Method for manufacturing laminate, method for manufacturing circuit wiring board, and 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] A pattern formation method using a transfer film is widely used because it requires only a few steps to obtain a desired pattern. Specifically, this method involves placing a photosensitive layer on a substrate using a transfer film, exposing the photosensitive layer through a mask, and then developing the layer to form a pattern.

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

[0004] [Patent Document 1] Patent No. 4477077 Summary of the Invention [Problem to be solved by the invention]

[0005] The present inventors, with reference to the exposure method described in Patent Document 1, investigated an exposure method in which a support (temporary support) is peeled off before exposure, and a photomask is placed on the photosensitive composition layer (photosensitive layer) exposed by the peeling, and then the method exposed. They found that when peeling the photomask after exposure, the photosensitive layer and the photomask may 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 the 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 the temporary support is not peeled off and exposure is performed by placing the photomask on the temporary support in order to prevent excessive adhesion between the photosensitive layer and the photomask, the presence of the temporary support separates the exposure light source from the photosensitive layer, which can cause a problem that it is difficult to form a fine pattern in which residues are reduced in areas corresponding to recesses in the pattern (for example, areas corresponding to non-exposed areas in the case of a negative photosensitive layer) (in other words, the resolution is likely to be poor). Therefore, when considering a method for preventing excessive adhesion between the photosensitive layer and the photomask after exposure, it is necessary to ensure excellent resolution.

[0006] Therefore, an object of the present invention is to provide a method for producing a laminate that can suppress excessive adhesion between the photosensitive layer and the photomask after exposure and that also provides excellent resolution of the pattern formed from the photosensitive layer. Another object of the present invention is to provide a method for manufacturing a circuit wiring board. Another object of the present invention is 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 which also has excellent resolution. [Means for solving the problem]

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

[0008] [1] A step of laminating a transfer film having a temporary support, an intermediate layer, and a photosensitive layer to a substrate so that a surface of the photosensitive layer opposite to the intermediate layer side of the transfer film contacts the substrate; a step of peeling off the temporary support between the temporary support and the intermediate layer; a step of bringing the exposed intermediate layer into contact with a mask to perform an exposure process, and then performing a development process after the exposure to form a pattern; The surface free energy of the surface of the intermediate layer on the temporary support side is 68.0 mJ / m 2 The following is a method for producing a laminate. [2] The method for producing a laminate according to [1], wherein the intermediate layer has a surface on the temporary support side with an arithmetic mean roughness Ra of 50 nm or less. [3] The surface free energy of the intermediate layer side of the temporary support is 25.0 to 50.0 mJ / m 2 The method for producing a laminate according to [1] or [2], [4] The 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 a laminate according to [4], wherein the content of the polyvinyl alcohol is 5 to 95% by mass based on the total mass of the intermediate layer. [6] The method for producing a laminate according to any one of [1] to [5], wherein the intermediate layer further contains polyvinylpyrrolidone. [7] The method for producing a laminate according to any one of [1] to [6], wherein the intermediate layer further contains 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 a laminate according to [7], wherein the content of the 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] The method for producing a laminate according to [7] or [8], wherein the compound X includes hydroxypropyl methylcellulose.

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

[11] The method for producing a laminate according to any one of [1] to

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

[12] A method for producing circuit wiring, comprising the method for producing the laminate according to any one of [1] to

[11] , forming a seed layer on the substrate to form a substrate with a seed layer; a step of laminating the transfer film, which has a temporary support, an intermediate layer, and a photosensitive layer, to the substrate with a seed layer so that a surface of the transfer film opposite to the intermediate layer side of the photosensitive layer is in contact with the substrate with a 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; a step of peeling off the temporary support between the temporary support and the intermediate layer; a step of bringing the exposed intermediate layer into contact with a mask to perform an exposure treatment, and then performing a development treatment after the exposure to form a pattern; forming a metal plating layer on the seed layer in an area where the pattern is not disposed by plating; forming a protective layer on the metal plating layer; removing the pattern; removing the exposed seed layer to obtain thin conductive wires; The surface free energy of the surface of the intermediate layer on the temporary support side 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 of the intermediate layer on the temporary support side is 68.0 mJ / m 2 is as follows: The transfer film, wherein the surface of the intermediate layer on the temporary support side has an arithmetic mean roughness Ra of 50 nm or less.

[14] The surface free energy of the intermediate layer side of the temporary support is 25.0 to 50.0 mJ / m 2 The transfer film according to

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

[17] The transfer film according to any one of

[13] to

[16] , wherein the 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 the 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 includes hydroxypropylmethylcellulose.

[21] The transfer film according to any one of

[13] to

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

[22] The transfer film according to any one of

[13] to

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

[0009] According to the present invention, it is possible to provide a method for producing a laminate that can suppress excessive adhesion between a photosensitive layer and a photomask after exposure and can form a pattern with excellent resolution formed from the photosensitive layer. The present invention also provides a method for manufacturing a circuit wiring board. 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 drawings]

[0010] [Figure 1]FIG. 2 is a schematic diagram showing an example of a transfer film X1. [Figure 2] FIG. 10 is a schematic diagram showing an example of a transfer film X2. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In the present specification, in the numerical ranges described in stages, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in the present specification, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples.

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

[0013] In this specification, the term "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, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

[0014] In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​measured by a gel permeation chromatography (GPC) analyzer using a TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation) column, THF (tetrahydrofuran) as an eluent, a differential refractometer as a detector, and polystyrene as a standard substance, and converted using polystyrene as the standard substance. In this specification, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight (Mw). In this specification, unless otherwise specified, the content of metal elements is a value measured using an inductively coupled plasma (ICP) spectroscopic analyzer. In this specification, unless otherwise specified, the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm. In this specification, unless otherwise specified, the hue is a value measured using a color difference meter (CR-221, manufactured by Minolta Co., Ltd.).

[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 aqueous sodium carbonate 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-mentioned solubility conditions.

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

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

[0019] [Method of manufacturing laminate] The method for producing the laminate of the present invention includes the steps of: a step of laminating the transfer film, which has a temporary support, an intermediate layer, and a photosensitive layer, to the substrate so that the surface of the transfer film opposite to the intermediate layer side of the photosensitive layer is in contact with the substrate (hereinafter also referred to as a "transfer film laminating step"); a step of peeling off the temporary support between the temporary support and the intermediate layer (hereinafter also referred to as a "temporary support peeling step"); a step of bringing the exposed intermediate layer into contact with a mask to perform an exposure treatment, and further performing a development treatment after the exposure to form a pattern (hereinafter also referred to as a "pattern formation step"); The surface free energy of the surface of the intermediate layer on the temporary support side is 68.0 mJ / m 2 The following is the result.

[0020] The laminate manufacturing method of the present invention is characterized by providing an intermediate layer between the temporary support and the photosensitive layer, and by setting the surface free energy of this intermediate layer on the temporary support side to a predetermined range or less. According to the laminate manufacturing method of the present invention, excessive adhesion between the photosensitive layer and the photomask after exposure can be suppressed, and the resolution is also excellent.

[0021] The mechanism by which the method for producing a laminate of the present invention achieves the desired effect is not clear, but the present inventors speculate as follows. First, in the method for producing a laminate of the present invention, an intermediate layer is provided between the temporary support and the photosensitive layer, and thus, in the pattern formation step after the temporary support peeling step, the mask and the photosensitive layer are not in direct contact with each other due to the presence of the intermediate layer, and as a result, excessive adhesion between the photosensitive layer and the mask after exposure is suppressed. The present inventors have further investigated the 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 2The present inventors have found that if the thickness exceeds 100 nm, 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 the surface of the intermediate layer becomes rough after peeling the temporary support (increasing the arithmetic mean roughness Ra of the surface of the intermediate layer). Specifically, they have found that if peeling does not occur at the interface between the intermediate layer and the temporary support and partial exposure of the photosensitive layer occurs, excessive adhesion occurs between the exposed photosensitive layer and the mask, making it difficult to peel the mask after exposure. Furthermore, they have found that even if exposure and development can be performed after peeling the temporary support, uniform exposure may be hindered due to the above-mentioned exposure of the photosensitive layer and / or roughening of the surface of the intermediate layer (increasing the arithmetic mean roughness Ra of the surface of the intermediate layer), making it difficult to form a fine pattern with reduced residue in the recessed areas of the pattern.

[0022] Hereinafter, the method for producing a laminate of the present invention will be described in detail for each step. Note that the following explanation of the constituent elements may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In addition, hereinafter, 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 the ability to form a fine pattern with reduced residue in recessed areas of the pattern (hereinafter also referred to as "better resolution") will also be referred to as "better effects of the present invention."

[0023] [First embodiment] The first embodiment of the method for producing a laminate includes the following steps in this order: a transfer film laminating step, a temporary support peeling step, and a pattern forming step. Transfer film laminating step: A step of laminating a transfer film (hereinafter also referred to as "transfer film X") having a temporary support, an intermediate layer, and a photosensitive layer to the substrate so that the surface of the photosensitive layer opposite to the intermediate layer side (the surface of transfer film X opposite to the temporary support side) of the transfer film X is in contact with the substrate. Temporary support peeling step: A step of peeling off the temporary support between the temporary support and the intermediate layer. Pattern formation step: A step of bringing the exposed intermediate layer into contact with a mask to perform an exposure treatment, and then performing a development treatment after the exposure to form a pattern (hereinafter also referred to as the "pattern formation step"). In addition, 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 The following is the result.

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

[0025] <Transfer film lamination process> The transfer film laminating step is a step of laminating a transfer film (transfer film X) having a temporary support, an intermediate layer, and a photosensitive layer to a substrate so that the surface of the transfer film (transfer film X) opposite the intermediate layer side of the photosensitive layer contacts the substrate. Note that if the transfer film X has a protective film, the protective film is peeled off before the laminating step is carried out.

[0026] In laminating, the substrate and the transfer film X are pressed together so that the surfaces of the photosensitive layer on the side opposite to the intermediate layer side are in contact with each other. The method of pressure bonding is not particularly limited, and known transfer methods and lamination methods can be used. Among them, it is preferable to place the surface of the transfer film X opposite to the intermediate layer side of the photosensitive layer on the substrate, and then apply pressure and heat using a roll or the like. For lamination, known laminators such as a vacuum laminator and an auto-cut laminator can be used. The lamination temperature is not particularly limited, but is preferably 70 to 130°C, for example.

[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 the support substrate include a resin substrate, a glass substrate, and a semiconductor substrate. A preferred embodiment of the support substrate is described, for example, in paragraph

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

[0029] From the viewpoints of conductivity and fine line formability, the conductive layer is preferably at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer. Furthermore, the support substrate may have one or more conductive layers disposed thereon. When two or more conductive layers are disposed, it is preferable that the conductive layers are made of different materials. A preferred embodiment of the conductive layer is described, for example, in paragraph

[0141] of WO 2018 / 155193, the contents of which are incorporated herein by reference.

[0030] The conductive substrate is preferably a substrate having at least one of a transparent electrode and a wiring line, and the conductive substrate having such a configuration can be suitably used as a substrate for a touch panel. The transparent electrode can function favorably as an electrode for a touch panel, and is preferably made of a metal oxide film such as ITO (indium tin oxide) or IZO (indium zinc oxide), or a metal mesh or a metal nanowire. Examples of thin metal wires include thin wires of silver and copper, etc. Among these, conductive silver materials such as silver mesh and silver nanowires are preferred.

[0031] The material of the lead wiring is preferably metal. Examples of metals that can be used for the wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, as well as alloys of two or more of these metal elements. The wiring is preferably made of copper, molybdenum, aluminum, or titanium, with copper being particularly preferred.

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

[0033] <<Temporary support peeling process>> 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 off 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 Japanese Patent Application Laid-Open No. 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 The following is the result. The surface free energy of the surface of the intermediate layer on the temporary support side (hereinafter referred to as the "surface free energy E I") refers to the surface free energy of the surface of the intermediate layer on the temporary support side that is exposed by peeling off the temporary support in the temporary support peeling step (the surface of the intermediate layer that is exposed after peeling off the temporary support). Surface free energy E I The upper limit is 68.0 mJ / m 2 65.0 mJ / m or less, and the effect of the present invention is more excellent. 2 Preferably less than 63.0 mJ / m 2 Less than 60.0 mJ / m is more preferable. 2 The lower limit is, for example, 45.0 mJ / m 2 More than 50.0 mJ / m is preferable. 2 More preferably, 55.0 mJ / m or more 2 The above is more preferable. In this specification, the surface free energy E I is calculated by the following method:

[0036] (Method of measuring and calculating surface energy) The surface energy is measured by the contact angle θ of pure water H2O and methylene iodide CH2I2. H2O and θ CH2I2 The surface energy can be determined by the Owens equation (simultaneous equations (A) and (B)) shown below using the above formula. In measuring the surface energy below, the method for peeling the support and the type of the substrate are not particularly limited.

[0037] (Water contact angle (θ H2O )) First, the contact angle of water (θ H2O ) is measured by the following method. After the transfer film is laminated onto the substrate, the temporary support is peeled off. Next, 12 μL of pure water was dropped onto the surface of the intermediate layer facing the temporary support (the surface exposed after the temporary support was peeled off) in an atmosphere of room temperature 25°C and relative humidity 50%, and the contact angle was measured after 20 seconds using a contact angle meter CA-D model (Kyowa Interface Science Co., Ltd.). This measurement was performed a total of five times. The arithmetic mean of the three measurements, excluding the maximum and minimum values, was calculated as the water contact angle (θ H2O )

[0038] (Contact angle of diiodomethane (θ CH2I2 )) Next, the contact angle of diiodomethane (θ CH2I2 ) is measured by the following method. After laminating the transfer film onto the substrate, the temporary support is peeled off. Next, 12 μL of diiodomethane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dropped onto the surface of the intermediate layer facing the temporary support (the surface exposed after peeling off the temporary support) in an atmosphere of 25°C and 50% relative humidity, and the contact angle was measured after 20 seconds using a contact angle meter CA-D model (Kyowa Interface Science Co., Ltd.). This measurement was performed a total of five times. The arithmetic mean of the three measurements excluding the maximum and minimum values ​​of the five measurements was calculated as the contact angle of diiodomethane (θ CH2I2 )

[0039] (Calculation of surface energy based on Owens' formula) θ measured by the above method H2O and θ CH2I2 The values ​​of γ in Table 1 below are substituted into the simultaneous equations (A) and (B) below to obtain the "γs d +γs h The value of "surface energy" is defined as the surface energy. In the following table, when L is H2O, for example, γ L d is γ H2O d When L is CH2I2, for example, γ L d is γ CH2I2 d It is expressed as:

[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 of the intermediate layer on the temporary support side> The arithmetic mean roughness Ra of the surface of the intermediate layer on the temporary support side refers to the arithmetic mean roughness Ra of the surface of the intermediate layer on the temporary support side that is exposed when the temporary support is peeled off in the temporary support peeling process (the surface of 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 of the intermediate layer on the temporary support side is preferably 50 nm or less, more preferably 30 nm or less, and even more preferably 20 nm or less, in order to obtain a more excellent effect of the present invention. The lower limit is, for example, preferably 0 nm or more, more preferably 1 nm or more. In this specification, the arithmetic mean roughness Ra of the surface of the intermediate layer on the temporary support side is a value measured by the following method.

[0043] The arithmetic mean roughness Ra of the surface of the intermediate layer on the temporary support side is measured using the following method. A three-dimensional optical profiler (New View 7300, Zygo) is used to obtain a surface profile of the object under the following conditions. MetroPro version 8.3.2 Microscope Application is used as the measurement and analysis software. Next, the Surface Map screen is displayed using the software, and histogram data is obtained on the Surface Map screen. The arithmetic mean roughness Ra of the surface of the object is obtained from the obtained histogram data.

[0044] <Thickness of the middle layer> The thickness of the intermediate layer is not particularly limited, and the upper limit is, for example, 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, from the viewpoint of achieving superior effects of the present invention. The lower limit is, for example, preferably 50 nm or more, more preferably 100 nm or more, from the viewpoint of achieving superior oxygen permeability. The thickness of the intermediate layer is calculated as the average value of measurements taken at any five points by cross-sectional observation using an SEM (Scanning Electron Microscope).

[0045] <Surface free energy of the intermediate layer side of the temporary support> The surface free energy of the surface of the intermediate layer side of the temporary support (hereinafter referred to as "surface free energy E S ") refers to the surface free energy of the surface of the temporary support on the intermediate layer side that is exposed by peeling off the temporary support in the temporary support peeling step (the surface of the temporary support that is exposed after separation from the intermediate layer). Surface free energy E S The upper limit is, for example, 60.0 mJ / m 2 Preferably less than 54.0 mJ / m 2 Less than 50.0 mJ / m is more preferable. 2 The lower limit is, for example, 20.0 mJ / m 2 The above is preferable, and 25.0 mJ / m is preferable in that the effect of the present invention is more excellent.2 The above is more preferable. In this specification, the surface free energy E S is the surface free energy E of the surface of the intermediate layer on the temporary support side. I This value is calculated in the same manner as above.

[0046] In addition, the surface free energy E I and the surface free energy E S It is also preferable that the following relationship (1) and / or (2) is 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 ) difference is 3.0~40mJ / m 2 (Preferably, 3.0 to 30 mJ / m 2 )

[0047] <<Pattern formation process>> The pattern forming step is a step in which the exposed intermediate layer is brought into contact with a mask to perform an exposure process, and then a development process is performed to form a pattern.

[0048] <Exposure processing> The exposure treatment is a treatment in which the temporary support is peeled off to expose the intermediate layer, and the photosensitive layer of the laminate is then exposed in a pattern. The term "pattern exposure" refers to a form of patterned exposure, that is, exposure in which exposed areas and non-exposed areas exist. The positional relationship between the exposed and unexposed areas in the pattern exposure is not particularly limited and may be adjusted as appropriate. In the exposure treatment, a mask having openings at predetermined positions is placed so as to be in close contact with the intermediate layer exposed by peeling off the temporary support, and then the exposure treatment is carried out. For example, when the photosensitive layer is a negative photosensitive layer, the exposure treatment can cause a curing 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). By performing a development treatment (particularly an alkali development treatment) after the exposure treatment, the unexposed areas of the photosensitive layer are removed, thereby forming a pattern.

[0049] Furthermore, when the photosensitive layer is a negative 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 at least 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 to 200 mJ / cm 2 is preferred, and 10 to 200 mJ / cm 2 is more preferred.

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

[0146] to

[0147] of WO 2018 / 155193, the contents of which are incorporated herein by reference.

[0051] In the first embodiment of the method for producing a laminate, it is preferable to peel off the mask (photomask) used in the exposure treatment after the exposure treatment and before the development treatment is carried out.

[0052] <Development processing> The development process is a process in which the photosensitive layer that has been exposed to light in a pattern obtained by the exposure process is developed to form a pattern. The photosensitive layer can be developed using a developer. For example, when the photosensitive layer is a negative photosensitive layer, the unexposed portions of the photosensitive layer are removed by development using an alkaline developer, thereby forming a pattern in which the openings of the mask are convex.

[0053] In the development treatment, an alkaline aqueous solution is preferably used as the developer. Examples of alkaline compounds that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0054] Examples of the development method include puddle development, shower development, spin development, and dip development.

[0055] In the present specification, examples of the developer that can be suitably used include the developer described in paragraph

[0194] of WO 2015 / 093271, and examples of the development method that can be suitably used include the development method described in paragraph

[0195] of WO 2015 / 093271.

[0056] <<Post-exposure process and post-bake process>> The first embodiment of the method for producing a laminate may include a step of exposing the pattern obtained by the development treatment to light (post-exposure step) and / or a step of heating (post-bake step). When both the post-exposure step and the post-bake step are included, it is preferable to carry out the post-bake step after the post-exposure step. The post-exposure exposure dose is 100 to 5000 mJ / cm 2 is preferred, and 200 to 3000 mJ / cm 2 is more preferred. The post-baking temperature is preferably 80 to 250°C, more preferably 90 to 160°C. The post-baking time is preferably 1 to 180 minutes, more preferably 10 to 60 minutes.

[0057] The position and size of the pattern formed on the substrate through the above-mentioned procedure are not particularly limited. The pattern is preferably a thin line pattern, and its width is preferably 20 μm or less, more preferably 15 μm or less. The lower limit is not particularly limited, but is, for example, 1 μm or more, preferably 5 μm or more.

[0058] <Transfer Film X> Next, the transfer film X will be described. The transfer film X has 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 / m 2 There are no particular limitations on the transfer film as long as it satisfies the following conditions, and any known transfer film can be used. Hereinafter, an embodiment of the transfer film X will be described.

[0059] The configuration of the transfer film X is not particularly limited, and examples thereof include the following configurations. (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-described configurations, the photosensitive layer is preferably a negative photosensitive layer, and is also preferably a colored resin layer. The transfer film X of (1) above may have a two-layer intermediate layer. Specifically, it may have a structure of "temporary support / second intermediate layer / first intermediate layer / photosensitive layer / protective film." Furthermore, the pattern obtained by the laminate manufacturing method of the present invention can be applied to a seed layer protection pattern in a circuit wiring manufacturing method, a wire protection film pattern in a wire protection film manufacturing method, etc., as described below. Therefore, the transfer film X may also be a transfer film for etching resist, or a transfer film for wire protection film. When the transfer film X is a transfer film for etching resist, the configuration of the transfer film X is preferably, for example, the configuration (1) described above. When the transfer film X is a transfer film for wire protection film, the configuration of the transfer film X is preferably, for example, the configuration (1) described above.

[0060] From the viewpoint of preventing the generation of bubbles during the lamination step in the manufacturing method of the laminate described above, the maximum waviness width 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 width is 0 μm or more, preferably 0.1 μm or more, and more preferably 1 μm or more. The maximum width of the undulations of the transfer film X is a value measured by the following procedure. First, transfer film X is cut perpendicular to the main surface to a size of 20 cm long x 20 cm wide to prepare a test sample. If transfer film X has a protective film, the protective film is peeled off. Next, the test sample is placed on a flat, horizontal stage with the surface of the temporary support facing the stage. After placement, a 10 cm square area in the center of the test sample is scanned with a laser microscope (e.g., Keyence VK-9700SP) to obtain a three-dimensional surface image. The minimum concave height is subtracted from the maximum convex height observed in the obtained three-dimensional surface image. This procedure is performed on 10 test samples, and the arithmetic average value is taken as the "maximum waviness width of transfer film X."

[0061] In the following, the intermediate layer and the temporary support will first be described, and then the overall configuration of the transfer film X will be described by taking an example of a specific embodiment. The transfer film X1 of the first embodiment, which will be described later as a specific embodiment of the transfer film X, has a configuration that can be suitably used as a transfer film for etching resist, and the transfer film X2 of the second embodiment has a configuration that can be suitably used as a transfer film for wiring protection film.

[0062] (middle class) The intermediate layer of the transfer film X has a surface free energy (surface free energy E I ) is 68.0 mJ / m 2 The following is the result. In addition, the surface free energy E I means the surface free energy of the surface of the intermediate layer on the temporary support side that is exposed when the temporary support is peeled off from the transfer film X. Surface free energy E I The preferred embodiment and measurement method of are as described above.

[0063] The upper limit of the arithmetic mean roughness Ra of the surface of the intermediate layer of the transfer film X on the temporary support side is preferably 50 nm or less, in order to obtain a better effect of the present invention. The arithmetic mean roughness Ra of the surface of the intermediate layer on the temporary support side is intended to be the arithmetic mean roughness Ra of the surface of the intermediate layer exposed when the temporary support is peeled off from the transfer film X. The preferred embodiment and measurement method for the arithmetic mean roughness Ra of the surface of the intermediate layer are as described above.

[0064] The upper limit of the thickness of the intermediate layer of the transfer film X is preferably 10 μm or less, in terms of achieving better effects of the present invention. The preferred embodiment and measuring 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 ability. The intermediate layer having oxygen blocking ability is preferable because it improves sensitivity during exposure, reduces the time load on the exposure machine, and improves productivity. Furthermore, when the photosensitive layer in the transfer film X is a negative photosensitive layer containing a radical polymerizable compound, there is also the advantage that oxygen inhibition is less likely to occur in the polymerization reaction during exposure. Among these, the intermediate layer is preferably a layer that exhibits low oxygen permeability and disperses or dissolves in water or an alkaline aqueous solution (a 1% by mass aqueous solution of sodium carbonate at 22° C.).

[0066] The intermediate layer preferably contains a resin. The resin preferably contains a water-soluble resin as a part or the whole thereof. Examples of resins that can be used as the water-soluble resin include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins (e.g., water-soluble cellulose derivatives such as hydroxypropyl cellulose and hydroxypropylmethyl cellulose), 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, a copolymer of (meth)acrylic acid / vinyl compound can also be used. As the copolymer of (meth)acrylic acid / vinyl compound, a copolymer of (meth)acrylic acid / allyl (meth)acrylate is preferred, and a copolymer of methacrylic acid / allyl methacrylate is more preferred. When the water-soluble resin is a copolymer of (meth)acrylic acid / vinyl compound, the composition ratio (mol%) of each is, for example, preferably 90 / 10 to 20 / 80, and more preferably 80 / 20 to 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, and the upper limit is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less. The dispersity (Mw / Mn) of the water-soluble resin is preferably 1-10, and more preferably 1-5.

[0068] The water-soluble resin preferably contains one or more of polyvinyl alcohol and polyvinylpyrrolidone, more preferably contains polyvinyl alcohol, and even more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone, in terms of achieving better effects of the present invention and / or better oxygen blocking ability. It is also 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 more preferable to use one or more of polyvinyl alcohol and polyvinylpyrrolidone in combination with a water-soluble cellulose derivative.

[0069] The water-soluble cellulose derivative is not particularly limited, but examples thereof include hydroxyethyl cellulose, hydroxypropylmethyl cellulose, hydroxypropyl cellulose, methyl cellulose, and ethyl cellulose. Examples of polyethers include polyethylene glycol and polypropylene glycol.

[0070] The water-soluble resins may be used alone or in combination of two or more. The content of the water-soluble resin is not particularly limited, but is preferably 50% by mass or more, more preferably 70% by mass or more, relative to the total mass of the intermediate layer, from the viewpoint of achieving better effects of the present invention and / or better oxygen blocking ability. The upper limit is not particularly limited, but is, for example, 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] The intermediate layer may also contain components other than the above resins. The upper limit of the molecular weight of the other component is not particularly limited, and 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, the surface free energy E I In terms of ease of adjusting the viscosity, polyhydric alcohols, alkylene oxide adducts of polyhydric alcohols, phenol derivatives, and amide compounds are preferred, and polyhydric alcohols or phenol derivatives are more preferred. The number of hydroxyl groups contained in the polyhydric alcohols is not particularly limited, and is preferably 2 to 10, for example. Examples of polyhydric alcohols include glycerin, diglycerin, and diethylene glycol. Examples of alkylene oxide adducts of polyhydric alcohols include compounds in which ethylene oxide, propylene oxide, etc. are added to the above-mentioned polyhydric alcohols. The average number of additions is not particularly limited and is, 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 the amide compound include N-methylpyrrolidone.

[0073] When the intermediate layer contains the other components, the other components may be used alone or in combination of two or more. The content of the other components 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% by mass or more, relative to the total mass of the intermediate layer, in order to obtain a more excellent effect of the present invention. The upper limit is not particularly limited, but is preferably less than 30% by mass, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0074] In particular, the intermediate layer preferably contains at least one of polyvinyl alcohol and polyvinylpyrrolidone and a compound X selected from the group consisting of water-soluble cellulose derivatives, polyethers, phenol derivatives, and glycerin, in terms of achieving better effects of the present invention and / or better oxygen blocking ability. When the intermediate layer has the above-mentioned composition, compound X is likely to be unevenly distributed on the surface of the intermediate layer on the temporary support side, and / or a WBL (weak boundary layer) layer due to mixing of the intermediate layer and the photosensitive layer is unlikely to be formed, and the surface free energy E I The arithmetic mean roughness Ra of the surface is easily adjusted to a more appropriate value. I Furthermore, if the arithmetic mean roughness Ra on the surface is adjusted to a more appropriate value, peeling at the interface between the temporary support and the intermediate layer will occur more easily without causing cohesive failure of the intermediate layer when the temporary support is peeled off, and a pattern with excellent resolution will be more easily formed. The composition of the intermediate layer more preferably contains at least one of polyvinyl alcohol and polyvinyl pyrrolidone, and at least one of a water-soluble cellulose derivative and a polyether as the compound X, and is even more preferably contains at least one of polyvinyl alcohol and polyvinyl pyrrolidone, and at least one of a water-soluble cellulose derivative as the compound X, in that plasticization of the intermediate layer is more easily suppressed, and is particularly preferably contains at least one of polyvinyl alcohol and polyvinyl pyrrolidone, and at least one of hydroxypropyl methyl cellulose as the compound X, in that temporary support releasability is more excellent. It is also 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, more preferably 70% by mass or more, based on the total mass of the intermediate layer, in order to achieve the effects of the present invention more effectively. The upper limit is not particularly limited, but is, for example, 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. When the intermediate layer has the above composition, the content of polyvinyl alcohol is preferably 5 to 95% by mass relative to the total mass of the intermediate layer. When the intermediate layer has the above composition, the blending ratio (mass ratio) of polyvinyl alcohol to polyvinylpyrrolidone is preferably 5 / 95 to 95 / 5, more preferably 20 / 80 to 80 / 20, still 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 better achieving the 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. The upper limit is preferably less than 30% by mass, 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 components forming the intermediate layer is easily suppressed, and the resulting roughening of the surface of the intermediate layer is less likely to occur, resulting in better resolution.

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

[0076] The temporary support may have a single-layer structure or a multi-layer structure. The temporary support is preferably a film, more preferably a resin film, which is flexible and does not significantly deform, shrink, or stretch under pressure or under pressure and heat. Examples of the film include polyethylene terephthalate film (for example, biaxially stretched polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film. Among these, a polyethylene terephthalate film is preferred as the temporary support. Furthermore, it is preferable that the film used as the temporary support is free from deformations such as wrinkles and scratches.

[0077] The temporary support preferably has high transparency so that pattern exposure can be performed through the temporary support, and the transmittance at 365 nm is preferably 60% or more, more preferably 70% or more. From the viewpoints of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, it is preferable that the haze of the temporary support is small. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less. From the viewpoint of pattern formation during pattern exposure through the temporary support and the transparency of the temporary support, it is preferable that the number of fine particles, foreign matter, and defects contained in the temporary support is small. The number of fine particles, foreign matter, and defects with a diameter of 1 μm or more in the temporary support is 50 / 10 mm. 2 Preferably less than 10 pieces / 10mm 2 Less than 3 pieces / 10mm is more preferable. 2 Less than 0 / 10mm is more preferable. 2 is particularly preferred.

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

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

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

[0017] to

[0018] of JP 2014-085643 A, paragraphs

[0019] to

[0026] of JP 2016-027363 A, paragraphs

[0041] to

[0057] of WO 2012 / 081680 A, and paragraphs

[0029] to

[0040] of WO 2018 / 179370 A, the contents of which are incorporated herein by reference.

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

[0082] The surface free energy of the surface of the intermediate layer side of the temporary support (surface free energy E S ) is 60.0mJ / m 2 The following is preferred: In addition, the surface free energy E S means the surface free energy of 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 The preferred embodiment and measurement method of are as described above.

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

[0084] (Overall structure of transfer film X) Next, a specific example of the embodiment will be given to explain the overall configuration of the transfer film X. As described above, the transfer film X1 of the first embodiment has a configuration suitable for use as a transfer film for an etching resist, and the transfer film X2 of the second embodiment has a configuration suitable for use as a transfer film for a wiring protection film. The thickness of the photosensitive layer is not particularly limited, but is often 30 μm or less, and is preferably 20 μm or less, more preferably 15 μm or less, even more preferably 10 μm or less, and particularly preferably 5.0 μm or less, from the viewpoint of obtaining a superior effect of the present invention. The lower limit of the thickness is preferably 0.60 μm or more, more preferably 1.5 μm or more, and even more preferably 2.0 μm or more, from the viewpoint of obtaining a film having excellent strength by curing the photosensitive layer. The thickness of the photosensitive layer is calculated as the average value of measurements taken at any five points by cross-sectional observation using an SEM (Scanning Electron Microscope).

[0085] Transfer film X1 of the first embodiment An example of the transfer film X1 of the first embodiment will be described below. The transfer film 10 shown in FIG. 1 has a temporary support 1, a composition layer 7 including an intermediate layer 3 and a photosensitive layer 5, and a protective film 9 in this order. Although the transfer film 10 shown in FIG. 1 has a protective film 9 disposed thereon, the protective film 9 does not necessarily have to be disposed. In FIG. 1, each layer except for the protective film 9 that can be disposed on the temporary support 1 is referred to as a composition layer 7. The elements constituting the transfer film X1 will be described below. Note that the configurations of the intermediate layer and temporary support constituting the transfer film X1 are as described above.

[0086] ·Photosensitive layer After the photosensitive layer is transferred onto the transfer-receiving member, it is exposed to light and developed, thereby forming a pattern on the transfer-receiving member. The photosensitive layer is preferably a negative photosensitive layer. Note that a negative photosensitive layer is a photosensitive layer in which the solubility of the exposed portion in a developer decreases upon exposure. When the photosensitive layer is a negative photosensitive layer, the formed pattern corresponds to a hardened layer.

[0087] When the photosensitive layer is a negative photosensitive layer, it preferably contains a resin, a polymerizable compound, and a polymerization initiator. Furthermore, when the photosensitive layer is a negative photosensitive layer, it is also preferable that the resin contains an alkali-soluble resin (such as polymer A, which is an alkali-soluble resin) as part or all of the resin, as described below. That is, in one embodiment, it is preferable that the photosensitive layer contains a resin containing an alkali-soluble resin, a polymerizable compound, and a polymerization initiator. Such a photosensitive layer (negative photosensitive layer) preferably contains, based on the total mass of the photosensitive layer, 10 to 90 mass % of resin, 5 to 70 mass % of polymerizable compound, and 0.01 to 20 mass % of polymerization initiator. Each component will be described in turn below.

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

[0089] The acid value (mgKOH / g) is the mass [mg] of potassium hydroxide required to neutralize 1 g of sample. The acid value can be determined, for example, according to the method described in JIS K0070:1992. The acid value of polymer A may be adjusted by changing the type of structural unit constituting polymer A and the content of structural units containing an acid group.

[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. The weight-average molecular weight is more preferably 100,000 or less, and even more preferably 60,000 or less. On the other hand, a weight-average molecular weight of 5,000 or more is preferred from the viewpoint of controlling the properties of developed aggregates and the properties of the unexposed film, such as edge fusing and cut-chip resistance, when formed into a negative photosensitive resin laminate. The weight-average molecular weight is more preferably 10,000 or more, even more preferably 20,000 or more, and particularly preferably 30,000 or more. Edge fusing refers to the degree to which the negative photosensitive layer protrudes from the edge of a roll when wound into a roll as a negative photosensitive resin laminate. Cut-chip resistance refers to the degree to which chips fly off when the unexposed film is cut with a cutter. If these chips adhere to the upper surface of the negative photosensitive resin laminate, they will be transferred to a mask in a subsequent exposure step, causing defective products. The polydispersity of polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0. In the present disclosure, the polydispersity is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight). In the present disclosure, the weight average molecular weight and number average molecular weight are values ​​measured using gel permeation chromatography.

[0091] In the negative photosensitive layer, from the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position is shifted during exposure, it is preferable that the polymer A contains structural units based on a monomer having an aromatic hydrocarbon group. 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 the polymer A is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total mass of the polymer A. There is no particular upper limit, but it is preferably 95% by mass or less, more preferably 85% by mass or less. When multiple types of polymer A are included, it is preferable that the average content of structural units based on monomers having aromatic hydrocarbon groups falls within the above range.

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

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

[0094] Examples of the monomer having a phenyl alkyl group include phenylethyl (meth)acrylate.

[0095] Examples of the monomer 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. Of 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 structural unit 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, relative to the total mass of polymer A.

[0096] The polymer A containing a structural 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 type of first monomer described below and / or at least one type of second monomer described below.

[0097] The polymer A that does not contain a structural unit based on a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one type of first monomer described below, and more preferably obtained by copolymerizing at least one type of first monomer with at least one type of second monomer described below.

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

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

[0100] Polymer A containing a structural unit based on a monomer having an aralkyl group and / or a structural unit based on a monomer of styrene is preferred from the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position is shifted during exposure. For example, a copolymer containing a structural unit based on methacrylic acid, a structural unit based on benzyl methacrylate, and a structural unit based on styrene, or a copolymer containing a structural unit based on methacrylic acid, a structural unit based on methyl methacrylate, a structural unit based on benzyl methacrylate, and a structural unit based on styrene, is preferred. In one embodiment, polymer A is preferably a polymer containing 25 to 55 mass% of structural units based on a monomer having an aromatic hydrocarbon group, 20 to 35 mass% of structural units based on a first monomer, and 15 to 45 mass% of structural units based on a second monomer. In another embodiment, polymer A is preferably a polymer containing 70 to 90 mass% of structural units based on a monomer having an aromatic hydrocarbon group, and 10 to 25 mass% of structural units based on the first monomer.

[0101] The polymer A may have a linear structure, a branched structure, or an alicyclic structure in the side chain. By using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain, it is possible to introduce a branched structure or an alicyclic structure into the side chain of the polymer A. The group having an alicyclic structure may be monocyclic or polycyclic. Specific examples of monomers containing a group having a branched structure in the side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, tert-amyl (meth)acrylate, sec-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and tert-octyl (meth)acrylate, etc. Among these, isopropyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl methacrylate are preferred, and isopropyl methacrylate or tert-butyl methacrylate is more preferred. Specific examples of monomers containing a group having an alicyclic structure in the side chain include monomers having a monocyclic aliphatic hydrocarbon group and monomers having a polycyclic aliphatic hydrocarbon group, as well as (meth)acrylates having an alicyclic hydrocarbon group with 5 to 20 carbon atoms. More specific examples include (bicyclo[2.2.1]heptyl-2)(meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, 3-methyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-1-adamantyl (meth)acrylate, 3-ethyladamantyl (meth)acrylate, 3-methyl-5-ethyl-1-adamantyl (meth)acrylate, 3,5,8-triethyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-8-ethyl-1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 3-hydroxybenzoic acid (meth)acrylate, and 2-hydroxybenzoic acid (meth)acrylate. Examples include 1-adamantyl (meth)acrylate, octahydro-4,7-menthanoinden-5-yl (meth)acrylate, octahydro-4,7-menthanoinden-1-ylmethyl (meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl (meth)acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fenchyl (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, fenchyl (meth)acrylate, 1-menthyl (meth)acrylate, and tricyclodecane (meth)acrylate are preferred, and cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, and tricyclodecane (meth)acrylate are more preferred.

[0102] The polymer A may be used alone or in combination of two or more. When two or more types are used, it is preferable to mix two types of polymer A containing structural units based on a monomer having an aromatic hydrocarbon group, or to mix a polymer A containing structural units based on a monomer having an aromatic hydrocarbon group with a polymer A that does not contain structural units based on a monomer having an aromatic hydrocarbon group. In the latter case, the proportion of polymer A containing structural units based on a monomer having an aromatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more, based on the total mass of polymer A.

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

[0104] The glass transition temperature Tg of the polymer A is preferably 30 to 135°C. By using a polymer A having a Tg of 135°C or less, it is possible to suppress line width thickening and deterioration of resolution when the focal position is shifted during exposure. From this viewpoint, the Tg of the polymer A is more preferably 130°C or less, further preferably 120°C or less, and particularly preferably 110°C or less. Furthermore, using a polymer A having a Tg of 30°C or more is preferred from the viewpoint of improving edge fuse resistance. From this viewpoint, the Tg of the polymer A is more preferably 40°C or more, further preferably 50°C or more, particularly preferably 60°C or more, and most preferably 70°C or more.

[0105] The negative photosensitive layer may contain, as polymer A, a resin other than 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 the polymer A, an alkali-soluble resin, which will be described later in the description of the thermoplastic resin layer, 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 photosensitive layer. A content of polymer A of 90% by mass or less is preferred from the viewpoint of controlling the development time. On the other hand, a content of polymer A of 10% by mass or more is preferred from the viewpoint of improving edge fuse resistance.

[0108] ...polymerizable compound When the photosensitive layer is a negative photosensitive layer, the negative photosensitive layer preferably contains a polymerizable compound having a polymerizable group. In this specification, the term "polymerizable compound" refers to a compound that is polymerized by the action of a polymerization initiator described later, and is different from the polymer A described above.

[0109] The polymerizable group contained in the polymerizable compound is not particularly limited as long as it is a group that participates in a polymerization reaction, and examples thereof include groups having an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group; and groups having a cationically polymerizable group such as an epoxy group and an oxetane group. The polymerizable group is preferably a group having an ethylenically unsaturated group, more preferably an acryloyl group or a methacryloyl group.

[0110] As the polymerizable compound, a compound having one or more ethylenically unsaturated groups (ethylenically unsaturated compound) is preferred, and a compound having two or more ethylenically unsaturated groups in one molecule (polyfunctional ethylenically unsaturated compound) is more preferred, in that the photosensitivity of the negative-type photosensitive layer is superior. In terms of achieving better resolution and releasability, the number of ethylenically unsaturated groups that the ethylenically unsaturated compound has in one molecule is preferably 6 or less, more preferably 3 or less, and even more preferably 2 or less.

[0111] In order to obtain a better balance between the photosensitivity, resolution, and peelability of the negative photosensitive layer, it is preferable that the negative photosensitive layer contains a bifunctional or trifunctional ethylenically unsaturated compound having two or three ethylenically unsaturated groups in one molecule, and it is more preferable that the negative photosensitive layer contains a bifunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule. The content of the bifunctional ethylenically unsaturated compound relative to the total mass of the polymerizable compounds is preferably 20% by mass or more, more preferably more than 40% by mass, and even more preferably 55% by mass or more, relative to the total mass of the negative photosensitive layer, from the viewpoint of excellent peelability. The upper limit is not particularly limited, and may be 100% by mass. That is, all of the polymerizable compounds may be bifunctional ethylenically unsaturated compounds. Moreover, the ethylenically unsaturated compound is preferably a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group.

[0112] ...Polymerizable compound B1 The negative photosensitive layer preferably contains a polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups. The polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule, among the above-mentioned polymerizable compounds B.

[0113] In the negative photosensitive layer, the mass ratio of the content of the polymerizable compound B1 to the total mass of the polymerizable compounds is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 55% by mass or more, and particularly preferably 60% by mass or more, from the viewpoint of better resolution. The upper limit is not particularly limited, but from the viewpoint of peelability, it is, for example, 100% by mass or less, preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, and particularly preferably 85% by mass or less.

[0114] Examples of the aromatic ring that the polymerizable compound B1 has include aromatic hydrocarbon rings such as benzene ring, naphthalene ring, and anthracene ring, aromatic heterocycles such as thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring, and pyridine ring, and condensed rings thereof, and aromatic hydrocarbon rings are preferred, and benzene ring is more preferred. Note that the aromatic ring may have a substituent. The polymerizable compound B1 may have only one aromatic ring, or may have two or more aromatic rings.

[0115] The polymerizable compound B1 preferably has a bisphenol structure, from the viewpoint of improving resolution by suppressing swelling of the photosensitive layer due to a developer. Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), a bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and a bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), with the bisphenol A structure being preferred.

[0116] Examples of the polymerizable compound B1 having a bisphenol structure include a compound having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. The two polymerizable groups may be bonded to both ends of the bisphenol structure directly or via one or more alkyleneoxy groups. The alkyleneoxy groups added to both ends of the bisphenol structure are preferably ethyleneoxy groups or propyleneoxy groups, more preferably ethyleneoxy groups. The number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14 per molecule. The polymerizable compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP-A-2016-224162, the contents of which are incorporated herein by reference.

[0117] As the 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 Co., Ltd.), and 2,2-bis(4-(methacryloxydodecaethoxy)phenyl)propane. Examples of suitable ethoxylated bisphenol A diacrylates include 2,2-bis(4-(methacryloxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.), and ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0118] The polymerizable compound B1 is also preferably a compound represented by the following general formula (B1).

[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 each independently represent an integer of 1 to 39, and n1 + n3 is an integer of 2 to 40. n2 and n4 each independently represent an integer of 0 to 29, and n2 + n4 is an integer of 0 to 30. The arrangement of the -(AO)- and -(BO)- structural units 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. Furthermore, n2+n4 is preferably 0 to 10, more preferably 0 to 4, even more preferably 0 to 2, and particularly preferably 0.

[0121] The polymerizable compound B1 may be used alone or in combination of two or more. The content of the polymerizable compound B1 is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the negative photosensitive layer from the viewpoint of better resolution. The upper limit is not particularly limited, but from the viewpoints of transferability and edge fusion (a phenomenon in which a photosensitive resin oozes out from the edge of a transfer member), it is preferably 70% by mass or less, more preferably 60% by mass or less.

[0122] The negative photosensitive layer may contain a polymerizable compound other than the above-mentioned polymerizable compound B1. The polymerizable compound other than the polymerizable compound B1 is not particularly limited and can be appropriately selected from known compounds, such as a compound having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compound), a bifunctional ethylenically unsaturated compound having no aromatic ring, and a trifunctional or higher ethylenically unsaturated compound.

[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 the difunctional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate. Examples of alkylene glycol di(meth)acrylates include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate. 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. Commercially available products include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.).

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

[0126] Examples of alkylene oxide-modified tri- or higher functional ethylenically unsaturated compounds include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel-Allnex Corporation, etc.), ethoxylated glycerin triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), ARONIX (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), ARONIX M-520 (manufactured by Toagosei Co., Ltd.), and ARONIX M-510 (manufactured by Toagosei Co., Ltd.).

[0127] Furthermore, a polymerizable compound having an acid group (such as a carboxy group) may be used as the polymerizable compound. The acid group may form an acid anhydride group. Examples of polymerizable compounds having an acid group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and Aronix (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.). As the polymerizable compound having an acid group, for example, the polymerizable compounds having an acid group described in paragraphs 0025 to 0030 of JP-A No. 2004-239942 may be used.

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

[0129] The molecular weight (weight average molecular weight when the polymerizable compound (including polymerizable compound B1) has a molecular weight distribution) is preferably from 200 to 3,000, more preferably from 280 to 2,200, and even more preferably from 300 to 2,200.

[0130] Polymerization initiator When the photosensitive layer is a negative photosensitive layer, the negative photosensitive layer preferably contains a polymerization initiator. The polymerization initiator is selected depending on the type of polymerization reaction, and examples thereof include a thermal polymerization initiator and a photopolymerization initiator. The polymerization initiator may be a radical polymerization initiator or a cationic polymerization initiator.

[0131] The negative photosensitive layer preferably contains a photopolymerization initiator. A photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound when exposed to actinic rays such as ultraviolet light, visible light, and X-rays. The photopolymerization initiator is not particularly limited, and any known photopolymerization initiator can be used. Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferred.

[0132] Examples of the photoradical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α-aminoalkylphenone structure, a photopolymerization initiator having an α-hydroxyalkylphenone structure, a photopolymerization initiator having an acylphosphine oxide structure, and a photopolymerization initiator having an N-phenylglycine structure.

[0133] From the viewpoints of photosensitivity, visibility of exposed and unexposed areas, and resolution, the negative-type photosensitive layer preferably contains, as a photoradical polymerization initiator, at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof. Note that the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimers and derivatives thereof may be the same or different. Examples of derivatives of 2,4,5-triarylimidazole dimers 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 the photoradical polymerization initiator, for example, polymerization initiators described in paragraphs 0031 to 0042 of JP-A No. 2011-95716 and paragraphs 0064 to 0081 of JP-A No. 2015-14783 may be used.

[0135] Examples of the photoradical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (trade name: manufactured by Midori Chemical Industry Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (trade name: manufactured by Midori Chemical Industry Co., Ltd.), IrgacureOXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad651 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] Commercially available photoradical polymerization initiators include, for example, 1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), IRGACURE OXE-04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins), and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (trade name: IRGACURE OXE-03, manufactured by BASF). BV), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907, IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (trade name: Omnirad 127, IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (trade name: Omnirad 369, IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, IGM Resins BV), 1-hydroxycyclohexyl phenyl ketone (trade name: Omnirad 184, IGM Resins BV), BV), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651, IGM Resins BV), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, IGM Resins BV), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, IGM Resins BV)Manufactured by DKSH Japan), oxime ester photoinitiator (trade name: Lunar 6, manufactured by DKSH Japan), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (trade name: Omnirad 907FF, manufactured by IGM Resins BV), 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-butan-1-one (trade name: Omnirad 379, manufactured by IGM Resins BV). BV), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (trade name: B-CIM, Hampford), and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(o-benzoyloxime) (trade name: TR-PBG-305, Changzhou Strong Electronics New Examples of suitable oxime include 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyloxime) (trade name: TR-PBG-326, Changzhou Strong Electronic New Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, Changzhou Strong Electronic New Materials Co., Ltd.).

[0137] A cationic photopolymerization initiator (photoacid generator) is a compound that generates an acid when exposed to actinic rays. The cationic photopolymerization initiator is preferably a compound that responds to actinic rays with a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but the chemical structure is not limited. Even cationic photopolymerization initiators that are not directly sensitive to actinic rays with a wavelength of 300 nm or more can be preferably used in combination with a sensitizer, as long as they respond to actinic rays with a wavelength of 300 nm or more and generate an acid when used in combination with a sensitizer. The cationic photopolymerization initiator is preferably a cationic photopolymerization initiator that generates an acid with a pKa of 4 or less, more preferably a cationic photopolymerization initiator that generates an acid with a pKa of 3 or less, and particularly preferably a cationic photopolymerization initiator that generates an acid with a pKa of 2 or less. There is no particular restriction on the lower limit of the pKa, but it is preferably, for example, −10.0 or more.

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

[0139] Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Examples of trichloromethyl-s-triazines, diazomethane compounds, and imide sulfonate compounds include those described in paragraphs 0083 to 0088 of JP 2011-221494 A. Examples of oxime sulfonate compounds include those described in paragraphs 0084 to 0088 of WO 2018 / 179640 A.

[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 derivatives thereof.

[0141] The polymerization initiator may be used alone or in combination of two or more. 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, relative to the total mass of the negative-type 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, relative to the total mass of the negative-type photosensitive layer.

[0142] ···Pigment From the viewpoints of the visibility of exposed and unexposed areas, the pattern visibility after development, and resolution, the photosensitive layer preferably contains a dye (also referred to as "dye N") whose maximum absorption wavelength in the wavelength range of 400 to 780 nm during color development is 450 nm or more and whose maximum absorption wavelength changes in response to an acid, a base, or a radical. When dye N is contained, adhesion to adjacent layers (for example, a water-soluble resin layer) is improved, resulting in better resolution, although the detailed mechanism is unknown.

[0143] In this specification, the expression "the maximum absorption wavelength of a dye changes in response to an acid, a base, or a radical" may mean any of an embodiment in which a dye in a colored state is decolorized by an acid, a base, or a radical, an embodiment in which a dye in a decolorized state develops color in response to an acid, a base, or a radical, and an embodiment in which a dye in a colored state changes to a colored state of another hue. Specifically, dye N may be a compound that changes from a decolorized state to a colored state upon exposure, or a compound that changes from a colored state to a decolored state upon exposure. In this case, the dye may be one whose colored or decolored state changes when an acid, base, or radical is generated and acts within the photosensitive layer upon exposure, or one whose colored or decolored state changes when an acid, base, or radical changes the state (e.g., pH) within the photosensitive layer. Alternatively, the dye may be one whose colored or decolored state changes upon direct stimulation by an acid, base, or radical without exposure.

[0144] In particular, from the viewpoint of the visibility and resolution of exposed and unexposed areas, dye N is preferably a dye whose maximum absorption wavelength changes in response to an acid or a radical, and more preferably a dye whose maximum absorption wavelength changes in response to a radical. When the photosensitive layer is a negative photosensitive layer, the negative photosensitive layer preferably contains, as dye N, both a dye whose maximum absorption wavelength changes in response to radicals, and a photoradical polymerization initiator, from the viewpoints of visibility of exposed and unexposed areas and resolution. From the viewpoint of visibility of exposed and unexposed areas, dye N is preferably a dye that develops color in response to an acid, a base, or a radical.

[0145] An example of the color-developing mechanism of dye N is an embodiment in which a photoradical polymerization initiator, a cationic photopolymerization initiator (photoacid generator), or a photobase generator is added to the photosensitive layer, and after exposure, a radical-reactive dye, an acid-reactive dye, or a base-reactive dye (e.g., a leuco dye) develops color due to a radical, acid, or base generated from the photoradical polymerization initiator, the cationic photopolymerization initiator, or the photobase generator.

[0146] From the viewpoint of visibility of exposed and unexposed areas, dye N preferably has a maximum absorption wavelength of 550 nm or more in the wavelength range of 400 to 780 nm upon color development, more preferably 550 to 700 nm, and even more preferably 550 to 650 nm. Furthermore, dye N may have only one or two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm when it develops color. When dye N has two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm when it develops color, it is sufficient that the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths is 450 nm or longer.

[0147] The maximum absorption wavelength of dye N can be obtained by measuring the transmission spectrum of a solution containing dye N (liquid temperature 25°C) in the range of 400 to 780 nm using a spectrophotometer UV3100 (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 lose color upon exposure include leuco compounds. Examples of dyes that are decolorized by exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes. As the dye N, a leuco compound is preferred from the viewpoint of visibility of exposed and unexposed areas.

[0149] Examples of leuco compounds include leuco compounds having a triarylmethane skeleton (triarylmethane-based dyes), leuco compounds having a spiropyran skeleton (spiropyran-based dyes), leuco compounds having a fluoran skeleton (fluoran-based dyes), leuco compounds having a diarylmethane skeleton (diarylmethane-based dyes), leuco compounds having a rhodamine lactam skeleton (rhodamine lactam-based dyes), leuco compounds having an indolylphthalide skeleton (indolylphthalide-based dyes), and leuco compounds having a leucoauramine skeleton (leucoauramine-based dyes). Among these, triarylmethane dyes or fluoran dyes are preferred, and leuco compounds having a triphenylmethane skeleton (triphenylmethane dyes) or fluoran dyes are more preferred.

[0150] From the viewpoint of visibility of exposed and unexposed areas, the leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring. This allows the lactone ring, sultine ring, or sultone ring of the leuco compound to react with a radical generated from a photoradical polymerization initiator or an acid generated from a photocationic polymerization initiator, thereby converting the leuco compound into a ring-closed state and thereby discoloring, or converting the leuco compound into a ring-open state and thereby developing a color. The leuco compound is preferably a compound having a lactone ring, a sultine ring, or a sultone ring, which develops a color upon ring-opening of the lactone ring, the sultine ring, or the sultone ring by a radical or an acid, and more preferably a compound having a lactone ring, which develops a color upon ring-opening of the lactone ring by a radical or an acid.

[0151] Examples of the dye N include the following dyes and leuco compounds. Specific examples of dyes among the dyes N include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, quinaldine red, rose bengal, metanil yellow, thymolsulfophthalein, xylenol blue, methyl orange, paramethyl red, Congo red, benzopurpurin 4B, α-naphthyl red, Nile blue 2B, Nile blue A, methyl violet, malachite green, parafuchsin, Victoria Pure Blue 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.), and Oil Scarlet #308 (manufactured by Orient Chemical Co., Ltd.). Examples of suitable anti-inflammatory agents include Orient Chemical Industry Co., Ltd.), Oil Red OG (Orient Chemical Industry Co., Ltd.), Oil Red RR (Orient Chemical Industry Co., Ltd.), Oil Green #502 (Orient Chemical Industry Co., Ltd.), Spiron Red BEH Special (Hodogaya Chemical Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-pN,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0152] Specific examples of the leuco compounds among the dyes N include p,p',p"-hexamethyltriaminotriphenylmethane (leuco crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl leucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(Np-tolyl-N-ethyl)aminofluoran, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluoran, 3,6-dimethoxyfluoran, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluoran, 3-(N-cyclohexyl-N-methylamino)- 6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-xylidinofluoran, 3-(N,N-diethylamino)-6-methyl-7-chlorofluoran, 3-(N,N-diethylamino)-6-methoxy-7-aminofluoran, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluoran, 3-(N,N-diethylamino)-7-chlorofluoran, 3-(N,N-di 3-(N,N-Diethylamino)-7-benzylaminofluoran, 3-(N,N-Diethylamino)-7,8-benzofluoran, 3-(N,N-Dibutylamino)-6-methyl-7-anilinofluoran, 3-(N,N-Dibutylamino)-6-methyl-7-xylidinofluoran, 3-Piperidino-6-methyl-7-anilinofluoran, 3-Pyrrolidino-6-methyl-7-anilinofluoran, 3,3-Bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-Bis(1-n-butyl-2- 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthen-3-one.

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

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

[0155] The content of dye N means the content of dye when all of dye N contained in the total mass of the photosensitive layer is in a color-developing state. A method for quantifying the content of dye N will be explained below using a dye that develops color by radicals as an example. Solutions were prepared by dissolving 0.001 g and 0.01 g of dye in 100 mL of methyl ethyl ketone. The photoradical polymerization initiator Irgacure OXE01 (BASF Japan Ltd.) was added to each solution, and radicals were generated by irradiating with 365 nm light, causing all dyes to develop color. The absorbance of each solution was then measured at 25°C using a spectrophotometer (UV3100, Shimadzu Corporation) under atmospheric conditions, and a calibration curve was created. Next, the absorbance of the solution in which all the dye has developed is measured in the same manner as above, except that 3 g of the photosensitive layer is dissolved in methyl ethyl ketone instead of the dye.The content of the dye contained in the photosensitive layer is calculated based on the absorbance of the resulting solution containing the photosensitive layer and a calibration curve. The photosensitive layer 3g is the same as the total solid content 3g in the photosensitive composition.

[0156] ...thermally crosslinkable compound When the photosensitive layer is a negative photosensitive layer, it preferably contains a thermally crosslinkable compound from the viewpoints of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. In this specification, a thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is not considered to be a polymerizable compound but is considered to be a thermally crosslinkable compound. Examples of the thermally crosslinkable compound include methylol compounds and blocked isocyanate compounds. Among these, blocked isocyanate compounds are preferred from the viewpoints of the strength of the resulting cured film and the adhesiveness of the resulting uncured film. Since the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when a resin and / or a polymerizable compound or the like has at least one of a hydroxy group and a carboxy group, the hydrophilicity of the formed film tends to decrease, and the functionality tends to be enhanced when the film obtained by curing the negative photosensitive layer is used as a protective film. The blocked isocyanate compound refers to a compound having a structure in which the isocyanate group of an isocyanate is protected (so-called masked) with a blocking agent.

[0157] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160°C, more preferably 130 to 150°C. The dissociation temperature of a blocked isocyanate means "the temperature of the endothermic peak accompanying the deprotection reaction of the blocked isocyanate when measured by DSC (Differential Scanning Calorimetry) analysis using a differential scanning calorimeter." As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be suitably used, but the differential scanning calorimeter is not limited to this.

[0158] Examples of blocking agents having a dissociation temperature of 100 to 160°C include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)], and oxime compounds (compounds having a structure represented by -C(=N-OH)- in the molecule, such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, and cyclohexanoneoxime). Among these, as the blocking agent having a dissociation temperature of 100 to 160° C., at least one selected from oxime compounds is preferred from the viewpoint of storage stability, for example.

[0159] The blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the film and improving the adhesive strength to the transfer target. A blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by protecting hexamethylene diisocyanate by isocyanuration. Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure in which an oxime compound is used as a blocking agent are preferred from the viewpoints that the dissociation temperature can be more easily adjusted to a preferred range and development residues can be reduced compared to compounds not having an oxime structure.

[0160] The blocked isocyanate compound may have a polymerizable group. The polymerizable group is not particularly limited, and any known polymerizable group can be used, with a radical polymerizable group being preferred. Examples of the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloxy group, a (meth)acrylamide group, and a styryl group, as well as groups having an epoxy group such as a glycidyl group. Of these, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloxy group, and even more preferably an acryloxy group.

[0161] As the blocked isocyanate compound, commercially available products can be used. Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, and the like (all manufactured by Showa Denko K.K.), and the blocked Duranate series (e.g., Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, and the like, manufactured by Asahi Kasei Chemicals Corporation). Furthermore, as the blocked isocyanate compound, a compound having the following structure can also be used.

[0162] [ka]

[0163] The thermally crosslinkable compounds 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 from 1 to 50% by mass, more preferably from 5 to 30% by mass, based on the total mass of the photosensitive layer.

[0164] Other additives In addition to the above components, the photosensitive layer may contain known additives as needed. Examples of additives include radical polymerization inhibitors, sensitizers, plasticizers, heterocyclic compounds (such as triazoles), benzotriazoles, carboxybenzotriazoles, pyridines (such as isonicotinamide), purine bases (such as adenine), and surfactants. 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 is preferred. Other radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. In order to avoid impairing the sensitivity of the photosensitive layer, it is preferable to use nitrosophenylhydroxyamine aluminum salt as the 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 of 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. Examples of carboxybenzotriazoles that can be used include commercially available products such as CBT-1 (Johoku Chemical Industry Co., Ltd.).

[0168] The total content of benzotriazoles and carboxybenzotriazoles is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass, based on 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 improved. On the other hand, when the content is 3% by mass or less, the sensitivity is maintained and the decolorization of the dye is suppressed better.

[0169] The radical polymerization inhibitor is preferably, for example, a hindered phenol compound. Examples of the hindered phenol compound 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 tetrakis-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 the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds. Commercially available sensitizers include, for example, "SB-PI 701" (4,4'-bis(diethylamino)benzophenone) manufactured by Sanyo Trading Co., Ltd.

[0171] The sensitizers may be used alone or in combination of two or more. When the photosensitive layer contains a sensitizer, the content of the sensitizer can be appropriately selected depending on the purpose. From the viewpoints of improving sensitivity to the light source and improving the curing rate by balancing the polymerization rate and chain transfer, the content is preferably 0.01 to 5 mass %, and more preferably 0.05 to 1 mass %, relative to 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 the plasticizer and heterocyclic compound include the compounds described in paragraphs 0097 to 0103 and 0111 to 0118 of WO 2018 / 179640.

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

[0174] The photosensitive layer may further contain known additives such as metal oxide particles, antioxidants, rust inhibitors, dispersants, acid multipliers, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic suspending agents. It is also preferred to contain N-phenylcarbamoylmethyl-N-carboxymethylaniline and / or N,N-tetraethyl-4,4-diaminobenzophenone as a chain transfer agent. Additives contained in the photosensitive layer are described in paragraphs 0165 to 0184 of JP-A No. 2014-085643, the contents of which are incorporated herein by reference.

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

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

[0177] ...Impurities etc. The photosensitive layer may contain a certain amount of impurities. Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Among these, halide ions, sodium ions, and potassium ions are likely to be mixed in as impurities, so it is preferable to set the contents to the following ranges.

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

[0179] Methods for controlling the impurity content within the above range include selecting raw materials for the composition that contain a small amount of impurities, preventing impurities from being mixed in during the preparation of the photosensitive layer, and removing impurities by washing.

[0180] The amount of impurities can be determined by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0181] The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive layer is preferably small, and 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, by mass. The lower limit, based on mass, can be 10 ppb or more, or 100 ppb or more, based on the total mass of the photosensitive layer. The content of these compounds can be reduced in the same manner as for the metal impurities described above. Furthermore, they can be quantified by known measurement methods.

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

[0183] Pigments The photosensitive layer may be a colored resin layer containing a pigment. In order to protect the liquid crystal display window of recent electronic devices, a cover glass having a black frame-shaped light-shielding layer formed on the periphery of the back surface of a transparent glass substrate or the like is sometimes attached. A colored resin layer can be used to form such a light-shielding layer. The pigment may be appropriately selected according to the desired hue, and may be selected from black pigments, white pigments, and pigments of chromatic colors other than black and white. In particular, when a black pattern is to be formed, a black pigment is preferably selected as the pigment.

[0184] As the black pigment, any known black pigment (organic pigment, inorganic pigment, etc.) can be appropriately selected as long as the effects of the present invention are not impaired. Among them, 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 the carbon black, from the viewpoint of surface resistance, carbon black at least a portion of the surface of which is coated with a resin is preferred.

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

[0186] As a pigment other than black pigments, the white pigments described in paragraphs 0015 and 0114 of JP-A No. 2005-007765 can be used. Specifically, among the white pigments, inorganic pigments such as titanium oxide, zinc oxide, lithopone, precipitated calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, and barium sulfate are preferred, titanium oxide or zinc oxide is more preferred, and titanium oxide is even more preferred. As the inorganic pigment, rutile or anatase titanium oxide is more preferred, and rutile titanium oxide is particularly preferred. The surface of titanium oxide may be subjected to a silica treatment, alumina treatment, titania treatment, zirconia treatment, or organic treatment, or may be subjected to two or more of these treatments, which suppresses the catalytic activity of titanium oxide and improves heat resistance, fading resistance, etc. From the viewpoint of reducing the thickness of the photosensitive layer after heating, the surface treatment of the titanium oxide is preferably at least one of alumina treatment and zirconia treatment, and particularly preferably both alumina treatment and zirconia treatment.

[0187] Furthermore, when the photosensitive layer is a colored resin layer, it is also preferable that the photosensitive layer further contains a chromatic pigment other than a black pigment and a white pigment, from the viewpoint of transferability. When a chromatic pigment is contained, the particle size of the chromatic pigment is preferably 0.1 μm or less, and more preferably 0.08 μm or less, in terms of better dispersibility. Examples of chromatic pigments include Victoria Pure Blue BO (Color Index (CI) 42595), Auramine (CI 41000), Fat Black HB (CI 26150), Monolight Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11), Fastel Pink B Supra (CI Pigment Red 81), Monastral Fast Blue (CI Pigment Red 146), and Permanent Yellow GR (CI Pigment Yellow 17). Examples of pigments that can be used include CI Pigment Blue 15), Monolight Fast Black B (CI Pigment Black 1) and carbon, CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red 215, CI Pigment Green 7, CI Pigment Blue 15:1, CI Pigment Blue 15:4, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64, and CI Pigment Violet 23. Of these, CI Pigment Red 177 is preferred.

[0188] When the photosensitive layer contains a pigment, the content of the pigment is preferably more than 3% by mass and not more than 40% by mass, more preferably more than 3% by mass and not more than 35% by mass, even more preferably more than 5% by mass and not more than 35% by mass, and particularly preferably 10% by mass or more and not more than 35% by mass, relative to the total mass of the photosensitive layer.

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

[0190] When the photosensitive layer contains a black pigment and is formed from a photosensitive composition, the black pigment (preferably carbon black) is preferably introduced into the photosensitive composition in the form of a pigment dispersion. The dispersion may be prepared by premixing a black pigment and a pigment dispersant, adding the resulting mixture to an organic solvent (or vehicle), and dispersing the mixture using a disperser. The pigment dispersant may be selected depending on the pigment and solvent, and commercially available dispersants may be used, for example. The vehicle refers to the medium in which the pigment is dispersed when a pigment dispersion is prepared. The vehicle is liquid and includes a binder component that maintains the black pigment in a dispersed state and a solvent component (organic solvent) that dissolves and dilutes the binder component.

[0191] The dispersing machine is not particularly limited, and examples thereof include known dispersing machines such as a kneader, a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill. Furthermore, fine pulverization may be performed by utilizing frictional force through mechanical grinding. For details about dispersing machines and fine pulverization, please refer to the descriptions in "Pigment Dictionary" (Kunizo Asakura, 1st Edition, Asakura Shoten, 2000, pp. 438 and 310).

[0192] The thickness of the photosensitive layer is not particularly limited, but is often 30 μm or less, and is preferably 20 μm or less, more preferably 15 μm or less, even more preferably 10 μm or less, and particularly preferably 5.0 μm or less, from the viewpoint of obtaining a superior effect of the present invention. The lower limit of the thickness is preferably 0.60 μm or more, more preferably 1.5 μm or more, and even more preferably 2.0 μm or more, from the viewpoint of obtaining a film having excellent strength by curing the photosensitive layer. The thickness of the photosensitive layer is calculated as the average value of measurements taken at any five points by cross-sectional observation using an SEM (Scanning Electron Microscope).

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

[0194] The thickness of the protective film is preferably from 1 to 100 μm, more preferably from 5 to 50 μm, even more preferably from 5 to 40 μm, and particularly preferably from 15 to 30 μm. The thickness of the protective film is preferably 1 μm or more in terms of excellent mechanical strength, and is preferably 100 μm or less in terms of being relatively inexpensive.

[0195] In addition, the number of fisheyes with a diameter of 80 μm or more contained in the protective film is 5 / m 2 It is preferable that: "Fisheyes" are foreign matter, unmelted material, and oxidized degradation products of the material that are trapped in the film when the material is thermally melted and then kneaded, extruded, biaxially stretched, cast, or other methods are used to produce the film.

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

[0197] In order to provide good winding properties, the arithmetic mean roughness Ra of the surface of the protective film opposite to the surface 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, and is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less. In order to prevent defects during transfer, the surface roughness Ra of the protective film on the surface 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, and 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 in the measurement of the "arithmetic mean roughness Ra of the intermediate layer side of the temporary support" described above.

[0198] Optimal relationship between the physical properties of the temporary support, photosensitive layer, and protective film In the following description, it is preferable that the physical properties of the temporary support, the photosensitive layer, and the 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 "breaking elongation of the cured film of the photosensitive layer" is measured by exposing a 20 μm thick photosensitive layer to 120 mJ / cm 2 After curing by exposure to 400mJ / cm with a high-pressure mercury lamp 2 The cured film is then subjected to additional exposure at 145°C for 30 minutes, and then subjected to a tensile test. The method for measuring the "arithmetic mean roughness Ra of the intermediate layer side of the temporary support" is as described above. The "arithmetic mean roughness Ra of the surface on the photosensitive layer side of the protective film" is measured in the same manner as the above-mentioned "arithmetic mean roughness Ra of the intermediate layer side of the temporary support."

[0200] Preferred Embodiment 1 In the transfer film X1, the physical properties of the temporary support, the photosensitive layer, and the protective film preferably satisfy all of the following conditions (P1) to (P3). (P1) The cured film obtained by curing the photosensitive layer has a breaking elongation of 15% or more at 120°C. (P2) The arithmetic mean roughness Ra of the surface of the temporary support on the intermediate layer side is 50 nm or less. (P3) The arithmetic mean roughness Ra of the surface of the protective film on the photosensitive layer side is 150 nm or less.

[0201] Preferred Embodiment 2 It is preferable that the physical properties of the temporary support and the photosensitive layer of the transfer film X1 satisfy the following formula (1). X×Y<1500 Formula (1) In formula (1), X represents the breaking elongation (%) of the cured film obtained by curing the photosensitive layer at 120°C, and Y represents the arithmetic mean roughness Ra (nm) of the surface of the temporary support on the intermediate layer side. In the above formula (1), the value represented by X×Y is preferably 750 or less.

[0202] Preferred Embodiment 3 It is preferable that the physical properties of the photosensitive layer of the transfer film X1 satisfy the following condition (P4). (P4) The breaking elongation at 120°C is more than twice as large as the breaking elongation at 23°C of the cured film obtained by curing the photosensitive layer.

[0203] Preferred Embodiment 4 It is preferable that the physical properties of the temporary support and the photosensitive layer of the transfer film X1 satisfy the following formula (2). Y ≦ Z Equation (2) Here, in formula (2), Y represents the arithmetic mean roughness Ra (nm) of the surface of the temporary support on the intermediate layer side, and Z represents the arithmetic mean roughness Ra (nm) of the surface of the protective film on the photosensitive layer side.

[0204] Manufacturing method of transfer film X1 of the first embodiment The method for producing the transfer film X1 of the first embodiment is not particularly limited, and any known method can be used. Examples of methods for manufacturing the transfer film 10 include a method including the steps of applying a composition for forming an intermediate layer to the surface of the temporary support 1 to form a coating film, and then drying this coating film to form the intermediate layer 3, and applying a photosensitive composition to the surface of the intermediate layer 3 to form a coating film, and then drying this coating film to form the 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 reduced-pressure drying. The above-mentioned methods can be applied alone or in combination.

[0205] A protective film 9 is pressed onto the photosensitive layer 5 of the laminate produced by the above-described production method, thereby producing a transfer film 10. As a method for manufacturing the transfer film of the first embodiment, it is preferable to include a step of providing a protective film 9 so that it is in contact with the side of the photosensitive layer 5 opposite the side having the temporary support 1, thereby manufacturing a transfer film 10 comprising the temporary support 1, an intermediate layer 3, the photosensitive layer 5, and the protective film 9. After the transfer film 10 is manufactured by the above manufacturing method, the transfer film 10 may be wound up to produce and store a transfer film in roll form. The transfer film in roll form can be provided in its original form for the lamination step with a substrate in a roll-to-roll system described below.

[0206] Composition for forming an intermediate layer and method for forming an intermediate layer The composition for forming an intermediate layer preferably contains the various components for forming the intermediate layer described above and a solvent. Note that, in the composition for forming an intermediate layer, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the intermediate layer described above. The solvent is not particularly limited as long as it can dissolve or disperse the water-soluble resin, and is preferably at least one selected from the group consisting of water and water-miscible organic solvents, and more preferably water or a mixed solvent of water and a water-miscible organic solvent. Examples of water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, with alcohols having 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred. The solvents may be used alone or in combination of two or more. The content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.

[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 thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.).

[0208] As a method for drying the coating film of the composition for forming an intermediate layer, heat drying and reduced pressure drying are preferred. The drying temperature is preferably 80° C. or higher, more preferably 90° C. or higher, and the upper limit is preferably 130° C. or lower, more preferably 120° C. or lower. Drying can also be performed by changing the temperature continuously. 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 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 photosensitive layer In terms of superior productivity, it is desirable to form the photosensitive layer by a coating method using a photosensitive composition containing the components constituting the photosensitive layer described above (e.g., a binder polymer, a polymerizable compound, a polymerization initiator, etc.) and a solvent.

[0210] The photosensitive composition preferably contains the various components forming the photosensitive layer described above and a solvent. Note that the preferred range of the content of each component in the photosensitive composition 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. Specific examples include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol, ethanol, etc.), ketone solvents (acetone, 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 contains at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. Among these, a mixed solvent 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 more preferred, and a mixed solvent containing at least three of at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, a ketone solvent, and a cyclic ether solvent is even more preferred.

[0212] Examples of alkylene glycol ether solvents include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers (such as propylene glycol monomethyl ether acetate), propylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers, and dipropylene glycol dialkyl ethers. Alkylene glycol ether acetate solvents include, for example, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate. As the solvent, the solvents described in paragraphs 0092 to 0094 of WO 2018 / 179640 and the solvents described in paragraph 0014 of JP 2018-177889 A may be used, the contents of which are incorporated herein by reference. The solvents may be used alone or in combination of two or more. The content of the solvent 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, relative to 100 parts by mass of the total solid content of the composition.

[0213] Examples of methods for applying the photosensitive composition include printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (that is, slit coating).

[0214] As a method for drying the coating film of the photosensitive composition, heat drying and reduced pressure drying are preferred. The drying temperature is preferably 80° C. or higher, more preferably 90° C. or higher, and the upper limit is preferably 130° C. or lower, more preferably 120° C. or lower. Drying can also be performed by changing the temperature continuously. 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 upper limit to the drying time, but it is preferably 600 seconds or less, and more preferably 300 seconds or less.

[0215] Furthermore, by laminating a protective film to the photosensitive layer, the transfer film X1 of the first embodiment can be produced. The method for laminating the protective film to the photosensitive layer is not particularly limited, and known methods can be used. Examples of a device for laminating the protective film to the photosensitive layer include known laminators such as a vacuum laminator and an auto-cut laminator. The laminator is preferably equipped with any heatable roller such as a rubber roller and is capable of applying pressure and heat.

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

[0217] Transfer film X2 of the second embodiment An example of the transfer film X2 of the second embodiment will be described below. The transfer film 20 shown in FIG. 2 has a temporary support 11, an intermediate layer 13, a photosensitive layer 15, a composition layer 19 including a refractive index adjusting layer 17, and a protective film 21, in this order. Although the transfer film 20 shown in FIG. 2 has a protective film 21 disposed thereon, the protective film 21 does not necessarily have to be disposed. Furthermore, although the transfer film 20 shown in FIG. 2 has a refractive index adjusting layer 17 disposed thereon, the refractive index adjusting layer 17 does not necessarily have to be disposed. In FIG. 2, each layer except for the protective film 21 that may be disposed on the temporary support 11 is referred to as a composition layer 17 . The components constituting the transfer film X2 will be described below. The configurations of the intermediate layer and temporary support constituting the transfer film X2 are as described above. The configuration 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 the photosensitive layer is transferred onto the transfer-receiving member, it is exposed to light and developed, thereby forming a pattern on the transfer-receiving member. The photosensitive layer is preferably a negative photosensitive layer. Note that a negative photosensitive layer is a photosensitive layer in which the solubility of the exposed portion in a developer decreases upon exposure. When the photosensitive layer is a negative photosensitive layer, the formed pattern corresponds to a hardened layer.

[0219] Components that can be contained in the photosensitive layer will be described in detail below.

[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 reacting epoxy resins with (meth)acrylic acid, and acid-modified epoxy acrylate resins obtained by reacting epoxy acrylate resins with acid anhydrides.

[0221] One preferred embodiment of the binder polymer is a (meth)acrylic resin, which has excellent alkaline developability and film formability. In this specification, the term "(meth)acrylic resin" refers to a resin having structural units derived from (meth)acrylic compounds. The content of the structural units derived from (meth)acrylic compounds is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on the total structural units of the (meth)acrylic resin. The (meth)acrylic resin may be composed solely of structural units derived from (meth)acrylic compounds, or may contain structural units derived from polymerizable monomers other than (meth)acrylic compounds. That is, the upper limit of the content of structural units derived from (meth)acrylic compounds is 100% by mass or less of all structural units of the (meth)acrylic resin.

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

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

[0224] The (meth)acrylic resin may have a structural unit other than the structural unit derived from the (meth)acrylic compound. The polymerizable monomer that forms the structural unit is not particularly limited as long as it is a compound other than a (meth)acrylic compound that is copolymerizable with a (meth)acrylic compound, and may have a substituent at the α-position or on the aromatic ring, for example, styrene, vinyltoluene, α-methylstyrene, and the like. Examples of suitable carboxylic acids include styrene compounds, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid, maleic anhydride, maleic acid monoesters such as monomethyl maleate, monoethyl maleate, and monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, and crotonic acid. These polymerizable monomers may be used alone or in combination of two or more.

[0225] In order to improve alkaline developability, the (meth)acrylic resin preferably contains a structural unit having an acid group, such as a carboxy group, a sulfo group, a phosphate group, or a phosphonate group. In particular, the (meth)acrylic resin more preferably has a structural unit having a carboxy group, and even more preferably has a structural unit derived from the above-mentioned (meth)acrylic acid.

[0226] The content of structural units having an acid group in the (meth)acrylic resin (preferably structural units derived from (meth)acrylic acid) is preferably 10% by mass or more relative to the total mass of the (meth)acrylic resin in terms of excellent developability. While there is no particular upper limit, it is preferably 50% by mass or less, more preferably 40% by mass or less, in terms of excellent alkali resistance.

[0227] Furthermore, the (meth)acrylic resin more preferably has a structural unit derived from the above-mentioned alkyl (meth)acrylate ester. The content of structural units derived from alkyl (meth)acrylate in the (meth)acrylic resin is preferably 50 to 90 mass %, more preferably 60 to 90 mass %, and even more preferably 65 to 90 mass %, based on all structural units of the (meth)acrylic resin.

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

[0229] Furthermore, in order to achieve better effects of the present invention, the (meth)acrylic resin preferably has at least one selected from the group consisting of structural units derived from methacrylic acid and structural units derived from a methacrylic acid alkyl ester, and more preferably has both structural units derived from methacrylic acid and structural units derived from a methacrylic acid alkyl ester. The total content of the structural units derived from methacrylic acid and the structural units derived from alkyl methacrylate in the (meth)acrylic resin is preferably 40% by mass or more, more preferably 60% by mass or more, based on the total structural units of the (meth)acrylic resin, in order to obtain better effects of the present invention. The upper limit is not particularly limited, and may be 100% by mass or less, preferably 80% by mass or less.

[0230] In addition, in terms of achieving better effects of the present invention, it is also preferable that the (meth)acrylic resin has at least one selected from the group consisting of structural units derived from methacrylic acid and structural units derived from methacrylic acid alkyl esters, and at least one selected from the group consisting of structural units derived from acrylic acid and structural units derived from acrylic acid alkyl esters. In order to obtain better effects of the present invention, the total content of the structural units derived from methacrylic acid and the structural units derived from an alkyl methacrylate ester is preferably in a mass ratio of 60 / 40 to 80 / 20 relative to the total content of the structural units derived from acrylic acid and the structural units derived from an alkyl acrylate ester.

[0231] The (meth)acrylic resin preferably has an ester group at the end, in order to provide excellent developability of the photosensitive layer after transfer. The terminals of the (meth)acrylic resin are composed of moieties derived from the polymerization initiator used in the synthesis. A (meth)acrylic resin having an ester group at its terminal can be synthesized by using a polymerization initiator that generates a radical having an ester group.

[0232] Another preferred embodiment of the binder polymer is an alkali-soluble resin. From the viewpoint of developability, the binder polymer is preferably a binder polymer having an acid value of 60 mgKOH / g or more. Furthermore, the binder polymer is more preferably a resin having a carboxy group with an acid value of 60 mgKOH / g or more (so-called carboxy group-containing resin), and even more preferably a (meth)acrylic resin having a carboxy group with an acid value of 60 mgKOH / g or more (so-called carboxy group-containing (meth)acrylic resin), from the viewpoint that it is easy to thermally crosslink with the crosslinking component by heating and form a strong film. When the binder polymer is a resin having a carboxy group, the three-dimensional crosslinking density can be increased by, for example, adding a thermally crosslinkable compound such as a blocked isocyanate compound to thermally crosslink the resin. Furthermore, when the carboxy group of the resin having a carboxy group is dehydrated and made hydrophobic, the wet heat resistance can be improved.

[0233] The carboxyl group-containing (meth)acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited as long as it satisfies the above-mentioned acid value condition, and can be appropriately selected from known (meth)acrylic resins. For example, among the polymers described in paragraph

[0025] of JP-A No. 2011-095716, carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or more, and among the polymers described in paragraphs

[0033] to

[0052] of JP-A No. 2010-237589, carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or more can be preferably used.

[0234] Another preferred embodiment of the binder polymer is a styrene-acrylic copolymer. In this specification, a styrene-acrylic copolymer refers to a resin having structural units derived from a styrene compound and structural units derived from a (meth)acrylic compound, and the total content of the structural units derived from the styrene compound and the structural units derived from the (meth)acrylic compound is preferably 30% by mass or more, and more preferably 50% by mass or more, of all structural units of the copolymer. The content of the structural units derived from the styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 5 to 80% by mass, based on all structural units of the copolymer. The content of the structural units derived from the (meth)acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20 to 95% by mass, based on all structural units of the copolymer.

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

[0236] Examples of the monomer having a phenyl alkyl group include phenylethyl (meth)acrylate.

[0237] Examples of the monomer 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. Of these, benzyl (meth)acrylate is preferred.

[0238] Furthermore, the binder polymer more preferably has a structural unit represented by the following formula (S) (a structural unit derived from styrene), in terms of achieving better effects of the present invention.

[0239] [ka]

[0240] When the binder polymer has a structural unit having an aromatic ring structure, the content of the structural unit having an aromatic ring structure is preferably 5 to 90 mass %, more preferably 10 to 70 mass %, and even more preferably 20 to 60 mass %, based on the total structural units of the binder polymer, in terms of better effects of the present invention. Furthermore, the content of the structural 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 %, based on the total structural units of the binder polymer, in order to achieve better effects of the present invention. Furthermore, the content of the structural 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 %, based on the total structural units of the binder polymer, in order to achieve better effects of the present invention. In this specification, when the content of a "structural unit" is specified by a molar ratio, the "structural unit" is considered to have the same meaning as a "monomer unit." In addition, in this specification, the "monomer unit" may be modified after polymerization by a polymer reaction or the like. The same applies hereinafter.

[0241] The binder polymer preferably has an aliphatic hydrocarbon ring structure in order to obtain better effects of the present invention. That is, the binder polymer preferably has a structural unit having an aliphatic hydrocarbon ring structure. The aliphatic hydrocarbon ring structure may be monocyclic or polycyclic. In particular, the binder polymer more preferably has a ring structure in which two or more aliphatic hydrocarbon rings are condensed.

[0242] Examples of the ring that constitutes the aliphatic hydrocarbon ring structure in the structural unit having an aliphatic hydrocarbon ring structure include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, and an isoborone ring. Among these, in view of the superior effect of the present invention, a ring in which two or more aliphatic hydrocarbon rings are condensed is preferred, and a tetrahydrodicyclopentadiene ring (tricyclo[5.2.1.0] 2,6 ]decane ring) is more preferred. Examples of monomers that form a structural unit having an aliphatic hydrocarbon ring structure include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate. Furthermore, in terms of achieving better effects of the present invention, the binder polymer more preferably has a structural unit represented by the following formula (Cy), and more preferably has a structural unit represented by the above formula (S) and a structural unit represented by the following formula (Cy).

[0243] [ka]

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

[0245] R in formula (Cy) M is preferably a methyl group. R in formula (Cy) Cy is preferably a monovalent group having an aliphatic hydrocarbon ring structure of 5 to 20 carbon atoms, more preferably a monovalent group having an aliphatic hydrocarbon ring structure of 6 to 16 carbon atoms, and even more preferably a monovalent group having an aliphatic hydrocarbon ring structure of 8 to 14 carbon atoms, in terms of better effects of the present invention. Also, R in formula (Cy) Cy In terms of achieving better effects of the present invention, 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, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, and even more preferably a tetrahydrodicyclopentadiene ring structure. Furthermore, R in formula (Cy) Cy In terms of achieving better effects of the present invention, the aliphatic hydrocarbon ring structure in is preferably a ring structure in which two or more aliphatic hydrocarbon rings are condensed, and more preferably a ring in which two to four aliphatic hydrocarbon rings are condensed. Furthermore, R in formula (Cy) Cyis preferably a group in which the oxygen atom of —C(═O)O— in formula (Cy) is directly bonded to an aliphatic hydrocarbon ring structure, i.e., an aliphatic hydrocarbon ring group, more preferably a cyclohexyl group or a dicyclopentanyl group, and even more preferably a dicyclopentanyl group, in terms of achieving better effects of the present invention.

[0246] The binder polymer may have one type of structural unit having an aliphatic hydrocarbon ring structure, or may have two or more types of structural units. When the binder polymer has a structural unit having an aliphatic hydrocarbon ring structure, the content of the structural unit having an aliphatic hydrocarbon ring structure is preferably 5 to 90 mass %, more preferably 10 to 80 mass %, and even more preferably 20 to 70 mass %, based on the total structural units of the binder polymer, in terms of better effects of the present invention. Furthermore, the content of the structural 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 %, based on the total structural units of the binder polymer, in order to achieve better effects of the present invention. Furthermore, the content of the structural 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 %, based on the total structural units of the binder polymer, in order to achieve better effects of the present invention.

[0247] When the binder polymer has a structural unit having an aromatic ring structure and a structural unit having an aliphatic hydrocarbon ring structure, the total content of the structural units having an aromatic ring structure and the structural units having an aliphatic hydrocarbon ring structure is preferably 10 to 90 mass%, more preferably 20 to 80 mass%, and even more preferably 40 to 75 mass%, based on the total structural units of the binder polymer, in terms of better effects of the present invention. Furthermore, the total content of the structural units having an aromatic ring structure and the structural 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 %, based on the total structural units of the binder polymer, in order to achieve better effects of the present invention. Furthermore, the total content of the structural units represented by the above formula (S) and the structural units represented by the above 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 %, based on the total structural units of the binder polymer, in order to achieve better effects of the present invention. Furthermore, in order to obtain better effects of the present invention, the molar amount nS of the structural unit represented by the above formula (S) and the molar amount nCy of the structural unit represented by the above formula (Cy) in the binder polymer preferably satisfy the relationship shown in the following formula (SCy), more preferably satisfy the following formula (SCy-1), and even more preferably satisfy the following formula (SCy-2). 0.2≦nS / (nS+nCy)≦0.8 Formula (SCy) 0.30≦nS / (nS+nCy)≦0.75 Formula (SCy-1) 0.40≦nS / (nS+nCy)≦0.70 Formula (SCy-2)

[0248] The binder polymer preferably has a structural unit having an acid group, in order to obtain better effects of the present invention. Examples of the acid group include a carboxy group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, with a carboxy group being preferred. As the structural unit having an acid group, a structural unit derived from (meth)acrylic acid shown below is preferred, and a structural unit derived from methacrylic acid is more preferred.

[0249] [ka]

[0250] The binder polymer may have one type of structural unit having an acid group, or two or more types of structural units having an acid group. When the binder polymer has a structural unit having an acid group, the content of the structural unit having an acid group is preferably 5 to 50 mass %, more preferably 5 to 40 mass %, and even more preferably 10 to 30 mass %, based on the total structural units of the binder polymer, in terms of better effects of the present invention. Furthermore, the content of the structural units having an acid group in the binder polymer is preferably 5 to 70 mol %, more preferably 10 to 50 mol %, and even more preferably 20 to 40 mol %, based on the total structural units of the binder polymer, in order to achieve better effects of the present invention. Furthermore, the content of the (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 %, based on the total structural units of the binder polymer, in order to achieve better effects of the present invention.

[0251] The binder polymer preferably has a reactive group, and more preferably has a structural unit having a reactive group, in order to achieve better effects of the present invention. The reactive group is preferably a radically polymerizable group, more preferably an ethylenically unsaturated group. When the binder polymer has an ethylenically unsaturated group, the binder polymer preferably has a structural unit having an ethylenically unsaturated group in a side chain. In this specification, the term "main chain" refers to the relatively longest bond chain in the molecule of the polymer compound that constitutes the resin, and the term "side chain" refers to an atomic group branching off from the main chain. The ethylenically unsaturated group is more preferably an allyl group or a (meth)acryloxy group. Examples of structural units having a reactive group include, but are not limited to, those shown below.

[0252] [ka]

[0253] The binder polymer may have one type of structural unit having a reactive group, or two or more types of structural units. When the binder polymer has a structural unit having a reactive group, the content of the structural unit having a reactive group is preferably 5 to 70 mass %, more preferably 10 to 50 mass %, and even more preferably 20 to 40 mass %, based on the total structural units of the binder polymer, in terms of better effects of the present invention. Furthermore, the content of the structural unit having a reactive group in the binder polymer is preferably 5 to 70 mol %, more preferably 10 to 60 mol %, and even more preferably 20 to 50 mol %, based on the total structural units of the binder polymer, in order to achieve better effects of the present invention.

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

[0255] As the binder polymer, the following polymers X1 to X4 are preferred in terms of achieving better effects of the present invention. Note that the content ratios (a to d) of the respective structural units shown below and the weight average molecular weight Mw can be appropriately changed depending on the purpose, but the following structures are particularly preferred in terms of achieving better effects of 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] JPEG2025188224000009.jpg47106JPEG2025188224000010.jpg47103JPEG2025188224000011.jpg50108

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

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

[0259] [ka]

[0260] In formula P-1, R A1a represents a substituent, n 1a R A1a may be the same or different, and Z 1a represents a divalent group forming a ring containing -C(=O)-OC(=O)-, and n 1a represents an integer greater than or equal to 0.

[0261] R A1a Examples of the substituent represented by the formula include an alkyl group. Z 1a As the alkylene group, an alkylene group having 2 to 4 carbon atoms is preferable, an alkylene group having 2 or 3 carbon atoms is more preferable, and an alkylene group having 2 carbon atoms is even more preferable. n 1a represents an integer greater than or equal to 0. 1a When represents an alkylene group having 2 to 4 carbon atoms, n 1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0. n 1a If represents an integer of 2 or more, there are multiple R A1a may be the same or different. A1a may be bonded to each other to form a ring, but preferably do not bond to each other to form a ring.

[0262] As a structural unit having a carboxylic acid anhydride structure, a structural unit derived from an unsaturated carboxylic acid anhydride is preferred, a structural unit derived from an unsaturated cyclic carboxylic acid anhydride is more preferred, a structural unit derived from an unsaturated aliphatic cyclic carboxylic acid anhydride is even more preferred, a structural unit derived from maleic anhydride or itaconic anhydride is particularly preferred, and a structural unit derived from maleic anhydride is most preferred.

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

[0264] [ka]

[0265] [ka]

[0266] The polymer X may contain one type of structural unit having a carboxylic acid anhydride structure, or two or more types of structural units.

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

[0268] The photosensitive layer may contain only one type of polymer X, or may contain two or more types. When the photosensitive layer contains polymer X, 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, relative to the total mass of the photosensitive layer, in order to obtain better effects of the present invention.

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

[0270] The acid value of the binder polymer is preferably from 10 to 200 mgKOH / g, more preferably from 60 to 200 mgKOH / g, still more preferably from 60 to 150 mgKOH / g, and particularly preferably from 70 to 125 mgKOH / 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 dispersity of the binder polymer is preferably from 1.0 to 6.0, more preferably from 1.0 to 5.0, still more preferably from 1.0 to 4.0, and particularly preferably from 1.0 to 3.0.

[0271] The photosensitive layer may contain only one type of binder polymer, or may contain two or more types of binder polymer. The content of the binder polymer is preferably from 10 to 90% by mass, more preferably from 20 to 80% by mass, and even more preferably from 30 to 70% by mass, based on the total mass of the photosensitive layer, in terms of achieving better effects of the present invention.

[0272] ...polymerizable compound The photosensitive layer may contain a polymerizable compound. The polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include a radically polymerizable group and a cationic polymerizable group, and the radically polymerizable group is preferred.

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

[0274] One preferred embodiment of the 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 independently represents a (meth)acryloyloxy group, R 1 represents a divalent linking group having a chain structure.

[0275] Q in formula (M) 1 and Q 2 In terms of ease of synthesis, Q 1 and Q 2 are preferably the same group. Also, Q in formula (M) 1 and Q 2 is preferably an acryloyloxy group from the viewpoint of reactivity. R in formula (M) 1 As the alkylene group, an alkyleneoxyalkylene group (-L 1 -OL 1 -), or a polyalkyleneoxyalkylene group (-(L 1 -O) p -L 1 -) is preferred, a hydrocarbon group having 2 to 20 carbon atoms or a polyalkyleneoxyalkylene group is more preferred, an alkylene group having 4 to 20 carbon atoms is further preferred, and a linear alkylene group having 6 to 18 carbon atoms is particularly preferred. The hydrocarbon group may have a chain structure at least in part, and the portion other than the chain structure is not particularly limited and may be, for example, a branched, cyclic, or linear alkylene group having 1 to 5 carbon atoms, an arylene group, an ether bond, or a combination thereof. An alkylene group or a group combining two or more alkylene groups and one or more arylene groups is preferred, an alkylene group is more preferred, and a linear alkylene group is even more preferred. In addition, the above L 1each 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 of 2 to 10.

[0276] Also, Q in compound M 1 and Q 2 The number of atoms in the shortest linking chain between is preferably 3 to 50, more preferably 4 to 40, even more preferably 6 to 20, and particularly preferably 8 to 12, in terms of achieving better effects of the present invention. As used herein, "Q 1 and Q 2 The number of atoms in the shortest chain connecting the 1 Connect to R 1 Q from atoms in 2 Connect to R 1 is the shortest number of atoms that connects to the atom in

[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, di(meth)acrylate of hydrogenated bisphenol A, di(meth)acrylate of hydrogenated bisphenol F, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene glycol / propylene glycol) di(meth)acrylate, and polybutylene glycol di(meth)acrylate. The above ester monomers can also be used as a mixture. Among the above compounds, in terms of achieving better effects of the present invention, at least one compound selected from the group consisting of 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate is preferred, at least one compound selected from the group consisting of 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate is more preferred, and at least one compound selected from the group consisting of 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate is even more preferred.

[0278] One preferred embodiment of the polymerizable compound is a di- or higher functional ethylenically unsaturated compound. In this specification, the term "difunctional or higher functional ethylenically unsaturated compound" refers to a compound having two or more ethylenically unsaturated groups in one molecule. The ethylenically unsaturated group in the ethylenically unsaturated compound is preferably a (meth)acryloyl group. As the ethylenically unsaturated compound, a (meth)acrylate compound is preferred.

[0279] The difunctional ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds. Examples of the difunctional ethylenically unsaturated compound other than the compound M include tricyclodecane dimethanol di(meth)acrylate and 1,4-cyclohexanediol di(meth)acrylate.

[0280] Commercially available bifunctional ethylenically unsaturated compounds include tricyclodecane dimethanol diacrylate (trade name: NK Ester A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimenanol 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] The tri- or higher functional ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds. Examples of tri- or higher functional ethylenically unsaturated compounds include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerin tri(meth)acrylate skeleton.

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

[0283] Examples of the polymerizable compound include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel-Allnex Corporation, etc.), and ethoxylated glycerin triacrylate (NK Ester A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.).

[0284] The polymerizable compound also includes a urethane (meth)acrylate compound. Examples of urethane (meth)acrylates include urethane di(meth)acrylates, such as propylene oxide-modified urethane di(meth)acrylates and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates. Further, the urethane (meth)acrylate may be a trifunctional or higher functional urethane (meth)acrylate. The lower limit of the number of functional groups is preferably 6 or more, and more preferably 8 or more. The upper limit of the number of functional groups is preferably 20 or less. Examples of trifunctional or higher functional urethane (meth)acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), AH-600 (trade name) manufactured by Kyoeisha Chemical Co., Ltd., and UA-306H, UA-306T, UA-306I, UA-510H, and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).

[0285] One preferred embodiment of the polymerizable compound is an ethylenically unsaturated compound having an acid group. Acid groups include phosphate groups, sulfo groups, and carboxy groups. Of these, the acid group is preferably a carboxy group. Examples of the ethylenically unsaturated compound having an acid group include a tri- or tetrafunctional ethylenically unsaturated compound having an acid group [a compound having a carboxy group introduced into a pentaerythritol tri- or tetraacrylate (PETA) skeleton (acid value: 80 to 120 mg KOH / g)], a penta- or hexafunctional ethylenically unsaturated compound having an acid group [a compound having a carboxy group introduced into a dipentaerythritol penta- or hexaacrylate (DPHA) skeleton (acid value: 25 to 70 mg KOH / g)], and the like. These tri- or higher functional ethylenically unsaturated compounds having an acid group may be used in combination with a difunctional ethylenically unsaturated compound having an acid group, if necessary.

[0286] The ethylenically unsaturated compound having an acid group is preferably at least one selected from the group consisting of di- or higher functional ethylenically unsaturated compounds having a carboxy group and carboxylic acid anhydrides thereof. When the ethylenically unsaturated compound having an acid group is at least one selected from the group consisting of di- or higher functional ethylenically unsaturated compounds having a carboxy group and carboxylic acid anhydrides thereof, the developability and film strength are further improved. The di- or higher functional ethylenically unsaturated compound having a carboxy group is not particularly limited and can be appropriately selected from known compounds. Examples of difunctional or higher ethylenically unsaturated compounds having a carboxy group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and Aronix (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.).

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

[0025] to

[0030] of JP-A-2004-239942 is preferred, and the contents of this publication are incorporated herein by reference.

[0288] Examples of the polymerizable compound include compounds obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid, compounds obtained by reacting a glycidyl group-containing compound with an α,β-unsaturated carboxylic acid, urethane monomers such as (meth)acrylate compounds having a urethane bond, phthalic acid compounds such as γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-o-phthalate, and β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, and alkyl (meth)acrylates. These may be used alone or in combination of two or more.

[0289] Examples of compounds obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid include bisphenol A-based (meth)acrylate compounds such as 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane; polyethylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups; polypropylene glycol di(meth)acrylate having 2 to 14 propylene oxide groups; polyethylene polypropylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups and 2 to 14 propylene oxide groups; Examples of the acrylate include trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy tri(meth)acrylate, trimethylolpropane diethoxy tri(meth)acrylate, trimethylolpropane triethoxy tri(meth)acrylate, trimethylolpropane tetraethoxy tri(meth)acrylate, trimethylolpropane pentaethoxy tri(meth)acrylate, di(trimethylolpropane) tetraacrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Among these, ethylenically unsaturated compounds having a tetramethylolmethane structure or a trimethylolpropane structure are preferred, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane)tetraacrylate is more preferred.

[0290] Examples of the polymerizable compound include caprolactone-modified ethylenically unsaturated compounds (e.g., KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd.), alkylene oxide-modified ethylenically unsaturated compounds (e.g., KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel-Allnex Corporation), and ethoxylated glycerin triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0291] As the polymerizable compound (particularly, an ethylenically unsaturated compound), one containing an ester bond is particularly preferred, as it provides 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 the molecule. However, in terms of excellent effects of the present invention, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferred, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane)tetraacrylate is more preferred. From the viewpoint of providing reliability, the ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms and the above-mentioned ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure. Examples of ethylenically unsaturated compounds having an aliphatic structure with 6 or more carbon atoms include 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate.

[0292] One preferred embodiment of the polymerizable compound is a polymerizable compound having an aliphatic hydrocarbon ring structure (preferably a bifunctional ethylenically unsaturated compound). The polymerizable compound is preferably a polymerizable compound having a ring structure in which two or more aliphatic hydrocarbon rings are fused (preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure), more preferably a bifunctional ethylenically unsaturated compound having a ring structure in which two or more aliphatic hydrocarbon rings are fused, and even more preferably tricyclodecane dimethanol di(meth)acrylate. The aliphatic hydrocarbon ring structure is preferably a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure, or an isoborone structure, in terms of achieving better effects of the present invention.

[0293] The molecular weight of the polymerizable compound is preferably from 200 to 3,000, more preferably from 250 to 2,600, still more preferably from 280 to 2,200, and particularly preferably from 300 to 2,200. Among the polymerizable compounds contained in the photosensitive layer, the content ratio of polymerizable compounds having a molecular weight of 300 or less is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less, relative to the content of all polymerizable compounds contained in the photosensitive layer.

[0294] As one preferred embodiment of the photosensitive layer, the photosensitive layer preferably contains a difunctional or higher ethylenically unsaturated compound, more preferably a trifunctional or higher ethylenically unsaturated compound, and even more preferably a trifunctional or tetrafunctional ethylenically unsaturated compound.

[0295] In addition, as one of the preferred embodiments of the photosensitive layer, the photosensitive layer preferably contains a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and a binder polymer having a structural unit having an aliphatic hydrocarbon ring.

[0296] Furthermore, as one of the preferred embodiments of the photosensitive layer, the photosensitive layer preferably contains a compound represented by Formula (M) and an ethylenically unsaturated compound having an acid group, more preferably 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, and even more preferably 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a succinic acid-modified product of dipentaerythritol pentaacrylate.

[0297] Furthermore, as one of the preferred embodiments of the photosensitive layer, the photosensitive layer preferably contains a compound represented by Formula (M), an ethylenically unsaturated compound having an acid group, and a thermally crosslinkable compound described later, and more preferably contains a compound represented by Formula (M), an ethylenically unsaturated compound having an acid group, and a blocked isocyanate compound described later.

[0298] In addition, as one of the preferred embodiments of the photosensitive layer, the photosensitive layer preferably contains a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth)acrylate compound) and a trifunctional or higher functional ethylenically unsaturated compound (preferably a trifunctional or higher functional (meth)acrylate compound) from the viewpoints of suppressing development residues and rust prevention. The mass ratio of the content of the difunctional ethylenically unsaturated compound to the content of the tri- or higher functional ethylenically unsaturated compound is preferably 10:90 to 90:10, more preferably 30:70 to 70:30. The content of the difunctional ethylenically unsaturated compound relative to the total amount of all ethylenically unsaturated compounds is preferably from 20 to 80% by mass, more preferably from 30 to 70% by mass. The content of the difunctional ethylenically unsaturated compound in the photosensitive layer is preferably from 10 to 60% by mass, more preferably from 15 to 40% by mass.

[0299] In one preferred embodiment of the photosensitive layer, the photosensitive layer preferably contains a compound M and a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, from the viewpoint of rust prevention. In addition, as one preferred embodiment of the photosensitive layer, from the viewpoints of substrate adhesion, suppression of development residues, and rust prevention, the photosensitive layer preferably contains compound M and an ethylenically unsaturated compound having an acid group, more preferably contains compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and an ethylenically unsaturated compound having an acid group, still more preferably contains compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a tri- or higher functional ethylenically unsaturated compound, and an ethylenically unsaturated compound having an acid group, and particularly preferably contains compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a tri- or higher functional ethylenically unsaturated compound, an ethylenically unsaturated compound having an acid group, and a urethane (meth)acrylate compound. In addition, as one preferred embodiment of the photosensitive layer, from the viewpoints of substrate adhesion, suppression of development residues, and rust prevention, the photosensitive layer preferably contains 1,9-nonanediol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, preferably 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, more preferably 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, dipentaerythritol hexaacrylate, and an ethylenically unsaturated compound having a carboxylic acid group, and particularly preferably 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, an ethylenically unsaturated compound having a carboxylic acid group, and a urethane acrylate compound.

[0300] The photosensitive layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound. The content of the difunctional or higher functional ethylenically unsaturated compound in the ethylenically unsaturated compound is preferably 60 to 100 mass %, more preferably 80 to 100 mass %, and even more preferably 90 to 100 mass %, based on the total content of all ethylenically unsaturated compounds contained in the photosensitive layer.

[0301] The polymerizable compound (particularly, the ethylenically unsaturated compound) may be used alone or in combination of two or more kinds. The content of the polymerizable compound (particularly, the ethylenically unsaturated compound) in the photosensitive layer is preferably 1 to 70 mass %, more preferably 5 to 70 mass %, even more preferably 5 to 60 mass %, and particularly preferably 5 to 50 mass %, relative to the total mass of the photosensitive layer.

[0302] Polymerization initiator The photosensitive layer may contain a polymerization initiator. The polymerization initiator is preferably a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and any known photopolymerization initiator can be used. Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter also referred to as an "oxime-based photopolymerization initiator"), a photopolymerization initiator having an α-aminoalkylphenone structure (hereinafter also referred to as an "α-aminoalkylphenone-based photopolymerization initiator"), a photopolymerization initiator having an α-hydroxyalkylphenone structure (hereinafter also referred to as an "α-hydroxyalkylphenone-based polymerization initiator"), a photopolymerization initiator having an acylphosphine oxide structure (hereinafter also referred to as an "acylphosphine oxide-based photopolymerization initiator"), and a photopolymerization initiator having an N-phenylglycine structure (hereinafter also referred to as an "N-phenylglycine-based photopolymerization initiator").

[0303] The photopolymerization initiator preferably contains 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 contains 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 the photopolymerization initiator, for example, the polymerization initiators described in paragraphs

[0031] to

[0042] of JP 2011-95716 A and paragraphs

[0064] to

[0081] of JP 2015-014783 A may be used.

[0305] Commercially available photopolymerization initiators include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime) [trade name: IRGACURE® OXE-01, manufactured by BASF], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) [trade name: IRGACURE® OXE-02, manufactured by BASF], IRGACURE® OXE03 (manufactured by BASF), IRGACURE® OXE04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [trade name: Omnirad® 379EG, manufactured by IGM Resins], and the like. BV], 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one [trade name: Omnirad® 907, IGM Resins BV], 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one [trade name: Omnirad® 127, IGM Resins BV], 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 [trade name: Omnirad® 369, IGM Resins BV], 2-hydroxy-2-methyl-1-phenylpropan-1-one [trade name: Omnirad® 1173, IGM Resins BV], 1-hydroxycyclohexyl phenyl ketone [trade name: Omnirad® 184, IGM Resins BV] BV)], 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad (registered trademark) 651, IGM Resins B.oxime esters [trade name: Lunar (registered trademark) 6, manufactured by DKSH Japan Co., Ltd.], 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade 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-carbazol-3-yl]-, 2-(O-acetyloxime) (trade name: TR-PBG -326, manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), and APi-307 (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, manufactured by Shenzhen UV-ChemTech Ltd.).

[0306] The photopolymerization initiator may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable to use an oxime-based photopolymerization initiator and at least one selected from an α-aminoalkylphenone-based photopolymerization initiator and an α-hydroxyalkylphenone-based polymerization initiator. When 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, and the upper limit is preferably 10% by mass or less, 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 ring contained in the heterocyclic compound may be either a monocyclic or polycyclic heterocyclic ring. Examples of heteroatoms contained in the heterocyclic compound include a nitrogen atom, an oxygen atom, and a sulfur atom. The heterocyclic compound preferably contains at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably contains a nitrogen atom.

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

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

[0310] [ka]

[0311] [ka]

[0312] Examples of the tetrazole compound include the following compounds.

[0313] [ka]

[0314] [ka]

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

[0316] [ka]

[0317] Examples of the triazine compound include the following compounds:

[0318] [ka]

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

[0320] [ka]

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

[0322] [ka]

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

[0324] [ka]

[0325] Examples of the benzimidazole compound include the following compounds:

[0326] [ka]

[0327] [ka]

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

[0329] [ka]

[0330] The heterocyclic compounds may be used alone 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 mass %, more preferably 0.10 to 10.0 mass %, still more preferably 0.30 to 8.0 mass %, and particularly preferably 0.50 to 5.0 mass %, relative to the total mass of the photosensitive layer.

[0331] Aliphatic thiol compounds The photosensitive layer may contain an aliphatic thiol compound. When the photosensitive layer contains an aliphatic thiol compound, the aliphatic thiol compound undergoes an ene-thiol reaction with the radical polymerizable compound having an ethylenically unsaturated group, thereby suppressing the cure shrinkage of the film formed and alleviating stress.

[0332] The aliphatic thiol compound is preferably a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, a di- or higher functional aliphatic thiol compound).

[0333] Among the above, polyfunctional aliphatic thiol compounds are preferred as the aliphatic thiol compounds from the viewpoint of the adhesion of the pattern to be formed (particularly the adhesion after exposure).

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

[0335] The polyfunctional aliphatic thiol compound is preferably a low molecular weight compound having a molecular weight of at least 100. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and even more preferably 150 to 1,000.

[0336] The number of functional groups in the polyfunctional aliphatic thiol compound is preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 6, from the viewpoint of the adhesion of the pattern to be formed.

[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-mercaptopropionyloxy)ethyl ester), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), ethylene glycol bisthiopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2'-(ethylenedithio)diethanethiol, meso-2,3-dimercaptosuccinic acid, and di(mercaptoethyl)ether.

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

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

[0340] The photosensitive layer may contain one kind of aliphatic thiol compound alone, or may contain two or more kinds of 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, relative to the total mass of the photosensitive layer.

[0342] ...thermally crosslinkable compound The photosensitive layer preferably contains a thermally crosslinkable compound from the viewpoints of the strength of the cured film obtained and the adhesiveness of the uncured film obtained. In this specification, a thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is not considered to be an ethylenically unsaturated compound but is considered to be a thermally crosslinkable compound. Examples of the thermally crosslinkable compound 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 adhesiveness of the resulting uncured film. The blocked isocyanate compound reacts with a hydroxy group and a carboxy group. Therefore, for example, when at least one of the binder polymer and the radically polymerizable compound having an ethylenically unsaturated group has at least one of a hydroxy group and a carboxy group, the hydrophilicity of the formed film tends to decrease and the function as a protective film tends to be enhanced. The blocked isocyanate compound refers to a compound having a structure in which the isocyanate group of an isocyanate is protected (so-called masked) with a blocking agent.

[0343] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160°C, more preferably 130 to 150°C. The dissociation temperature of a blocked isocyanate means "the temperature of the endothermic peak accompanying the deprotection reaction of the blocked isocyanate when measured by DSC (Differential Scanning Calorimetry) analysis using a differential scanning calorimeter." As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be suitably used. However, the differential scanning calorimeter is not limited to this.

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

[0345] The blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the film and improving the adhesive strength to the transfer target. A blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by protecting hexamethylene diisocyanate by isocyanuration. Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure in which an oxime compound is used as a blocking agent are preferred because the dissociation temperature can be more easily adjusted to a preferred range and development residues can be reduced compared to compounds not having an oxime structure.

[0346] The blocked isocyanate compound may have a polymerizable group. The polymerizable group is not particularly limited, and any known polymerizable group can be used, with a radical polymerizable group being preferred. Examples of the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloxy group, a (meth)acrylamide group, and a styryl group, as well as groups having an epoxy group such as a glycidyl group. Of these, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloxy group, and even more preferably an acryloxy group.

[0347] As the blocked isocyanate compound, commercially available products can be used. Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, and the like (all manufactured by Showa Denko K.K.), and the blocked Duranate series (e.g., Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, and the like, manufactured by Asahi Kasei Chemicals Corporation).

[0348] The thermally crosslinkable compound may be used alone or in combination of two or more kinds. When the photosensitive layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass, based on 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 JP-A-2009-237362.

[0350] The surfactant is preferably a nonionic surfactant, a fluorine-based surfactant, or a silicone-based surfactant, and more preferably a nonionic surfactant. Commercially available fluorine-based surfactants include, for example, 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), Fluorad FC430, FC431, FC171 (all manufactured by Sumitomo 3M Limited), 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), Futergent 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 Co., Ltd.), and U-120E (Unichem Co., Ltd.). Also suitable for use as fluorosurfactants are acrylic compounds that have a molecular structure with a functional group containing a fluorine atom, and when heated, the functional group containing the fluorine atom is cleaved, causing the fluorine atom to volatilize. Examples of such fluorosurfactants include the Megafac DS series manufactured by DIC Corporation (The Chemical Daily, February 22, 2016; The Nikkei Business Daily, February 23, 2016), such as Megafac DS-21. As the fluorine-based surfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. Furthermore, a block polymer can also be used as the fluorine-based surfactant. Furthermore, as the fluorine-based surfactant, a fluorine-containing polymer compound containing a structural unit derived from a (meth)acrylate compound having a fluorine atom and a structural unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups) can also be preferably used. As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used, such as Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation). From the viewpoint of improving environmental friendliness, compounds having a linear perfluoroalkyl group having 7 or more carbon atoms are preferably fluorine-based surfactants that use alternative materials to PFOA and PFOS.

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

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

[0353] Specific examples of surfactants include EXP.S-309-2, EXP.S-315, EXP.S-503-2, and 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, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), as well as X-22-4952, X-22-4272, and 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 Polymers) 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 BYK-Chemie).

[0354] The surfactants may be used alone or in combination of two or more. When the photosensitive layer contains a surfactant, the content of the surfactant 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, based on the total mass of the photosensitive layer.

[0355] Polymerization inhibitor The photosensitive layer may contain a polymerization inhibitor. The polymerization inhibitor means a compound having the function of delaying or inhibiting a polymerization reaction. As the polymerization inhibitor, for example, a known compound used as a polymerization inhibitor can be used.

[0356] Examples of the polymerization inhibitor include 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 tetrakis 3-(3,5-di-te nitroso compounds or salts thereof 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. Among these, in terms of achieving better effects of the present invention, the polymerization inhibitor is preferably at least one selected from the group consisting of phenothiazine compounds, nitroso compounds or salts thereof, and hindered phenol compounds, and more preferably 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.

[0357] The polymerization inhibitor may be used alone or in combination of two or more kinds. When the photosensitive layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.001 to 5.0 mass%, more preferably 0.01 to 3.0 mass%, and even more preferably 0.02 to 2.0 mass%, relative to the total mass of the photosensitive layer. The content of the polymerization inhibitor is preferably 0.005 to 5.0 mass%, more preferably 0.01 to 3.0 mass%, and even more preferably 0.01 to 1.0 mass%, relative to the total mass of the polymerizable compounds.

[0358] Hydrogen-donating compounds The photosensitive layer may contain a hydrogen donating compound. The hydrogen donor compound has the effect of further improving the sensitivity of the photopolymerization initiator to actinic rays and suppressing inhibition of polymerization of the polymerizable compound by oxygen.

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

[0360] Examples of amines include compounds described in MRSander et al., Journal of Polymer Society, Vol. 10, p. 3173 (1972), JP-B-44-020189, JP-A-51-082102, JP-A-52-134692, JP-A-59-138205, JP-A-60-084305, JP-A-62-018537, JP-A-64-033104, and Research Disclosure No. 33825. More specific examples include 4,4'-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (also known as leuco crystal violet), triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, and p-methylthiodimethylaniline. Among these, at least one amine selected from the group consisting of 4,4'-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane is preferred as the amine, as it provides better effects of the present invention.

[0361] Examples of the amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Among these, N-phenylglycine is preferred as the amino acid compound in that it provides a more excellent effect of the present invention.

[0362] Further, examples of the hydrogen donor compound include organometallic compounds (such as tributyltin acetate) described in JP-B-48-042965, hydrogen donors described in JP-B-55-034414, and sulfur compounds (such as trithiane) described in JP-A-6-308727.

[0363] The hydrogen donor compounds may be used alone or in combination of two or more. When the photosensitive layer contains a hydrogen donor compound, the content of the hydrogen donor compound is preferably 0.01 to 10.0 mass %, more preferably 0.01 to 8.0 mass %, and even more preferably 0.03 to 5.0 mass %, relative to the total mass of the photosensitive layer, from the viewpoint of improving the curing rate through a balance between the polymerization growth rate and chain transfer.

[0364] ...Impurities etc. The photosensitive layer may contain a certain amount of impurities. Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Among these, halide ions, sodium ions, and potassium ions are likely to be mixed in as impurities, so it is preferable to set the contents to the following values.

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

[0366] Methods for keeping the impurity content within the above range include selecting raw materials for the photosensitive layer that contain a small amount of impurities, preventing impurities from being mixed in during the formation of the photosensitive layer, and removing them by washing. By using these methods, the amount of impurities can be kept within the above range.

[0367] The amount of impurities can be determined by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0368] The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive layer is preferably low. The content of these compounds 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, and even more preferably 100 ppb or more, by mass. The content of these compounds can be reduced in the same manner as for the metal impurities described above. Furthermore, they can be quantified by known measurement methods.

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

[0370] Residual monomers The photosensitive layer may contain residual monomers of the constituent units of the alkali-soluble resin described above. From the viewpoints of patterning property and reliability, the content of the residual monomer is preferably 5,000 ppm by mass or less, more preferably 2,000 ppm by mass or less, and even more preferably 500 ppm by mass or less, relative to the total mass of the alkali-soluble resin. Although there is no particular lower limit, it is preferably 1 ppm by mass or more, and more preferably 10 ppm by mass or more. From the viewpoints of patterning ability and reliability, the residual monomer content of each structural unit of the alkali-soluble resin is preferably 3,000 ppm by mass or less, more preferably 600 ppm by mass or less, and even more preferably 100 ppm by mass or less, relative to the total mass of the photosensitive layer. Although there is no particular lower limit, it is preferably 0.1 ppm by mass or more, and more preferably 1 ppm by mass or more.

[0371] The amount of residual monomers in the synthesis of an alkali-soluble resin by a polymer reaction is also preferably within the above range. For example, when the alkali-soluble resin is synthesized by reacting glycidyl acrylate with a carboxylic acid side chain, the content of glycidyl acrylate is preferably 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 already described (hereinafter also referred to as "other components"). Examples of other components include colorants, antioxidants, and particles (e.g., metal oxide particles). Other components also include other additives described in paragraphs

[0058] to

[0071] of JP-A No. 2000-310706.

[0373] -particle- The particles are preferably metal oxide particles. The metals in the metal oxide particles also include metalloids such as B, Si, Ge, As, Sb, and Te. The average primary particle size of the particles is preferably from 1 to 200 nm, more preferably from 3 to 80 nm, from the viewpoint of the transparency of the cured film, for example. The average primary particle size of particles is calculated by measuring the particle sizes of 200 random particles using an electron microscope and calculating the arithmetic mean of the measurement results. If the particle shape is not spherical, the particle size is taken to be the longest side.

[0374] When the photosensitive layer contains particles, it may contain only one type of particles or two or more types of particles differing in metal type, size, etc. The photosensitive layer does not contain particles, or if it does contain particles, the particle content is preferably more than 0 mass % and not more than 35 mass % relative to the total mass of the photosensitive layer; more preferably, the photosensitive layer does not contain particles or the particle content is more than 0 mass % and not more than 10 mass % relative to the total mass of the photosensitive composition; even more preferably, the photosensitive layer does not contain particles or the particle content is more than 0 mass % and not more than 5 mass % relative to the total mass of the photosensitive layer; even more preferably, the photosensitive layer does not contain particles or the particle content is more than 0 mass % and not more than 1 mass % relative to the total mass of the photosensitive layer; and particularly preferably, the photosensitive layer does not contain particles.

[0375] -Coloring agent- The photosensitive layer may contain a small amount of colorant (pigment, dye, etc.), but preferably does not substantially contain a colorant, for example, from the viewpoint of transparency. When the photosensitive layer contains a colorant, the content of the colorant is preferably less than 1% by mass, more preferably less than 0.1% by mass, based on the total mass of the photosensitive layer.

[0376] -Antioxidants- Examples of antioxidants include 3-pyrazolidones such as 1-phenyl-3-pyrazolidone (also known as phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorohydroquinone; paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, and paraphenylenediamine. Among these, 3-pyrazolidones are preferred as the antioxidant, and 1-phenyl-3-pyrazolidone is more preferred, as they provide better effects of the present invention.

[0377] When the photosensitive layer contains an antioxidant, the content of the antioxidant is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and even more preferably 0.01% by mass or more, relative to the total mass of the photosensitive layer. There is no upper limit, but it is preferably 1% by mass or less.

[0378] Thickness of the photosensitive layer The thickness of the photosensitive layer is not particularly limited, but is often 30 μm or less, and is preferably 20 μm or less, more preferably 15 μm or less, even more preferably 10 μm or less, and particularly preferably 5.0 μm or less, from the viewpoint of obtaining a superior effect of the present invention. The lower limit of the thickness is preferably 0.60 μm or more, more preferably 1.5 μm or more, and even more preferably 2.0 μm or more, from the viewpoint of obtaining a film having excellent strength by curing the photosensitive layer. The thickness of the photosensitive layer is calculated as the average value of measurements taken at any five points by cross-sectional observation using an SEM (Scanning Electron Microscope).

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

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

[0381] The pattern obtained by curing the photosensitive layer (cured film of the photosensitive layer) is preferably achromatic. Specifically, total reflection (incident angle 8°, light source: D-65 (2° field of view)) is * The value is preferably 10 to 90, and the pattern a * The value is preferably -1.0 to 1.0, and the b * The value is preferably between -1.0 and 1.0.

[0382] Moisture permeability of the photosensitive layer The moisture permeability of the pattern (cured film of the photosensitive layer) obtained by curing the photosensitive layer at a film thickness of 40 μm is set to 500 g / m from the viewpoint of rust prevention. 2 / 24hr or less is preferable, and 300g / m 2 / 24hr or less is more preferable, and 100g / m 2 It is more preferable that the time is 24 hours or less. The moisture permeability was measured by exposing the photosensitive layer to i-rays at an exposure dose of 300 mJ / cm 2After exposure to light at 100° C., the photosensitive layer is post-baked at 145° C. for 30 minutes to harden the photosensitive layer, and the hardness is measured on the hardened film.

[0383] Refractive index adjustment layer The transfer film X2 of the second embodiment preferably has a refractive index adjusting layer. The refractive index adjusting layer may be a known refractive index adjusting layer. Examples of materials contained 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 adjusting layer is not particularly limited, and examples thereof include a method of using a resin having a predetermined refractive index alone, a method of using a resin and particles, and a method of using a complex of a metal salt and a resin.

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

[0385] Examples of particles include metal oxide particles and metal particles. The type of metal oxide particles is not particularly limited, and known metal oxide particles can be used. The metals in the metal oxide particles include semimetals such as B, Si, Ge, As, Sb, and Te.

[0386] The average primary particle size of the particles is preferably from 1 to 200 nm, more preferably from 3 to 80 nm, from the viewpoint of the transparency of the cured film, for example. The average primary particle size of particles is calculated by measuring the particle sizes of 200 random particles using an electron microscope and calculating the arithmetic mean of the measurement results. If the particle shape is not spherical, the particle size is taken to be the longest side.

[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, at least one type of metal oxide particles selected from the group consisting of zirconium oxide particles and titanium oxide particles is more preferred, for example, because the refractive index can be easily adjusted.

[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 (Nanouse OZ-S30M, manufactured by Nissan Chemical Industries, Ltd.), and zirconium oxide particles (Nanouse OZ-S30K, manufactured by Nissan Chemical Industries, Ltd.).

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

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

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

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

[0393] The transfer film 20 is produced by pressing a protective film 21 onto the refractive index adjusting layer 17 of the laminate produced by the above-mentioned production method. As a manufacturing method for the transfer film of the second embodiment, it is preferable to include a step of providing a protective film 21 so that it is in contact with the side of the refractive index adjusting layer 17 opposite the side having the temporary support 11, thereby manufacturing a transfer film 20 having the temporary support 11, an intermediate layer 13, a photosensitive layer 15, a refractive index adjusting layer 17, and a protective film 21. After the transfer film 20 is manufactured by the above manufacturing method, the transfer film 20 may be wound up to produce and store a transfer film in a roll form. The transfer film in a roll form can be provided in that form as it is to the lamination step with a substrate in a roll-to-roll system described below.

[0394] In addition, the manufacturing method of the above-mentioned transfer film 20 may be a method in which an intermediate layer 13 and a photosensitive layer 15 are formed on a temporary support 11, a refractive index adjustment layer 17 is separately formed on a protective film 21, and the refractive index adjustment layer 17 is bonded to the photosensitive layer 15.

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

[0396] Photosensitive composition and method for forming photosensitive layer In terms of superior productivity, the photosensitive layer in the transfer film X2 is desirably formed by a coating method using a photosensitive composition containing the components constituting the photosensitive layer described above (e.g., a binder polymer, a polymerizable compound, and a polymerization initiator) and a solvent. Specifically, a preferred method for producing the transfer film of the second embodiment is a method in which a photosensitive composition is applied to a temporary support to form a coating film, and this coating film is dried at a predetermined temperature to form a photosensitive layer.

[0397] The solvent that can be contained in the photosensitive composition is preferably an organic solvent, such as 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, as the solvent, an organic solvent having a boiling point of 180 to 250° C. (high boiling point solvent) can also be used, if necessary.

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

[0400] The viscosity of the photosensitive composition at 25°C is, for example, 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. 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 viscometers.

[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. For example, a surface tensiometer manufactured by Kyowa Interface Science Co., Ltd. (trade name: Automatic Surface Tensiometer CBVP-Z) can be suitably used. However, the surface tensiometer is not limited to the above-mentioned surface tensiometer.

[0402] Examples of methods for applying the photosensitive composition include printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (that is, slit coating).

[0403] As a method for drying the coating film of the photosensitive composition, heat drying and reduced pressure drying are preferred. The drying temperature is preferably 80° C. or higher, more preferably 90° C. or higher, and the upper limit is preferably 130° C. or lower, more preferably 120° C. or lower. Drying can also be performed by changing the temperature continuously. 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 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 composition for forming the refractive index adjusting layer preferably contains the various components for forming the refractive index adjusting layer described above and a solvent. Note that in the composition for forming the refractive index adjusting layer, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the refractive index adjusting layer described above. The solvent is not particularly limited as long as it can dissolve or disperse the components contained in the refractive index adjusting layer, and at least one selected from the group consisting of water and water-miscible organic solvents is preferred, and water or a mixed solvent of water and a water-miscible organic solvent is more preferred. Examples of water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, with alcohols having 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred. The solvents may be used alone or in combination of two or more. The content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.

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

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

[0407] Moreover, by laminating a protective film to the refractive index adjusting layer, the transfer film of the second embodiment can be produced. The method for attaching the protective film to the refractive index adjusting layer is not particularly limited, and known methods can be used. Examples of a device for laminating the protective film to the refractive index adjusting layer include known laminators such as a vacuum laminator and an auto-cut laminator. The laminator is preferably equipped with any heatable roller such as a rubber roller and is capable of applying pressure and heat.

[0408] Optimal relationship between the physical properties of the temporary support, photosensitive layer, and protective film As with the transfer film X1 of the first embodiment described above, the physical properties of the temporary support, the photosensitive layer, and the protective film of the transfer film X2 of the second embodiment preferably satisfy one or more, and more preferably all, of Preferred Mode 1, Preferred Mode 2, Preferred Mode 3, Preferred Mode 4, and Preferred Mode 5. Preferred Modes 1, 2, 3, 4, and 5 are as described above.

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

[0410] The method for producing circuit wiring of the present invention comprises: A method for producing circuit wiring, including the method for producing the laminate of the present invention, a step of forming a seed layer on a substrate to form a substrate with a seed layer (hereinafter also referred to as a "seed layer forming step"); a step of laminating the transfer film, which has a temporary support, an intermediate layer, and a photosensitive layer, to the substrate with a seed layer so that the side of the transfer film opposite to the temporary support side is in contact with the substrate with a 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 (transfer film laminating step); a step of peeling off the temporary support between the temporary support and the intermediate layer (temporary support peeling step); a step of bringing the exposed intermediate layer into contact with a mask to perform an exposure treatment, and then performing a development treatment after the exposure to form a pattern (a pattern formation step); a step of forming a metal plating layer by plating on the seed layer in an area where the pattern is not arranged (hereinafter also referred to as a "metal plating layer forming step"); a step of forming a protective layer on the metal plating layer (hereinafter also referred to as a "protective layer forming step"); a step of removing the pattern (hereinafter also referred to as a "pattern removing step"); a step of removing the exposed seed layer to obtain conductive thin wires (hereinafter also referred to as a "conductive thin wire forming step"); The surface free energy of the surface of the intermediate layer on the temporary support side is 68.0 mJ / m 2 The following is the result.

[0411] The method for producing circuit wiring according to the present invention will be described in detail below for each step. Note that the following description of the components may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

[0412] [First embodiment] The first embodiment of the method for producing circuit wiring includes a seed layer forming step, a transfer film attaching step, a temporary support peeling step, a pattern forming step, a metal plating layer forming step, a protective layer forming step, a pattern removing step, and a conductive thin wire forming step in this order, and the surface free energy of the surface of the intermediate layer on the temporary support side is 68.0 mJ / m 2 The following is the result. The transfer film laminating process, temporary support peeling process, and pattern forming process are the same as those in the first embodiment of the laminate manufacturing method described above, except that the substrate is a substrate with a seed layer, and the preferred aspects are also the same.

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

[0414] <Seed layer> The metal contained in the seed layer is not particularly limited, and known metals can be used. Examples of the main component (so-called main metal) contained in the seed layer include copper, chromium, lead, nickel, gold, silver, tin, zinc, etc. The main component refers to the metal with the largest content 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, more preferably 100 nm or more. There is no particular upper limit, but it is preferably 2 μm or less.

[0416] The method for forming the seed layer is not particularly limited, and examples thereof include known methods such as a method of applying a dispersion liquid in which metal fine particles are dispersed and sintering the coating film, a sputtering method, and a vapor deposition method.

[0417] <<Metal plating layer formation process>> The metal plating layer forming step is a step of forming a metal plating layer by plating on the seed layer in the area where no pattern is arranged. Examples of plating treatment include electrolytic plating and electroless plating, with electrolytic plating being preferred from the viewpoint of productivity.

[0418] The metal contained in the metal plating layer is not particularly limited, and any known metal can be used. The metal plating layer may include, 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, in order to provide the conductive thin wire with better conductivity. Also, in order to provide the conductive thin wire with better conductivity, the metal plating layer preferably contains copper as the main component.

[0419] The lower limit of the thickness of the metal plating layer is not particularly limited, but is preferably 0.1 μm or more, more preferably 1 μm, and the upper limit is not particularly limited, but is preferably 20 μm or less.

[0420] <<Protective layer formation process>> The protective layer laminating step is a step of forming a protective layer on the metal plating layer. The material of the protective layer is preferably a material that is resistant to the remover or etching solution used in the removal step or the conductive thin wire formation step. Examples include metals such as nickel, chromium, tin, zinc, magnesium, gold, and silver, alloys thereof, and resins. Among these, nickel or chromium is preferred as the material of the protective layer.

[0421] Examples of methods for forming the protective layer include electroless plating and electroplating, with electroplating being preferred.

[0422] The thickness of the protective layer is not particularly limited to a lower limit, but is preferably 0.3 μm or more, more preferably 0.5 μm or more, and is not particularly limited to an upper limit, but is preferably 3.0 μm or less, more preferably 2.0 μm or less.

[0423] <<Pattern removal process>> The pattern removal step is a step of removing the pattern. The method for removing the pattern is not particularly limited, but includes a method of removing the pattern by chemical treatment, and a method of removing the pattern using a remover is preferred. The temperature of the removal liquid is preferably 30 to 80°C, and more preferably 50 to 80°C. A preferred embodiment of the removal method is a method in which a substrate having a pattern to be removed is immersed in a stirring removal liquid at a liquid temperature of 50 to 80° C. for 1 to 30 minutes.

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

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

[0426] The method for removing a portion of the seed layer is not particularly limited, 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 mixed solution, and phosphoric acid-hydrogen peroxide mixed solution.

[0427] The upper limit of the width of the formed conductive thin wires is preferably 8 μm or less, more preferably 6 μm or less, and the lower limit is not particularly limited, but is often 2 μm or more.

[0428] <<Other processes>> The first embodiment of the method for manufacturing a circuit wiring may include any steps (other steps) other than the steps described above. For example, examples include a process for reducing visible light reflectance described in paragraph

[0172] of WO 2019 / 022089, and a process for forming a new conductive layer on an insulating film described in paragraph

[0172] of WO 2019 / 022089, but are not limited to these processes.

[0429] <Step of reducing visible light reflectance> The first embodiment of the method for manufacturing circuit wiring may include a step of performing a process for reducing the visible light reflectance of some or all of the plurality of conductive layers of the substrate. An example of a treatment for reducing the visible light reflectance is oxidation treatment. When the substrate has a conductive layer containing copper, the visible light reflectance of the conductive layer can be reduced by oxidizing the copper to copper oxide and blackening the conductive layer. Treatments for reducing visible light reflectance are described in paragraphs 0017 to 0025 of JP 2014-150118 A and paragraphs 0041, 0042, 0048, and 0058 of JP 2013-206315 A, and the contents of these publications are incorporated herein by reference.

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

[0431] [Circuit wiring applications] The circuit wiring manufactured by the first embodiment of the circuit wiring manufacturing method is preferably used as circuit wiring arranged on a supporting substrate such as a sheet, metal substrate, ceramic substrate, or glass in a manufacturing process film for a semiconductor package, a printed circuit board, or an interposer rewiring layer.

[0432] [Circuit Wiring Manufacturing Method (Circuit Wiring Manufacturing Method 2)] In the upper part, a method for forming a conductive thin line pattern on a substrate by a semi-additive method is described, but the method for manufacturing circuit wiring to which the laminate manufacturing method of the present invention is applied is not limited to this. Other circuit wiring manufacturing methods include: A method for producing circuit wiring, including the method for producing the laminate of the present invention, a step (transfer film lamination step) of laminating a transfer film having a temporary support, an intermediate layer, and a photosensitive layer to a conductive substrate (a conductive substrate is a substrate having at least a support substrate and a conductive layer disposed on the support substrate, as described above) so that the surface of the transfer film opposite the intermediate layer side of the photosensitive layer of the transfer film is in contact with the substrate, thereby obtaining a substrate with a photosensitive layer having the conductive substrate, the photosensitive layer, the intermediate layer, and the temporary support in this order (however, the conductive layer of the conductive substrate is disposed so that it faces the photosensitive layer); a step of peeling off the temporary support between the temporary support and the intermediate layer (temporary support peeling step); a step of bringing the exposed intermediate layer into contact with a mask to perform an exposure treatment, and then performing a development treatment after the exposure to form a pattern (a pattern formation step); an etching step (etching step) of etching the conductive layer in an area where the pattern is not arranged, The surface free energy of the surface of the intermediate layer on the temporary support side is 68.0 mJ / m 2 The following manufacturing methods are mentioned. The transfer film laminating process, temporary support peeling process, and pattern forming process are the same as those in the first embodiment of the laminate manufacturing method described above, except that the substrate is a substrate having a conductive layer, and the preferred aspects are also the same.

[0433] The etching step is a step of etching the conductive layer in the areas where no pattern is arranged. As the etching method, known methods can be applied, and examples thereof include the method described in paragraphs

[0209] to

[0210] of JP 2017-120435 A, the method described in paragraphs

[0048] to

[0054] of JP 2010-152155 A, a wet etching method in which the substrate is immersed in an etching solution, and a dry etching method such as plasma etching.

[0434] An example of a device having circuit wiring manufactured by the above manufacturing method is an input device, preferably a touch panel, more preferably a capacitive touch panel. The input device can be applied to display devices such as organic electroluminescence (EL) display devices and liquid crystal display devices. In the second embodiment of the circuit wiring manufacturing method, it is also preferable to sequentially or simultaneously form circuits on both surfaces of the substrate. With this configuration, it is possible to form a circuit wiring for a touch panel 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 a circuit wiring for a touch panel with this configuration from both surfaces of the substrate by roll-to-roll.

[0435] [Transfer film] The present invention also relates to a transfer film. 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 of the intermediate layer on the temporary support side is 68.0 mJ / m 2 is as follows: The intermediate layer has an arithmetic mean roughness Ra of a surface on the temporary support side of 50 nm or less. The transfer film is suitable for an exposure method in which the temporary support is peeled off before exposure, and can suppress excessive adhesion between the photosensitive layer and the photomask after exposure, and also has excellent resolution.

[0437] The transfer film of the present invention corresponds to one embodiment of the above-mentioned transfer film X. The configuration and preferred embodiments of the transfer film X are as described above. [Example]

[0438] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment details, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below. Unless otherwise specified, "parts" and "%" are by mass. In the following examples, the weight average molecular weight of the resin is the weight average molecular weight determined by gel permeation chromatography (GPC) in terms of polystyrene, and the acid value is the theoretical acid value.

[0439] [Various components of transfer film] First, the various components used in the preparation of the transfer film will be described below.

[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" (Kuraray Co., Ltd.)) PVP: (Polypyrrolidone: Product name "Polyvinylpyrrolidone K-30" (Nippon Shokubai Co., Ltd.)) HPMC: (Hydroxypropyl methylcellulose: Product name "Metolose 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: (Hydroxypropyl cellulose: product name "HPC-SSL", manufactured by NISSO Co., Ltd.) 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 Industries, Ltd.

[0441] <<Composition for forming intermediate layer>> After mixing the components according to the description in Table 4, a solvent (solvent: a mixed solvent of ion-exchanged water and methanol (manufactured by Mitsubishi Gas Chemical Co., Inc.) in a mixing ratio (mass ratio) of 40 / 60) was added to prepare a composition for forming an intermediate layer. In Table 4, the numerical values ​​corresponding to each component listed in the column "Composition of intermediate layer (type and amount of component (mass %)" indicate the content of each component relative to the total mass of the intermediate layer.

[0442] [Photosensitive layer] The compositions of the 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 by known methods, and the weight average molecular weights (Mw) of the synthesized polymers were measured by gel permeation chromatography (GPC) under the following conditions:

[0445] (GPC conditions) Apparatus: Tosoh high-speed GPC apparatus HLC-8420GPC (product name), manufactured by Tosoh Corporation Guard column: Tosoh Corporation, HZ-L Separation column: Three columns of TSK gel Super HZM-N (trade name) 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] (Polymer synthesis) In the following synthesis examples, the following abbreviations represent the following compounds, respectively. St: Styrene (Fujifilm Wako Pure Chemical Industries, Ltd.) MAA: methacrylic acid (Fujifilm Wako Pure Chemical Industries, Ltd.) MMA: Methyl methacrylate (Fujifilm Wako Pure Chemical Industries, Ltd.) BA: Butyl acrylate (Fujifilm Wako Pure Chemical Industries, Ltd.) PGMEA: Propylene glycol monomethyl ether acetate (Showa Denko K.K.) MEK: Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.) V-601: Dimethyl-2,2'-azobis(2-methylpropionate) (Fujifilm Wako Pure Chemical Industries, Ltd.)

[0447] Synthesis of polymer P-1 PGMEA (116.5 parts) was placed in a three-neck 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 over 2 hours to the solution in the flask maintained at 90°C ± 2°C. After completion of the dropwise addition, 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 in the same manner as for polymer P-1, except for changing the types and amounts of the monomers used. The solid content of the solution containing polymer P-2 was 30% by mass.

[0449] The type of each monomer used to synthesize each polymer, as well as the content (mass %) and weight average molecular weight of the structural unit derived from each monomer in each polymer are shown below. The polymers P-1 and P-2 all fall under the category of alkali-soluble resins.

[0450] [Table 3]

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

[0452] (Polymerization initiator) B-CIM: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, Hampford Irgacure OXE-02 (oxime ester photoinitiator, 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) Leuco Crystal Violet: manufactured by Tokyo Chemical Industry Co., Ltd. N,N-Tetraethyl-4,4-diaminobenzophenone: manufactured by Hodogaya Chemical N-phenylcarbamoylmethyl-N-carboxymethylaniline (Fujifilm Wako Pure Chemical Industries, Ltd.)

[0455] (coloring agent) Brilliant Green: 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 phenolic antioxidant, manufactured by BASF

[0456] (antioxidant) 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone (Fujifilm Wako Pure Chemical Industries, Ltd.) (surfactant) Megafac F-552: surfactant, manufactured by DIC

[0457] <<Photosensitive compositions 1-4>> The components were mixed according to the description in Table 2, and then methyl ethyl ketone was added to prepare photosensitive compositions 1 to 4, each having a solids concentration adjusted to 25% by mass. The numerical values ​​corresponding to each component listed in the component column in Table 2 represent parts by mass of solid content. In other words, each numerical value indicates the blend amount excluding solvents such as dilution solvents.

[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 temporary support produced by the method described below was used. Temporary support C: Toyobo ester film E5000 (manufactured by Toyobo Co., Ltd.) Temporary support D: Uni-Peel TR-1 (manufactured by Unitika Ltd.) Temporary support E: Therapeel 25WZ (manufactured by Toray Industries, Inc.) Temporary support F: Cosmoshine A4300 (manufactured by Toyobo Co., Ltd.)

[0459] <Method of 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 Filter Systems Co., Ltd.) and then subjected to membrane degassing using a 2×6 Radial Flow Superphobic (manufactured by Polypore Co., Ltd.).

[0460] Acrylic polymer (AS-563A, manufactured by Daicel FineChem Co., Ltd., solid content 27.5% by mass) 167 parts 0.7 parts of nonionic surfactant (Naroacty CL95, manufactured by Sanyo Chemical Industries, Ltd., solid content 100% by mass) 114.4 parts of anionic surfactant (Rapisol A-90, manufactured by NOF Corporation, diluted with water to a solids content of 1% by mass) 7 parts of carnauba wax dispersion (Cellosol 524, manufactured by Chukyo Yushi Co., Ltd., solid content 30% by mass) 20.9 parts of carbodiimide compound (Carbodilite V-02-L2, manufactured by Nisshinbo, Inc., diluted with water to a solid content of 10% by mass) Matting agent (Snowtex XL, manufactured by Nissan Chemical Industries, Ltd., solid content 40% by mass, average particle size 50 nm) 2.8 parts ·Wednesday 690.2 parts

[0461] (Extrusion molding) Pellets of polyethylene terephthalate using a citric acid chelate organic titanium complex as a polymerization catalyst, as described in Japanese Patent No. 5575671, were dried to a moisture content of 50 ppm or less, then placed in the hopper of a 30 mm diameter single-screw kneading extruder and melted and extruded at 280°C. The melt was passed through a filter (pore size 3 μm) and then extruded from a 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 extruded onto a cooling roll and solidified by the above method was sequentially biaxially stretched by 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 stretching The unstretched film was stretched in the machine direction (machine direction) by passing it between two pairs of nip rolls with different peripheral speeds. 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% / sec.

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

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

[0466] (heat fixation, heat relaxation) Subsequently, the biaxially stretched film after the longitudinal stretching and transverse stretching was heat-set under the following conditions: 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) After heat setting and heat relaxation, both ends were trimmed, and the ends were knurled to a width of 10 mm, and then wound up at a tension of 40 kg / m. The width was 1.5 m and the wound length was 6,300 m. The obtained film roll was used as temporary support B.

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

[0469] In addition, by the above procedure, for example, a transfer film having a temporary support of type A, an intermediate layer of type 1, and a photosensitive layer of type 1 is prepared as the transfer film used in Example 1.

[0470] Comparative Examples 1 to 4 Photosensitive transfer films each composed of a temporary support and a photosensitive layer were prepared so as to have the configuration shown in Table 4. The films were prepared in the same manner as the transfer film used in Example 1, except that no intermediate layer was formed.

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

[0472] [Various evaluations] [Evaluation 1: Temporary support peelability] A copper layer having a thickness of 200 nm was formed on a PET substrate having a thickness of 0.1 mm by vapor deposition to prepare a PET substrate with a copper layer. After peeling off the protective film from the prepared transfer film, the film was laminated onto the above-mentioned copper-layered PET substrate so that the copper layer and the photosensitive layer were in contact with each other under lamination conditions of a roll temperature of 100°C, a linear pressure of 1.0 MPa, and a linear speed of 4.0 m / min. After the temporary support was peeled off at an angle of 180°, the temporary support and the surface of the photosensitive layer were visually observed 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 there is noise when peeling off. "C": When the temporary support is peeled off, the intermediate layer peels off, the temporary support tears, and / or cohesive failure occurs.

[0473] [Evaluation 2: Mask non-adhesion] After the above exposure operation, the surface of the photosensitive layer was visually observed 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 there is a noise when peeling it off. "C": The photosensitive layer adheres to the mask (the mask can be peeled off, but the photosensitive layer peels off)

[0474] [Rating 3: Resolution] A copper layer having a thickness of 200 nm was formed on a PET substrate having a thickness of 0.1 mm by vapor deposition to prepare a PET substrate with a copper layer. After peeling off the protective film from the prepared transfer film, the film was laminated onto the above-mentioned copper-layered PET substrate so that the copper layer and the photosensitive layer were in contact with each other under lamination conditions of a roll temperature of 100°C, a linear pressure of 1.0 MPa, and a linear speed of 4.0 m / min. Next, a photomask with a specified line (μm) / space (μm) pattern was used, and after peeling off the temporary support, the film was brought into contact with the mask and exposed. A high-pressure mercury lamp with i-line (365 nm) as the dominant exposure wavelength was used for exposure. The exposure dose was set arbitrarily so that the top shape of each pattern matched the mask opening. Next, shower development was carried out with a 1% aqueous solution of sodium carbonate 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 description, "resolvable without residue between patterns" means that recessed areas of the pattern (positions corresponding to unexposed areas) can be resolved without residue. (Evaluation criteria) "AA": L / S=3μm / 3μm can be resolved without residue between patterns. "A": L / S=6μm / 6μm can be resolved without residue between patterns. "B": L / S=8μm / 8μm can be resolved without residue between patterns. "C": L / S=8μm / 8μm cannot be resolved

[0475] [Overall rating from 1 to 3] Based on the results of evaluations 1 to 3, a comprehensive evaluation was performed 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 releasability are rated A. "B": The resolution is rated A, and one of the mask non-adhesion property and the temporary support releasability is rated A, and the other is rated B. "C": The resolution is rated B, and the mask non-adhesion property and temporary support releasability are rated either A or B. "D": The resolution is rated C, or the mask non-adhesion is rated C. The temporary support may be rated either way.

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

[0477] [Table 4]

[0478] [Table 5]

[0479] [Table 6]

[0480] [Table 7]

[0481] The results in Table 4 clearly show that the manufacturing method of the laminate of the example can suppress excessive adhesion between the photosensitive layer and the photomask after exposure (in other words, excellent mask non-adhesion), and can form a fine pattern with suppressed residue in the recessed areas of the pattern (in other words, excellent resolution).

[0482] On the other hand, in Comparative Examples 1 to 7, the desired effects were not obtained. As shown in Comparative Examples 1 and 3, when exposure was carried out by directly adhering the photosensitive layer and the mask without forming an intermediate layer, the mask non-adhesion was poor. Furthermore, as shown in Comparative Examples 3 and 4, when no intermediate layer was formed and exposure was carried out through the temporary support without carrying out the temporary support peeling step, the resolution was poor. Furthermore, as shown in Comparative Example 5, when an intermediate layer was formed but exposure was carried out through the temporary support without carrying out the temporary support peeling step, the resolution was poor. In addition, as shown in Comparative Examples 6 and 7, the surface free energy E I is 68.0 mJ / cm 2 When the thickness exceeds 100 μm, both the mask non-adhesion property and the resolution are poor.

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

[0484] [Example 49: Manufacturing method of printed wiring board] The transfer film of Example 48 shown in Table 4 was used as the resist pattern forming material in paragraph 0050 of JP 2019-121740 A, and the printed wiring board manufacturing method disclosed in the above patent publication was carried out. A substrate with good wiring without erosion was obtained. It was confirmed that the transfer films of the examples are also suitable for obtaining resist patterns for the semi-additive process. [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 is as follows: A transfer film, wherein the surface of the intermediate layer on the temporary support side has an arithmetic mean roughness Ra of 50 nm or less.

2. The surface free energy of 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 or 2, wherein the intermediate layer comprises polyvinyl alcohol.

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

5. The transfer film according to any one of claims 1 to 4, wherein the intermediate layer further contains polyvinylpyrrolidone.

6. The transfer film according to any one of claims 1 to 5, 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.

7. The transfer film according to claim 6 , wherein the content of the 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.

8. The transfer film according to claim 6 or 7, wherein the compound X comprises hydroxypropyl methylcellulose.

9. The transfer film according to any one of claims 1 to 8, wherein the intermediate layer has a thickness of 3.0 µm or less.

10. The transfer film according to any one of claims 1 to 9, wherein the photosensitive layer has a thickness of 2.0 to 20 µm.

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