etching solution used in the removal process or the conductive fine wire formation process. Examples include metals such as nickel, chromium, tin, zinc, magnesium, gold, and silver, their alloys, and resins. Among these, nickel or chromium is preferred as the protective layer material.

[0421] Methods for forming the protective layer include, for example, electroless plating and electroplating, with electroplating being preferred.

[0422] There are no particular restrictions on the lower limit of the thickness of the protective layer, but it is preferably 0.3 μm or more, and more preferably 0.5 μm or more. There are no particular restrictions on the upper limit, but it is preferably 3.0 μm or less, and more preferably 2.0 μm or less.

[0423] <<Pattern Removal Process>> The pattern removal process is the process of removing patterns. There are no particular limitations on the method for removing the pattern, but one method is removal by chemical treatment, and a method using a removal solution is preferred. The temperature of the removal solution is preferably 30 to 80°C, and more preferably 50 to 80°C. A preferred method of removal involves immersing a substrate having the pattern to be removed in a removal solution that is being stirred and has a liquid temperature of 50 to 80°C for 1 to 30 minutes.

[0424] Examples of removal solutions include those obtained by dissolving an inorganic or organic alkaline component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixture thereof. Examples of inorganic alkaline components include sodium hydroxide and potassium hydroxide. Examples of organic alkaline components include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds. Alternatively, the substance may be removed using a removal solution by known methods such as the spray method, shower method, and paddle method.

[0425] <<Seed layer removal process>> The seed layer removal process is a process of removing the exposed seed layer to obtain a conductive nanowire. In the seed layer removal process, the metal plating layer formed in the metal plating layer formation process is used as an etching resist to etch the seed layer located in the non-pattern formation region (in other words, the region not protected by the metal plating layer).

[0426] There are no particular limitations on the method for removing part of the seed layer, but it is preferable to use a known etching solution. Examples of known etching solutions include ferric chloride solution, cupric chloride solution, ammonia alkali solution, sulfuric acid-hydrogen peroxide mixture, and phosphoric acid-hydrogen peroxide mixture.

[0427] The upper limit of the wire width of the formed conductive nanowire is preferably 8 μm or less, and more preferably 6 μm or less. There is no particular limit on the lower limit, but it is often 2 μm or more.

[0428] <<Other processes>> The first embodiment of the method for manufacturing circuit wiring may include any steps other than those described above (other steps). For example, the process may include, but is not limited to, the steps described in paragraph

[0172] of International Publication No. 2019 / 022089 for reducing the visible light reflectance, or the step of forming a new conductive layer on an insulating film as described in paragraph

[0172] of International Publication No. 2019 / 022089.

[0429] <Process to reduce visible light reflectance> The first embodiment of the method for manufacturing circuit wiring may include a step of performing a process to reduce the visible light reflectance of some or all of the multiple conductive layers having a substrate. One treatment that reduces visible light reflectivity is oxidation. If the substrate has a conductive layer containing copper, the copper can be oxidized to copper oxide, which blackens the conductive layer and reduces its visible light reflectivity. Treatments for reducing visible light reflectance are described in paragraphs 0017 to 0025 of Japanese Patent Publication No. 2014-150118 and in paragraphs 0041, 0042, 0048, and 0058 of Japanese Patent Publication No. 2013-206315, and the contents described in these publications are incorporated herein by reference.

[0430] <Steps for forming an insulating film, and for forming a new conductive layer on the surface of the insulating film> The first embodiment of the method for manufacturing circuit wiring may also preferably include 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. Through the above process, a second electrode pattern insulated from the first electrode pattern can be formed. The process for forming the insulating film is not particularly limited and includes known methods for forming permanent films. Alternatively, an insulating film with a desired pattern may be formed by photolithography using an insulating photosensitive material. The process of forming a new conductive layer on an insulating film is not particularly limited, and for example, a new conductive layer with a desired pattern may be formed by photolithography using a conductive photosensitive material.

[0431] [Applications of circuit wiring] The circuit wiring manufactured by the first embodiment of the method for manufacturing circuit wiring is preferably used as circuit wiring placed on a support substrate such as a sheet, metal substrate, ceramic substrate, and glass in the manufacturing process film of semiconductor packages, printed circuit boards, and interposer redistribution layers.

[0432] [Manufacturing method for circuit wiring (Manufacturing method for circuit wiring 2)] Although the upper section described a method for forming conductive fine wire patterns on a substrate using a semi-additive method, the method for manufacturing circuit wiring using the laminate manufacturing method of the present invention is not limited thereto. Other methods for manufacturing circuit wiring include: A method for manufacturing circuit wiring, including the method for manufacturing a laminate according to the present invention as described above, A transfer film having a temporary support, an intermediate layer, and a photosensitive layer, is bonded to a conductive substrate (a conductive substrate is, as described above, a substrate comprising at least a support substrate and a conductive layer disposed on the support substrate) such that the surface of the photosensitive layer of the transfer film, opposite to the intermediate layer side, is in contact with the conductive substrate, thereby obtaining a photosensitive substrate having the conductive substrate, the photosensitive layer, the intermediate layer, and the temporary support in this order (however, the conductive substrate is arranged so that the conductive layer faces the photosensitive layer) (transfer film bonding step), Between the above-mentioned temporary support and the above-mentioned intermediate layer, there is a step of peeling off the temporary support (temporary support peeling step), The process involves bringing the exposed intermediate layer into contact with the mask and performing an exposure process, and then performing a development process after exposure to form a pattern (pattern formation process), This includes an etching step (etching step) for etching the conductive layer in areas where the above pattern is not arranged, The surface free energy of the surface on the temporary support side of the intermediate layer is 68.0 mJ / m 2 The following are examples of manufacturing methods. Furthermore, the transfer film lamination step, the temporary support peeling step, and the pattern formation step are the same as in the first embodiment of the method for manufacturing the laminate described above, except that the substrate is a substrate having a conductive layer, and the preferred embodiment is also the same.

[0433] The etching process is a process of etching the conductive layer in areas where no pattern is placed. As for the etching process, known methods can be applied, for example, the methods described in paragraphs

[0209] to

[0210] of Japanese Patent Publication No. 2017-120435, the methods described in paragraphs

[0048] to

[0054] of Japanese Patent Publication No. 2010-152155, etc., wet etching by immersion in an etching solution, and dry etching methods such as plasma etching.

[0434] An example of a device equipped with circuit wiring manufactured by the above manufacturing method is an input device, preferably a touch panel, and more preferably a capacitive touch panel. Furthermore, the above input device can be applied to display devices such as organic EL displays and liquid crystal displays. In a second embodiment of the method for manufacturing circuit wiring, it is also preferable to form the circuit sequentially or simultaneously on both surfaces of the substrate. With this configuration, it is possible to form a touch panel circuit wiring in which a first conductive pattern is formed on one surface of the substrate and a second conductive pattern is formed on the other surface. It is also preferable to form such a touch panel circuit wiring from both sides of the substrate using a roll-to-roll method.

[0435] [Transfer film] This invention also relates to transfer films. The transfer film of the present invention will be described below.

[0436] The transfer film of the present invention is A transfer film having a temporary support, an intermediate layer, and a photosensitive layer, The surface free energy of the surface on the temporary support side of the intermediate layer is 68.0 mJ / m 2 The following: The arithmetic mean roughness Ra of the surface of the intermediate layer on the temporary support side is 50 nm or less. The above transfer film is suitable for exposure methods in which a temporary support is peeled off before exposure, and it can suppress excessive adhesion between the photosensitive layer and the photomask after exposure, while also having excellent resolution.

[0437] The transfer film of the present invention corresponds to one embodiment of the transfer film X described above. The structure and preferred embodiment of the transfer film X are as previously described. [Examples]

[0438] The present invention will be described in more detail below based on the following examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples. Unless otherwise specified, "parts" and "%" are based on mass. Furthermore, in the following examples, the weight-average molecular weight of the resin is the weight-average molecular weight obtained by gel permeation chromatography (GPC) on a polystyrene basis. The acid value used is the theoretical acid value.

[0439] [Various components of transfer film] Below, we will first explain the various components used in the preparation of the transfer film.

[0440] [Middle class] <<Various components of the middle layer>> The various components of the intermediate layer shown in Table 4 are as follows: PVA: (Polyvinyl alcohol: Product name "Kuraray Poval PVA-205" (manufactured by Kuraray Co., Ltd.)) PVP: (Polypyrrolidone: Product name "Polyvinylpyrrolidone K-30" (manufactured by Nippon Shokubai Co., Ltd.)) HPMC: (Hydroxypropyl methylcellulose: Product name "Metrol 60SH-03", manufactured by Shin-Etsu Chemical Co., Ltd.) PEG: (Polyethylene glycol: Product name "Polyethylene Glycol 1,000" (Molecular weight: 900-1000), manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) HPC: (Hydroxypropylcellulose: Product name "HPC-SSL", manufactured by NISSO Corporation) Glycerin: Product name "Glycerin" (Molecular weight: 92.09), manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Bisphenol A: Product name "4,4'-Isopropylidenediphenol" (Molecular weight: 228.29), manufactured by Fujifilm Wako Pure Chemical Corporation.

[0441] <<Composition for forming intermediate layer>> After mixing each component according to the information in Table 4, an intermediate layer-forming composition was prepared by adding a solvent (solvent: a mixed solvent prepared by mixing ion-exchanged water and methanol (manufactured by Mitsubishi Gas Chemical Co., Ltd.) in a mixing ratio (mass ratio) of 40 / 60). Note that the numerical values ​​corresponding to each component listed in the "Composition of the Intermediate Layer (Type and Amount of Components (mass%))" column in Table 4 represent the content of each component relative to the total mass of the intermediate layer.

[0442] [Photosensitive layer] The compositions of photosensitive layers 1 to 4, shown in Table 4, are shown in Table 2.

[0443] [Table 2]

[0444] <<Various components of the photosensitive layer>> The components of the photosensitive layer shown in Table 2 are as follows: <polymer> Polymers P-1 and P-2 were synthesized using known methods. The weight-average molecular weight (Mw) of the synthesized polymers was measured by gel permeation chromatography (GPC) under the following conditions.

[0445] (GPC conditions) Equipment: Tosoh Corporation, Tosoh High-Speed ​​GPC System HLC-8420GPC (product name) Guard column: Manufactured by Tosoh Corporation, HZ-L Separation column: A column consisting of three TSK gel Super HZM-N (product name) columns manufactured by Tosoh Corporation, connected in series. Measurement temperature: 40℃ Eluent: THF (tetrahydrofuran) Flow rate: Sample pump 0.35 mL / min, Reference pump 0.175 mL / min Injection volume: 10μL Detector: Differential refractometer GPC column calibration standard solution: Standard polystyrene manufactured by Tosoh Corporation

[0446] (Synthesis of polymers) In the following synthesis examples, the following abbreviations represent the following compounds, respectively. St: Styrene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) MAA: Methacrylic acid (manufactured by Fujifilm Wako Pure Chemical Corporation) MMA: Methyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) BA: Butyl acrylate (manufactured by Fujifilm Wako Pure Chemical Corporation) PGMEA: Propylene glycol monomethyl ether acetate (manufactured by Showa Denko Corporation) MEK: Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.) V-601: Dimethyl-2,2'-azobis(2-methylpropionate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0447] Synthesis of polymer P-1 PGMEA (116.5 parts) was placed in a three-necked flask and heated to 90°C under a nitrogen atmosphere. A solution containing St (52.0 parts), MAA (29.0 parts), MMA (19.0 parts), V-601 (4.0 parts), and PGMEA (116.5 parts) was added dropwise to the flask solution maintained at 90°C ± 2°C over 2 hours. After the addition was complete, the solution in the flask was stirred at 90°C ± 2°C for 2 hours to obtain polymer P-1 (solid content concentration 30.0% by mass).

[0448] Synthesis of polymer P-2 A solution containing polymer P-2 was obtained by changing the type and amount of monomers used, and under the same conditions as polymer P-1, using the same method. The solid content concentration of the solution containing polymer P-2 was set to 30% by mass.

[0449] The following shows the types of monomers used to synthesize each polymer, as well as the mass percentage and weight-average molecular weight of the constituent units derived from each monomer in each polymer. Polymers P-1 to P-2 are all alkali-soluble resins.

[0450] [Table 3]

[0451] <Other ingredients> The other components contained in the photosensitive layer shown in Table 2 are listed below. (polymerizable compound) BPE-500: 2,2-bis(4-(meth)acryloxypentaethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. • M-270: Polypropylene glycol diacrylate (n≒12), manufactured by Toagosei Co., Ltd. A-TMPT: Trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.

[0452] (Polymerization initiator) • B-CIM: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, Hampford • Irgacure OXE-02 (oxime ester-based photopolymerization initiator, manufactured by BASF Japan) Omnirad 907FF: 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, manufactured by IGM Resins BV. Omnirad 379: 2-Dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-butan-1-one, manufactured by IGM Resins BV.

[0453] (Sensitizer) SB-PI 701: 4,4′-Bis(diethylamino)benzophenone, manufactured by Sanyo Trading Co., Ltd.

[0454] (Chain transfer agent) • Leucocrystal violet: Manufactured by Tokyo Chemical Industry Co., Ltd. • N,N-tetraethyl-4,4-diaminobenzophenone: Manufactured by Hodogaya Chemical Co., Ltd. • N-phenylcarbamoylmethyl-N-carboxymethylaniline (manufactured by Fujifilm Wako Pure Chemical Industries)

[0455] (Coloring agent) • Brilliant Green: Manufactured by Tokyo Chemical Industry Co., Ltd. (Rust inhibitor) • CBT-1: Carboxybenzotriazole, manufactured by Johoku Chemical Co., Ltd. (Polymerization inhibitor) • TDP-G: Phenothiazine, manufactured by Kawaguchi Chemical Co., Ltd. Irganox 245: Hindered phenol antioxidant, manufactured by BASF.

[0456] (Antioxidant) 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone (manufactured by Fujifilm Wako Pure Chemical Industries) (Surfactants) • Megafuck F-552: Surfactant, manufactured by DIC Corporation

[0457] <<Photosensitive compositions 1-4>> Photosensitive compositions 1 to 4 were prepared by mixing each component according to the instructions in Table 2, and then adding methyl ethyl ketone to adjust the solid content concentration to 25% by mass. Note that the numerical values ​​corresponding to each component listed in the component column of Table 2 represent the parts by mass of solids. In other words, each of the above values ​​is intended to represent the blending amount excluding solvents such as diluents.

[0458] [Temporary support] The temporary supports (temporary supports A to F) in Table 4 are shown below. Temporary support A: Lumirror 16KS40 (manufactured by Toray Industries, Inc.) Temporary support B: A support manufactured by the method described later was used. Temporary support C: Toyobo Ester Film E5000 (manufactured by Toyobo Co., Ltd.) Temporary support D: Unipeel TR-1 (manufactured by Unitika Ltd.) Temporary support E: Therapeuil 25WZ (manufactured by Toray Industries, Inc.) Temporary support F: Cosmoshine A4300 (manufactured by Toyobo Co., Ltd.)

[0459] <Method for manufacturing temporary support B> (Preparation of particle-containing layer-forming composition 1) The components were mixed according to the formulation shown below to obtain particle-containing layer-forming composition 1. After preparing particle-containing layer-forming composition 1, it was filtered through a 6 μm filter (F20, manufactured by MAHLE FILM Systems, Inc.), and then degassed using a 2×6 radial flow superphobic filter (manufactured by Polypore, Inc.).

[0460] • Acrylic polymer (AS-563A, manufactured by Daicel Finechem Co., Ltd., solids content 27.5% by mass) 167 parts • Nonionic surfactant (Naroacty CL95, manufactured by Sanyo Chemical Industries, Ltd., solid content 100% by mass) 0.7 parts • Anionic surfactant (Rapizol A-90, manufactured by NOF Corporation, diluted with water to 1% solids by mass) 114.4 parts • Carnauba wax dispersion (Celosol 524, manufactured by Chukyo Oil & Fat Co., Ltd., solid content 30% by mass) 7 parts • Carbodiimide compound (Carbodilite V-02-L2, manufactured by Nisshinbo Inc., diluted with water to 10% solids by mass) 20.9 parts • Matting agent (Snowtex XL, manufactured by Nissan Chemical Corporation, solid content 40% by mass, average particle size 50 nm) 2.8 parts ·Wednesday 690.2 parts

[0461] (Extrusion molding) Pellets of polyethylene terephthalate, polymerized using a citric acid chelate organotitanium complex as described in Japanese Patent Publication No. 5575671, were dried to a moisture content of 50 ppm or less. These pellets were then placed in the hopper of a 30 mm diameter single-screw kneading extruder, melted at 280°C, and extruded. The molten material was passed through a filter (3 μm pore size) and then extruded from the die onto a cooling roll at 25°C to obtain an unstretched film. The extruded melt was then brought into close contact with the cooling roll using an electrostatic application method.

[0462] (stretching, coating) The unstretched film, which was extruded onto a cooling roll using the method described above and solidified, was then subjected to sequential biaxial stretching using the following method to obtain a temporary support having a polyester film with a thickness of 16 μm and a particle-containing layer with a thickness of 40 nm.

[0463] (a) Longitudinal extension An unstretched film was passed between two pairs of nip rolls with different peripheral speeds and stretched in the longitudinal direction (conveying direction). The preheating temperature was 75°C, the stretching temperature was 90°C, the stretching ratio was 3.4 times, and the stretching speed was 1300% / second.

[0464] (b) Application Particle-containing layer-forming composition 1 was applied to one side of a longitudinally stretched film using a bar coater to a thickness of 40 nm after film formation.

[0465] (c) Lateral stretching The film, which had undergone the longitudinal stretching and coating described above, was then stretched transversely using a tenter under the following conditions. -Horizontal stretching conditions- Preheating temperature: 110℃ Stretching temperature: 120℃ Stretching ratio: 4.2x Stretching speed: 50% / sec

[0466] (heat fixation, heat relaxation) Next, the biaxially oriented film, after longitudinal and transverse stretching, was heat-set under the following conditions. Furthermore, after heat-setting, the tenter width was reduced and the film was heat-relaxed under the following conditions. -Heat fixation conditions- Heat fixing temperature: 227℃ Heat setting time: 6 seconds -Thermal relaxation conditions- Thermal relaxation temperature: 190℃ Thermal relaxation rate: 4%

[0467] (winding up) After heat setting and heat relaxation, both ends were trimmed, the ends were knurled with a width of 10 mm, and then the film was wound up under a tension of 40 kg / m. The width was 1.5 m and the length of the roll was 6300 m. The resulting film roll was used as temporary support B.

[0468] [Preparation of photosensitive transfer film] [Examples 1-48, Comparative Examples 5-7] Photosensitive transfer films were prepared, each consisting of a temporary support, an intermediate layer, and a photosensitive layer, as shown in Table 4. Specifically, they were as follows: First, the intermediate layer-forming composition shown in Table 4 was applied to the temporary support shown in Table 4 using a slit nozzle, ensuring that the coating width was 1.0 m and the film thickness was as indicated in Table 4 after drying. The mixture was then passed through an 80°C drying zone for 40 seconds to form the intermediate layer. Furthermore, a photosensitive composition for forming the photosensitive layer shown in Table 4 was applied to the intermediate layer using a slit-shaped nozzle so that, after drying, the coating width was 1.0 m and the film thickness was the value indicated in Table 4. The mixture was then passed through an 80°C drying zone for 40 seconds to form a negative-type photosensitive layer. A polyethylene film (OSM-N, manufactured by Tredeger) was then pressed onto this as a protective film to create a photosensitive transfer film, which was then wound up into a roll.

[0469] Furthermore, following the procedure described above, for example, a transfer film is prepared for use in Example 1, comprising a temporary support of type A, an intermediate layer of type 1, and a photosensitive layer of type 1.

[0470] [Comparative Examples 1-4] Photosensitive transfer films were prepared, each consisting of a temporary support and a photosensitive layer, to have the configuration shown in Table 4. Except for the absence of an intermediate layer, the transfer films were prepared using the same method as those used in Example 1.

[0471] [Surface free energy E on the surface of the temporary support side of the intermediate layer] I , Surface free energy E on the intermediate layer surface of the temporary support s [Arithmetic mean roughness Ra on the surface of the temporary support side of the intermediate layer] The temporary support of the fabricated transfer film is peeled off by any method, and the surface free energy E on the intermediate layer side surface of the temporary support is obtained. s (mJ / cm 2 ), and the surface free energy E on the surface of the temporary support side of the intermediate layer. I (mJ / cm 2 The arithmetic mean roughness Ra of the surface on the temporary support side of the intermediate layer was measured. The measurement method is as previously described. Table 4 shows the measurement results.

[0472] [Various evaluations] [Evaluation 1: Temporary support peelability] A copper layer with a thickness of 200 nm was prepared by vapor deposition on a PET substrate with a thickness of 0.1 mm. After peeling off the protective film from the prepared transfer film, it was laminated onto the copper-layered PET substrate under the following lamination conditions: roll temperature 100°C, linear pressure 1.0 MPa, and linear speed 4.0 m / min, so that the copper layer and the photosensitive layer were in contact. After peeling off the temporary support at a 180° angle, the temporary support and the surface of the photosensitive layer were visually inspected and evaluated based on the following evaluation criteria. Table 4 shows the measurement results. (Evaluation Criteria) "A": The temporary support can be peeled off smoothly. "B": The temporary support can be peeled off, but it makes a sound when peeled off. "C": When the temporary support is removed, the intermediate layer peels off, the temporary support tears, and / or cohesive failure occurs.

[0473] [Evaluation 2: Non-adhesive mask] After the exposure procedure described above, the surface of the photosensitive layer was visually inspected and evaluated based on the following evaluation criteria. Table 4 shows the measurement results. (Evaluation Criteria) "A": The photosensitive layer does not adhere to the mask. "B": The photosensitive layer does not adhere to the mask, but it makes a sound when peeled off. "C": The photosensitive layer adheres to the mask (the mask can be peeled off, but the photosensitive layer will peel off).

[0474] [Rating 3: Resolution] A copper layer with a thickness of 200 nm was prepared by vapor deposition on a PET substrate with a thickness of 0.1 mm. After peeling off the protective film from the prepared transfer film, it was laminated onto the copper-layered PET substrate under the following lamination conditions: roll temperature 100°C, linear pressure 1.0 MPa, and linear speed 4.0 m / min, so that the copper layer and the photosensitive layer were in contact. Next, a photomask with a predetermined line (μm) / space (μm) pattern was used, and after peeling off the temporary support, it was brought into contact with the mask and exposed. A high-pressure mercury lamp with the i-line (365 nm) as the main exposure wavelength was used for exposure. The exposure amount was arbitrarily set so that the top shape of each pattern matched the opening of the mask. Next, shower development was performed with a 1% sodium carbonate aqueous solution at a liquid temperature of 25°C, followed by rinsing with water to form a predetermined pattern on the copper. Next, the resolution was evaluated based on the following evaluation criteria. Table 4 shows the measurement results. In the following, "resolution without inter-pattern residue" means that the recessed areas of the pattern (corresponding to unexposed areas) can be resolved without any residue. (Evaluation Criteria) "AA": L / S = 3μm / 3μm can be resolved without inter-pattern residue. "A": L / S = 6μm / 6μm can be resolved without inter-pattern residue. "B": L / S = 8μm / 8μm can be resolved without inter-pattern residue. "C": L / S = 8μm / 8μm cannot be resolved.

[0475] [Overall rating from 1 to 3] Based on the evaluation results from evaluations 1 to 3, an overall evaluation was conducted according to the following evaluation criteria. <Evaluation Criteria> "AA": Resolution is rated AA, and both mask non-adhesion and temporary support peelability are rated A. "A": Resolution is rated A, and both mask non-adhesion and temporary support peelability are rated A. "B": Resolution is rated A, and either mask non-adhesion or temporary support peelability is rated A, while the other is rated B. "C": Resolution is rated B, and mask non-adhesion and temporary support peelability are rated A or B. "D": Either the resolution is rated C, or the mask non-adhesion is rated C. The provisional support evaluation may be either rating.

[0476] Table 4 is shown below. In Table 4, "Type of photosensitive layer" corresponds to the photosensitive layer number shown in Table 2, as described above. Furthermore, in Table 4, "Presence or absence of temporary support peeling process" indicates whether or not the temporary support peeling process was performed. "A" represents the case where the temporary support peeling process was performed in the manufacturing method of the laminate, and "B" represents the case where the temporary support peeling process was not performed in the manufacturing method of the laminate. Furthermore, in Comparative Examples 1-4 (without an intermediate layer), the surface free energy in the "Type and Properties of Temporary Support" column represents the surface free energy on the photosensitive layer side of the temporary support.

[0477] [Table 4]

[0478] [Table 5]

[0479] [Table 6]

[0480] [Table 7]

[0481] From the results in Table 4, it is clear that in the manufacturing method of the laminate of the example, excessive adhesion between the photosensitive layer and the photomask after exposure can be suppressed (in other words, it has excellent mask non-adhesion properties), and a fine pattern can be formed with suppressed residue in the recessed areas of the pattern (in other words, it also has excellent resolution).

[0482] On the other hand, the desired effect was not obtained in Comparative Examples 1 to 7. As shown in Comparative Examples 1 and 3, when the photosensitive layer and the mask were directly bonded and exposure was performed without forming an intermediate layer, the non-adhesion of the mask was poor. Furthermore, as shown in Comparative Examples 3 and 4, when exposure was performed through a temporary support without forming an intermediate layer and without performing a temporary support peeling step, the resolution was inferior. Furthermore, as shown in Comparative Example 5, when exposure was performed through a temporary support without carrying out the temporary support peeling process, even though an intermediate layer had been formed, the resolution was inferior. Furthermore, as shown in Comparative Examples 6 and 7, the surface free energy E of the surface on the temporary support side of the intermediate layer I 68.0 mJ / cm² 2 When the value exceeded this, both the mask's non-adhesion and resolution were inferior.

[0483] Furthermore, the results from Examples 1-6 and 9 confirmed that resolution is superior when the thickness of the photosensitive layer is 2.0-20 μm (preferably 2.0-10 μm). Furthermore, from the results of Examples 1, 7, 8, 10, 11, and 21-23, it was confirmed that resolution is superior when the upper limit of the compound X content in the intermediate layer is less than 30% by mass (preferably 15% by mass or less) relative to the total mass of the intermediate layer. In addition, it was confirmed that the temporary support peelability is superior when the upper limit of the compound X content in the intermediate layer is 0.5% by mass or more relative to the total mass of the intermediate layer. Furthermore, the results from Examples 1 and 12-14 confirmed that resolution is superior when the thickness of the intermediate layer is 3.0 μm or less. Furthermore, a comparison between Example 1 and Example 15, and between Example 1 and Example 19, confirmed that when compound X is a high molecular weight (preferably a water-soluble cellulose derivative), film plasticization is more suppressed, resulting in superior mask non-adhesion (compound X used in Examples 15 and 19 has a small molecular weight and is easily plasticized). Also, a comparison between Example 1 and Example 17 confirmed that when hydroxypropyl methylcellulose is used among water-soluble cellulose derivatives, the temporary support peelability is superior. A comparison of Example 1 with Examples 24-27 confirmed that the temporary support peelability was superior when the intermediate layer contained compound X. A comparison of Example 1 with Examples 28-33 confirmed that when polyvinyl alcohol, polyvinylpyrrolidone, and compound X are used in combination, the temporary support peelability and resolution are superior (it is presumed that polyvinyl alcohol has low compatibility with compound X, and the combination with polyvinylpyrrolidone improves compatibility, suppressing the deterioration of resolution due to phase separation). From a comparison of Example 1 and Examples 34-39, it was confirmed that when the intermediate layer contains polyvinyl alcohol and polyvinylpyrrolidone, and the mixing ratio (mass ratio) of polyvinyl alcohol to polyvinylpyrrolidone is 5 / 95 to 95 / 5, the mask non-adhesion and temporary support peelability are superior. From a comparison between Example 1 and Examples 43 and 44, the surface free energy of the intermediate layer surface of the temporary support was found to be 25.0 to 50.0 mJ / m². 2 In this case, it was confirmed that the temporary support peelability was superior. A comparison of Examples 44-46 confirmed that resolution is superior when the photosensitive layer material contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and their derivatives. Furthermore, the results of Example 47 confirmed that resolution is superior when the content of styrene-based structural units in the polymer is 30% by mass or more relative to the total mass of the polymer.

[0484] [Example 49: Method for manufacturing a printed circuit board] When the transfer film of Example 48 shown in Table 4 was used as the resist pattern forming material in paragraph 0050 of Japanese Patent Application Publication No. 2019-121740, and the printed circuit board manufacturing method disclosed in the above patent was carried out, a substrate with good wiring without erosion was obtained. The transfer film of the example was also confirmed to be suitable for obtaining a resist pattern for the semi-additive method. [Explanation of Symbols]

[0485] 10, 20 Transfer film 1, 11 Temporary support 3.13 Middle Class 5, 15 Photosensitive layer 7, 19 Composition layer 17 Refractive index adjustment layer 9, 21 Protective film

Claims

1. A transfer film having a temporary support, an intermediate layer, and a photosensitive layer, The surface free energy of the surface of the intermediate layer on the temporary support side is 68.0 mJ / m ２ The following: The arithmetic mean roughness Ra of the surface of the intermediate layer on the temporary support side is 50 nm or less. A transfer film in which the intermediate layer comprises polyvinyl alcohol, polyvinylpyrrolidone, and compound X, which is a water-soluble cellulose derivative and a type of polyether.

2. The surface free energy on the intermediate layer side of the temporary support is 25.0 to 50.0 mJ / m ２ The transfer film according to claim 1.

3. The transfer film according to claim 1, wherein the polyvinyl alcohol content is 5 to 95% by mass relative to the total mass of the intermediate layer.

4. The transfer film according to claim 1, wherein the content of compound X is 0.1% by mass or more and less than 30% by mass with respect to the total mass of the intermediate layer.

5. The transfer film according to claim 1, wherein the compound X comprises hydroxypropyl methylcellulose.

6. The transfer film according to claim 1, wherein the total content of the polyvinyl alcohol and the polyvinylpyrrolidone is 50% by mass or more.

7. The transfer film according to any one of claims 1 to 6, wherein the thickness of the intermediate layer is 3.0 μm or less.

8. The transfer film according to any one of claims 1 to 6, wherein the thickness of the photosensitive layer is 2.0 to 20 μm.

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