Manufacturing method for laminates having a conductive pattern

Abstract

The present invention addresses the problem of providing a production method for a laminate having a conductor pattern, the method enabling production of a laminate having a conductor pattern having an excellent shape.　This production method for a laminate having a conductor pattern comprises: a bonding step for bonding a transfer film which sequentially has a temporary support body, an intermediate layer, and a photosensitive layer to a substrate which has on a surface thereof a metal layer such that the photosensitive layer side comes into contact with the metal layer; an exposure step for pattern-exposing the photosensitive layer from a side opposite to the substrate side; a development step for executing development on the exposed photosensitive layer by using an alkaline developing agent and forming a resist pattern; an etching step for performing etching on a portion of the metal layer at a region where the resist pattern is not disposed or a plating step for performing plating on said portion; and a resist stripping step for stripping the resist pattern. The method further comprises, if comprising the plating step, a removal step for removing the metal layer exposed in the resist stripping step and forming a conductor pattern on the substrate. The method further comprises, between the bonding step and the exposure step or between the exposure step and the development step, a temporary support body stripping step for stripping the temporary support body. The photosensitive layer includes a crosslinkable alkali-soluble resin, an ethylenically unsaturated compound, and a photoinitiator.

Description

[Technical Field]

[0001] The present invention relates to a method for manufacturing a laminate having a conductive pattern. [Background technology]

[0002] Because it requires fewer steps to obtain a predetermined conductor pattern, a method is sometimes used in which a resist pattern is placed on an arbitrary substrate using a transfer film having a photosensitive layer, and then the conductor pattern is formed using this resist pattern.

[0003] Patent Document 1 discloses a photosensitive resin laminate (transfer film) comprising a support film and a photosensitive resin composition layer for resist material usable for etching a copper layer. The photosensitive resin composition layer contains an alkali-soluble polymer, a compound having an ethylenically unsaturated double bond of a predetermined structure, and a photopolymerization initiator in predetermined amounts. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2015-219336 [Overview of the project] [Problems that the invention aims to solve]

[0005] The present inventors attempted to form a laminate having a conductive pattern using a photosensitive resin laminate (transfer film) described in Patent Document 1, and found that the cross-sectional shape of the conductive pattern sometimes becomes an inverted trapezoid (in other words, the length on the substrate side of the cross-sectional shape of the conductive pattern is shorter than the length on the opposite side of the substrate), or the conductive pattern may become tilted. In other words, the inventors found that there is room to further improve the shape of the conductive pattern formed in a method for manufacturing a laminate having a conductive pattern using a transfer film. Incidentally, in recent years, when manufacturing laminates having a conductive pattern using transfer film, a method has been investigated in which a temporary support is peeled off, and then a mask is brought into close contact with the surface exposed by the peeling before performing the exposure treatment. Therefore, it is desirable that the manufacturing method for laminates having a conductive pattern also be applicable to the method of peeling off a temporary support and then bringing a mask into close contact with the surface exposed by the peeling before performing the exposure treatment.

[0006] Therefore, the object of the present invention is to provide a method for manufacturing a laminate having a conductive pattern that can produce a laminate having a conductive pattern with excellent shape characteristics. [Means for solving the problem]

[0007] The inventors have found that the above problems can be solved by the following configuration. [1] A bonding step of bonding the transfer film, which has a temporary support, an intermediate layer, and a photosensitive layer in this order, to the substrate such that the photosensitive layer side is in contact with the metal layer of the substrate having a metal layer on its surface, An exposure step of pattern-exposing the photosensitive layer from the side opposite to the side having the substrate, A developing step in which the exposed photosensitive layer is developed using an alkaline developer to form a resist pattern, An etching process or a plating process is performed on the metal layer in the region where the resist pattern is not placed. A resist stripping step for stripping the above resist pattern, Furthermore, if the above plating process is included, the method for manufacturing a laminate having a conductive pattern comprises a removal step of removing the metal layer exposed by the resist stripping step and forming a conductive pattern on the substrate, Between the bonding step and the exposure step, or between the exposure step and the development step, there is further a temporary support peeling step for peeling off the temporary support. A method for producing a laminate having a conductive pattern, wherein the photosensitive layer comprises a crosslinkable alkali-soluble resin, an ethylenically unsaturated compound, and a photopolymerization initiator. [2] A method for manufacturing a laminate having the conductive pattern described in [1], wherein the intermediate layer contains a water-soluble resin. [3] A method for producing a laminate having a conductive pattern according to [1] or [2], wherein the intermediate layer comprises one or more selected from the group consisting of water-soluble cellulose derivatives, polyhydric alcohols, alkylene oxide adducts of polyhydric alcohols, polyether resins, polyamide resins, polyvinylamide resins, polyallylamide resins, phenol derivatives, and amide compounds. [4] A method for producing a laminate having the conductive pattern described in any of [1] to [3], wherein the C=C value of the crosslinkable alkali-soluble resin is 0.1 to 3.0 mmol / g. [5] A method for producing a laminate having the conductive pattern described in any of [1] to [4], wherein the C=C value of the crosslinkable alkali-soluble resin is 0.4 to 2.0 mmol / g. [6] A method for manufacturing a laminate having a conductive pattern according to any one of [1] to [5], wherein the C=C value of the photosensitive layer is 1.0 to 3.0 mmol / g. [7] A method for manufacturing a laminate having a conductive pattern according to any one of [1] to [6], wherein the glass transition temperature of the crosslinkable alkali-soluble resin is 60 to 150°C. [8] A method for producing a laminate having a conductive pattern as described in any of [1] to [7], wherein the acid value of the above crosslinkable alkali-soluble resin is 60 to 200 mg KOH / g. [9] A method for manufacturing a laminate having a conductive pattern according to any one of [1] to [8], comprising the temporary support peeling step between the bonding step and the exposure step.

[10] Between the bonding step and the exposure step, there is a temporary support peeling step, A method for manufacturing a laminate having a conductive pattern according to any one of [1] to [9], wherein the exposure step is a step of performing pattern exposure through a photomask. 〔11〕Between the above bonding step and the above exposure step, there is the above temporary support peeling step, The above exposure step is a step of performing pattern exposure by bringing the surface of the exposed intermediate layer into contact with a photomask. A method for manufacturing a laminate having a conductor pattern according to any one of 〔1〕~〔10〕. 〔12〕Between the above exposure step and the above development step, there is the above temporary support peeling step, The above exposure step is a step of performing pattern exposure through a photomask. A method for manufacturing a laminate having a conductor pattern according to any one of 〔1〕~〔8〕. 〔13〕Between the above exposure step and the above development step, there is the above temporary support peeling step, The above exposure step is a step of performing pattern exposure by bringing the surface of the transfer film opposite to the side having the substrate into contact with a photomask. A method for manufacturing a laminate having a conductor pattern according to any one of 〔1〕~〔8〕. 〔14〕The above photomask includes a light-shielding portion arranged in a mesh shape. A method for manufacturing a laminate having a conductor pattern according to any one of 〔10〕~〔13〕. 〔15〕The above photomask includes a light-shielding portion arranged in a circular dot shape. A method for manufacturing a laminate having a conductor pattern according to any one of 〔10〕~〔13〕. 〔16〕The above photomask includes an opening portion arranged in a circular dot shape. A method for manufacturing a laminate having a conductor pattern according to any one of 〔10〕~〔13〕.

Advantages of the Invention

[0008] According to the present invention, it is possible to provide a method for manufacturing a laminate having a conductor pattern, which can produce a laminate having a conductor pattern with excellent shapeability.

Brief Description of the Drawings

[0009] [Figure 1] It is a schematic diagram showing an example of a transfer film. [Figure 2] It is a schematic diagram for explaining the trailing shape of a pattern. [Modes for carrying out the invention]

[0010] The present invention will be described in detail below. In this specification, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. In this specification, in numerical ranges described in stages, the upper or lower limit stated in one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in numerical ranges described in this specification, the upper or lower limit stated in one numerical range may be replaced with the values ​​shown in the examples.

[0011] In this specification, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes, as long as their intended purpose is achieved.

[0012] In this specification, unless otherwise specified, "transparent" means that the average transmittance of visible light with wavelengths of 400 to 700 nm is 80% or higher, and preferably 90% or higher. In this specification, the average transmittance of visible light is a value measured using a spectrophotometer, which can be measured using, for example, a Hitachi U-3310 spectrophotometer manufactured by Hitachi, Ltd.

[0013] In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are calculated using polystyrene as the standard material, measured by a gel permeation chromatography (GPC) analyzer using TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all product names of Tosoh Corporation) as the column, THF (tetrahydrofuran) as the eluent, a differential refractometer as the detector, and polystyrene as the standard material. Furthermore, unless otherwise specified in this specification, the molecular weight of a compound with a molecular weight distribution is the weight-average molecular weight (Mw). In this specification, unless otherwise specified, the content of metallic elements is measured using an inductively coupled plasma (ICP) spectrometer.

[0014] 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.

[0015] In this specification, "alkali-soluble" means that the solubility in 100 g of a 1% by mass sodium carbonate aqueous solution at a liquid temperature of 22°C is 0.1 g or more. Therefore, for example, an alkali-soluble resin refers to a resin that satisfies the above solubility conditions.

[0016] In this specification, "water-soluble" means that the solubility in 100g of water at a pH of 7.0 at a liquid temperature of 22°C is 0.1g or more. Therefore, for example, a water-soluble resin refers to a resin that satisfies the above-mentioned solubility conditions.

[0017] The "solid content" of a composition refers to the components that form the composition layer (e.g., the photosensitive layer or intermediate layer) formed using the composition. If the composition contains a solvent (e.g., an organic solvent and water), it refers to all components excluding the solvent. Furthermore, any liquid components that form the composition layer are also considered to be solid content.

[0018] [[Manufacturing method for laminates having conductive patterns]] The method for manufacturing a laminate having a conductive pattern of the present invention (hereinafter also simply referred to as the method of the present invention) is: A transfer film having a temporary support, an intermediate layer, and a photosensitive layer in this order, A bonding step in which the transfer film and the substrate are bonded together such that the photosensitive layer side is in contact with the metal layer of the substrate having a metal layer on its surface, An exposure step of pattern-exposing the photosensitive layer from the side opposite to the side having the substrate, A developing process is performed on the exposed photosensitive layer using an alkaline developer to form a resist pattern (hereinafter sometimes referred to as a "resin pattern"). An etching process or a plating process is performed on the metal layer in the region where the resist pattern is not placed. A resist stripping step for stripping the above resist pattern, Furthermore, if the above plating process is included, the method for manufacturing a laminate having a conductive pattern comprises a removal step of removing the metal layer exposed by the resist stripping step and forming a conductive pattern on the substrate, Between the bonding step and the exposure step, or between the exposure step and the development step, there is further a temporary support peeling step for peeling off the temporary support. The above photosensitive layer comprises a crosslinkable alkali-soluble resin, an ethylenically unsaturated compound, and a photopolymerization initiator.

[0019] Although the mechanism by which the above configuration solves the problems of the present invention is not necessarily clear, the inventors believe it to be as follows. First, one of the features of the present invention is the use of a transfer film having an intermediate layer between the temporary support and the photosensitive layer. As a result, even when the temporary support is peeled off, a mask is brought into close contact with the surface exposed by the peeling, and an exposure treatment is performed to form a resin pattern, and then the film is subjected to a process to manufacture a conductive pattern, the presence of the intermediate layer prevents the mask and the photosensitive layer from coming into direct contact, thus suppressing excessive adhesion between the mask and the photosensitive layer. Furthermore, it is possible to suppress the roughening of the photosensitive layer surface during temporary support peeling, which may occur due to excessive adhesion between the temporary support and the photosensitive layer. Excessive adhesion between the mask and the photosensitive layer, and roughening of the photosensitive layer surface during temporary support peeling, can be factors in the deterioration of the shape of the formed resin pattern. If such a resin pattern is used as a resist pattern to form a conductive pattern, it is presumed that this will also adversely affect the shape of the resulting conductive pattern.

[0020] Another characteristic feature of the method of the present invention is that the photosensitive layer includes a crosslinkable alkali-soluble resin, an ethylenically unsaturated compound, and a photopolymerization initiator. With the above-described configuration of the photosensitive layer, a strong cured film of the crosslinkable alkali-soluble resin and the ethylenically unsaturated compound can be formed in the exposed area during exposure treatment. As a result, the penetration of the developer into the exposed area during the development treatment (alkaline development treatment) after exposure is suppressed. If the developer penetrates deeply into the exposed area of ​​the photosensitive layer, the resin pattern formed from the photosensitive layer tends to have a wide base shape, and fluctuations in the shape of the base tend to increase. It is presumed that if such a resin pattern is used as a resist pattern to form a conductor pattern, it will also adversely affect the shape of the resulting conductor pattern.

[0021] The inventors believe that by providing an intermediate layer between the temporary support and the photosensitive layer, and then configuring the photosensitive layer as described above, it is possible to form a resin pattern in which the deterioration of the resin pattern's shape is significantly suppressed. As a result of forming a conductor pattern using this resin pattern as a resist pattern, the shape characteristics of the conductor pattern can be further improved. Hereinafter, the superior shape of the conductive pattern in the laminate is also referred to as the superior effect of the present invention.

[0022] [Embodiments of the present invention] The methods of the present invention can be broadly classified into two types: a method for producing a laminate having a conductive pattern via an etching process, and a method for producing a laminate having a conductive pattern via a plating process. Hereinafter, the method for manufacturing a laminate having a conductive pattern via an etching process will also be referred to as the first embodiment of the method of the present invention. Furthermore, the method for manufacturing a laminate having a conductive pattern via a plating process will also be referred to as the second embodiment of the method of the present invention. First, the first embodiment will be described, and then the second embodiment will be described.

[0023] [First Embodiment] A first embodiment of the present invention comprises at least the following steps (1-1) to (1-5) in order. • Process (1-1) (Lamination Process): A process of laminating a transfer film having a temporary support, an intermediate layer, and a photosensitive layer in that order, to a substrate such that the photosensitive layer side is in contact with the metal layer of the substrate having a metal layer on its surface. • Process (1-2) (exposure process): A process of pattern-exposing the photosensitive layer from the side opposite to the side having the substrate. • Process (1-3) (Development Process): A process in which the exposed photosensitive layer is developed using an alkaline developer to form a resist pattern. • Process (1-4) (Etching process): A process of performing an etching on the metal layer in areas where the above resist pattern is not placed. • Process (1-5) (Resist peeling process): A process for peeling off the above resist pattern. Furthermore, the first embodiment of the present invention includes the following step (1-A) between steps (1-1) and (1-2), or between steps (1-2) and (1-3). • Process (1-A) (Temporary support removal process): A process for removing the temporary support mentioned above.

[0024] <Process (1-1), lamination process> The lamination process involves laminating a transfer film having a temporary support, an intermediate layer, and a photosensitive layer in that order, to a substrate such that the photosensitive layer is in contact with the metal layer of the substrate having a metal layer on its surface. If the transfer film has a protective film as described later, it is preferable to perform the lamination process after peeling off the protective film. Transfer film will be discussed later.

[0025] In bonding, it is preferable to bring the photosensitive layer side of the transfer film (the surface opposite to the temporary support side) into contact with the metal layer on the substrate and press them together. Examples of bonding methods include known transfer methods and lamination methods, and a preferred method involves placing the surface of the photosensitive layer of the transfer film opposite to the temporary support side onto the substrate and applying pressure and heat using a roll or the like. As for lamination methods, for example, a method using a known laminator such as a vacuum laminator or an auto-cut laminator can be mentioned. A lamination temperature of 70 to 130°C is preferred.

[0026] A substrate having a metal layer on its surface (a substrate with a metal layer) comprises a substrate and a metal layer disposed on the surface of the substrate. A substrate with a metal layer may have any other layer formed on it as needed. In other words, it is preferable that a substrate with a metal layer has at least a substrate and a metal layer disposed on the surface of the substrate. Examples of substrates include resin substrates, glass substrates, ceramic substrates, and semiconductor substrates, with the substrate described in paragraph

[0140] of International Publication No. 2018 / 155193 being preferred. As the material for the resin substrate, polyethylene terephthalate, cycloolefin polymer, or polyimide are preferred. The thickness of the resin substrate is preferably 5 to 200 μm, and more preferably 10 to 100 μm. In particular, when using a photomask that includes light-shielding sections arranged in a mesh pattern during the exposure process, it is preferable to use a transparent substrate. In this context, "transparent" means that the transmittance of the exposure wavelength is 50% or more. The transmittance of the transparent substrate is preferably 80% or more, more preferably 90%, and even more preferably 95%. Examples of transparent substrates include resin substrates (e.g., resin films) and glass substrates. The resin substrate is preferably a resin substrate that transmits visible light. Preferred components of a visible light-transmitting resin substrate include, for example, polyamide resins, polyethylene terephthalate resins, polyethylene naphthalate resins, cycloolefin resins, polyimide resins, and polycarbonate resins. More preferred components of a visible light-transmitting resin substrate include, for example, polyamide, polyethylene terephthalate (PET), cycloolefin polymer (COP), polyethylene naphthalate (PEN), polyimide, and polycarbonate. The transparent substrates mentioned above are preferably polyamide films, polyethylene terephthalate films, cycloolefin polymers, polyethylene naphthalate films, polyimide films, or polycarbonate films, with polyethylene terephthalate films being more preferable. The thickness of the transparent substrate is not limited. The thickness of the transparent substrate is preferably 10 to 200 μm, more preferably 20 to 120 μm, and even more preferably 20 to 100 μm. The thickness of the transparent substrate is measured by the following method: A scanning electron microscope (SEM) is used to observe a cross-section of the transparent substrate perpendicular to its main surface (i.e., in the thickness direction). Based on the obtained observation image, the thickness of the transparent substrate is measured at 10 points. The average thickness of the transparent substrate is determined by arithmetic mean taking the measured values.

[0027] Furthermore, when using a photomask that includes light-shielding areas or openings arranged in a circular dot pattern, it is preferable to use a silicon substrate, a glass substrate, or an organic substrate such as FR4 (Flame Retardant Type 4) as the substrate. In this case, the thickness of the substrate is not particularly limited, and a wiring pattern may be formed on a part of the substrate, or a wiring layer may be laminated. Photomasks that include light-shielding areas or openings arranged in a circular dot pattern will be described in a later section.

[0028] The metal layer is a layer containing metal, and there are no particular restrictions on the metal; known metals can be used. Preferably, the metal layer is a conductive layer. Examples of the main components (so-called primary metals) of the metal layer include copper, chromium, lead, nickel, gold, silver, tin, and zinc. The primary components mentioned above refer to the metal present in the largest quantity among the metals contained within the metal layer.

[0029] The thickness of the metal layer is not particularly limited, but is preferably 50 nm or more, and more preferably 100 nm or more. There is no particular upper limit, but is preferably 2 μm or less.

[0030] The method for forming the metal layer is not particularly limited, and known methods include, for example, a method of applying a dispersion of metal fine particles and sintering the coating film, sputtering, and vapor deposition.

[0031] One or more metal layers may be placed on the substrate. When two or more metal layers are arranged, the metal layers may be the same or different, but it is preferable that they be made of different materials.

[0032] A substrate having at least one of transparent electrodes and routing wiring is also preferred, and such a substrate can be used as a touch panel substrate. Transparent electrodes can function as electrodes for touch panels. The transparent electrode is preferably composed of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide), as well as metal fine wires such as a metal mesh and metal nanowires. Examples of metal wires include silver and copper wires, and silver conductive materials such as silver mesh and silver nanowires are preferred.

[0033] Metal is preferred as the material for routing the wiring. Examples of the above metals include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, as well as alloys combining these. Copper, molybdenum, aluminum, or titanium are preferred, with copper being more preferred.

[0034] <Process (1-2), Exposure Process> The exposure process involves pattern-exposing the photosensitive layer from the side opposite to the side having the substrate (the side opposite to the side having the photosensitive layer substrate). "Pattern exposure" refers to a method of exposure that involves a pattern of exposure, where there are exposed and unexposed areas. The positional relationship between the exposed areas and the unexposed areas in pattern exposure can be adjusted as needed. The exposure process typically involves pattern exposure through a photomask. In the exposure process, the photomask and the laminate, which is the light-sensitive material, may or may not be in contact.

[0035] If a temporary support peeling step, described later, is performed between the lamination step and the exposure step, the exposure step is preferably one in which the surface of the laminate from which the temporary support obtained in the temporary support peeling step was peeled, opposite to the substrate side, is brought into contact with the photomask and a pattern is exposed. In other words, the exposure step is preferably one in which the surface of the laminate from which the temporary support was peeled, exposed by the peeling of the temporary support, is brought into contact with the photomask and a pattern is exposed on the photosensitive layer. The exposed surface in question is the surface of the intermediate layer when the transfer film has a three-layer structure consisting of a temporary support, an intermediate layer, and a photosensitive layer. By employing such an exposure process, a higher-resolution resist pattern can be obtained, and ultimately, a higher-resolution conductive pattern can be obtained. Such an exposure process is particularly preferable when a temporary support peeling process, described later, is performed between the lamination process and the exposure process. Furthermore, if a temporary support peeling step, described later, is performed between the exposure step and the development step, the exposure step is preferably one in which the photomask is brought into contact with the surface of the transfer film opposite to the side containing the substrate in the laminate of the substrate and the transfer film obtained by the lamination step, and a pattern is exposed.

[0036] In the exposure process for pattern exposure, a hardening reaction of components contained in the photosensitive layer may occur in the exposed area of ​​the photosensitive layer (the area corresponding to the opening of the photomask). After exposure, a development process is performed to remove the unexposed areas of the photosensitive layer, and a pattern is formed.

[0037] The method of the present invention may also preferably include a photomask peeling step between the exposure step and the development step, in which the photomask used in the exposure step is peeled off. Examples of photomask peeling processes include known peeling processes.

[0038] The light source for pattern exposure can be any light capable of emitting light in a wavelength range sufficient to cure the photosensitive layer (e.g., 365 nm and 405 nm), with 365 nm being preferred. "Main wavelength" refers to the wavelength with the highest intensity.

[0039] Examples of light sources include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps. The exposure dose is 5-200 mJ / cm². 2 Preferably, 10-200 mJ / cm² 2 This is preferable. Examples of light sources, exposure amounts, and exposure methods are given in paragraphs

[0146] to

[0147] of International Publication No. 2018 / 155193, the contents of which are incorporated herein by reference.

[0040] <Process (1-A), Temporary support removal process> A temporary support peeling step is performed between the lamination step and the exposure step, or between the exposure step and the development step. In particular, it is more preferable to have a peeling step between the bonding step and the exposure step. The peeling process is the process of peeling the temporary support from the laminate of the transfer film and the substrate with a metal layer. Examples of methods for peeling off the temporary support include known peeling methods. Specifically, the cover film peeling mechanism described in paragraphs

[0161] to

[0162] of Japanese Patent Application Publication No. 2010-072589 is an example.

[0041] <Process (1-3), development process> The developing process involves developing the exposed photosensitive layer using an alkaline developer to form a pattern. By performing the above developing process, the unexposed areas of the photosensitive layer are removed, and a resist pattern is formed with the openings of the photomask as convex parts.

[0042] Among the alkaline developers used as the developing solution, an alkaline aqueous solution containing an alkali metal salt is preferred. The alkali metal salts contained in the developing solution are preferably compounds that dissolve in water and exhibit alkalinity. Examples of alkali metal salts include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate. The developing solution may contain compounds other than alkali metal salts that dissolve in water and exhibit alkalinity. Examples of such compounds include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide). The water content in the developer is preferably 50% by mass or more and less than 100% by mass, and more preferably 90% by mass or more and less than 100% by mass, relative to the total mass of the developer. The alkali metal salt content in the developer is preferably 0.01 to 20% by mass, and more preferably 0.1 to 10% by mass, relative to the total mass of the developer.

[0043] Examples of development methods include well-known development methods. Specifically, these include paddle development, shower development, spin development, and dip development. As for the development method, the development method described in paragraph

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

[0044] After development, it is also preferable to perform a rinsing process to remove any remaining developer from the metal-layered substrate before proceeding to the next step. Water or the like can be used for the rinsing process. After developing and / or rinsing, a drying process may be performed to remove any excess liquid from the substrate with the metal layer.

[0045] The position and size of the resist pattern formed on the metal layer substrate are not particularly limited, but a fine linear shape is preferred. Specifically, the line width of the resist pattern is preferably 20 μm or less, more preferably 15 μm or less, even more preferably 10 μm or less, and particularly preferably 5 μm or less. The lower limit is, for example, 1.0 μm or more.

[0046] <Process (1-B) (Post-exposure process) and Process (1-C) (Post-bake process)> The first embodiment may include, between the development step and the etching step described later, a step of further exposing the resist pattern obtained on the metal layer substrate (hereinafter also referred to as "step (1-B)" or "post-exposure step") and / or heating it (hereinafter also referred to as "step (1-C)" or "post-bake step"). If the first embodiment includes both a post-exposure step and a post-bake step, it is preferable to perform the post-exposure step first, followed by the post-bake step. The exposure dose in the post-exposure process is 100-5000 mJ / cm². 2 Preferably, 200-3000 mJ / cm²2 This is preferable. The post-bake temperature in the post-bake process is preferably 80 to 250°C, and more preferably 90 to 160°C. The post-bake time in the post-bake process is preferably 1 to 180 minutes, and more preferably 10 to 60 minutes.

[0047] <Process (1-4), Etching Process> The etching process is a process of performing an etching treatment on the metal layer in areas where the resist pattern is not placed. Specifically, in the etching process, the resist pattern obtained up to the above-mentioned step is used as an etching resist, and the metal layer is etched. When the etching process is performed, the metal layer is removed at the openings in the resist pattern, and the metal layer ends up having a pattern shape similar to that of the resist pattern.

[0048] Examples of etching methods include known etching methods. Specifically, examples include the methods described in paragraphs

[0209] to

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

[0048] to

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

[0049] For wet etching, the etching solution used can be appropriately selected as either acidic or alkaline depending on the object being etched. Examples of acidic etching solutions include acidic aqueous solutions containing at least one acidic compound, and acidic mixed aqueous solutions of an acidic compound and at least one selected from the group consisting of ferric chloride, ammonium fluoride, and potassium permanganate. The acidic compound (a compound that dissolves in water and exhibits acidity) contained in the acidic aqueous solution is preferably at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid. Examples of alkaline etching solutions include alkaline aqueous solutions containing at least one alkaline compound, and alkaline aqueous mixed solutions of an alkaline compound and a salt (e.g., potassium permanganate). The alkaline compound (a compound that dissolves in water and exhibits alkalinity) contained in the alkaline aqueous solution is preferably at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide). It is preferable that the etching solution does not dissolve the resist pattern. The developing solution used in the development process may also serve as the etching solution used in the etching process. In this case, the development and etching processes may be carried out simultaneously.

[0050] After the etching process, it is also preferable to perform a rinsing process to remove any remaining etching solution from the metal-layered substrate before proceeding to the next step. Water or the like can be used for the rinsing process. After etching and / or rinsing, a drying process may be performed to remove any excess liquid from the substrate with the metal layer.

[0051] <Process (1-5), Resist Stripping Process> The resist stripping process is a step that removes the remaining resist pattern after the etching process. Methods for removing the remaining resist pattern include, for example, removal by chemical treatment, with a preferred method being removal using a stripping solution. Methods for removing remaining resist patterns include, for example, using a stripping solution and removing them by known methods such as the spray method, shower method, or paddle method.

[0052] Examples of stripping solutions include a removal solution obtained by dissolving an alkaline compound in at least one selected from the group consisting of water, dimethyl sulfoxide, and N-methylpyrrolidone. Examples of alkaline compounds (compounds that dissolve in water and exhibit alkalinity) include alkaline inorganic compounds such as sodium hydroxide and potassium hydroxide, as well as alkaline organic compounds such as primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds. Additionally, other stripping agents such as propylene glycol monomethyl ether acetate (PGMEA) can be used. The liquid temperature of the stripping solution is preferably 23 to 80°C, more preferably 30 to 80°C, and even more preferably 50 to 80°C. A preferred method for removal is to immerse a substrate having the pattern to be removed in a stripping solution that is being stirred and has a liquid temperature of 50 to 80°C for 1 to 30 minutes. It is also preferable that the stripping solution does not dissolve the metal layer.

[0053] After removing the resist pattern with a stripping solution, it is also preferable to perform a rinsing process to remove any remaining stripping solution from the substrate. Water or the like can be used for the rinsing process. After stripping the resist pattern with a stripping solution and / or rinsing, a drying process may be performed to remove any excess solution from the substrate.

[0054] When the resist stripping process is performed, the remaining resist pattern is removed from the substrate, and the metal layer that existed between the substrate and the resist pattern (a metal layer having a pattern shape similar to the removed resist pattern) is exposed on the surface, resulting in a laminate having a conductive pattern.

[0055] [Second Embodiment] A second embodiment of the present invention comprises at least the following steps (2-1) to (2-6) in order. • Process (2-1) (Lamination Process): A process of laminating a transfer film having a temporary support, an intermediate layer, and a photosensitive layer in that order, to a substrate such that the photosensitive layer side is in contact with the metal layer of the substrate having a metal layer on its surface. • Process (2-2) (Exposure process): A process of pattern exposure of the photosensitive layer from the side opposite to the side having the substrate. • Process (2-3) (Development Process): A process in which the exposed photosensitive layer is developed using an alkaline developer to form a resist pattern. • Process (2-4) (Plating process): A process of performing a plating treatment on the metal layer in the area where the resist pattern is not placed. • Process (2-5) (Resist Peeling Process): A process for peeling off the above resist pattern. • Process (2-6) (Removal Process): A removal process to remove the metal layer exposed by the resist peeling process and to form a conductive pattern on the substrate. Furthermore, a second embodiment of the present invention includes the following step (2-A) between steps (2-1) and (2-2), or between steps (2-2) and (2-3). • Process (2-A) (Temporary support removal process): A process for removing the temporary support mentioned above.

[0056] <Steps (2-1)~(2-3), (2-A)~(2-C)> Steps (2-1) to (2-3) and (2-A) in the second embodiment are the same as those described as steps (1-1) to (1-3) and (1-A) in the first embodiment. Furthermore, in the second embodiment, between step (2-3) (development step) and step (2-4) described later, there may be a step of further exposing (hereinafter also referred to as "step (2-B)" or "post-exposure step") and / or heating (hereinafter also referred to as "step (2-C)" or "post-bake step") the resist pattern obtained on the metal layer substrate. Steps (2-B) and (2-C) in the second embodiment are the same as those described as steps (1-B) and (1-C) in the first embodiment, respectively.

[0057] <Process (2-4), Plating Process> The plating process is a process in which a plating layer is formed by plating treatment on a metal layer in an area where a resist pattern is not placed (a metal layer exposed on the surface by the developing process). Examples of plating methods include electrolytic plating and electroless plating, and electrolytic plating is preferred from the viewpoint of productivity. When the plating process is performed, a plating layer is obtained on the metal layer substrate that has a pattern shape similar to the areas where the resist pattern is not placed (openings in the resist pattern).

[0058] Examples of metals included in the plating layer include well-known metals. Specifically, these include metals such as copper, chromium, lead, nickel, gold, silver, tin, and zinc, as well as alloys of these metals. In particular, the plating layer preferably contains copper or an alloy thereof, as this provides superior conductivity of the conductive pattern. Furthermore, the plating layer preferably contains copper as its main component, as this provides superior conductivity of the conductive pattern.

[0059] The thickness of the plating layer is preferably 0.1 μm or more, and more preferably 1 μm. The upper limit is preferably 20 μm or less.

[0060] <Process (2-D), protective layer formation process> In the second embodiment, it is also preferable to have a protective layer formation step between the plating step and the resist stripping step described later. The protective layer lamination process is a process of forming a protective layer on top of the plated layer. The protective layer material is preferably one that has resistance to the stripping solution and / or etching solution used in the resist stripping and / or removal process. Examples include metals such as nickel, chromium, tin, zinc, magnesium, gold, and silver, their alloys, and resins. Among these, nickel or chromium is preferred as the protective layer material.

[0061] Methods for forming the protective layer include, for example, electroless plating and electroplating, with electroplating being preferred.

[0062] There are no particular restrictions on the lower limit of the thickness of the protective layer, but it is preferably 0.3 μm or more, and more preferably 0.5 μm or more. There are no particular restrictions on the upper limit, but it is preferably 3.0 μm or less, and more preferably 2.0 μm or less.

[0063] <Process (2-5), Resist Stripping Process> The resist stripping process is a step that removes any remaining resist pattern after the plating process or protective layer formation process. Steps (2-5) can be carried out in the same manner as steps (1-5) described in the first embodiment.

[0064] <Step (2-6), removal step> The removal process involves removing the metal layer exposed by the resist stripping process to obtain a conductive pattern on the substrate. In the removal process, the plating layer formed by the plating process is used as an etching resist to etch the metal layer located in the non-pattern formation region (in other words, the region not protected by the plating layer).

[0065] There are no particular limitations on the method for removing a portion of the metal layer, but it is preferable to use a known etching solution. Examples of known etching solutions include ferric chloride solution, cupric chloride solution, ammonia alkali solution, sulfuric acid-hydrogen peroxide mixture, and phosphoric acid-hydrogen peroxide mixture.

[0066] When the removal process is performed, the metal layer exposed on the surface of the substrate is removed, while the plated layer (conductor pattern) with a pattern shape remains, resulting in a laminate having a conductor pattern.

[0067] The upper limit of the line width of the formed conductor pattern is preferably 8 μm or less, and more preferably 6 μm or less. There is no particular limit on the lower limit, but it is often 2 μm or more.

[0068] [Other processes] The method of the present invention (first embodiment and / or second embodiment) may include other steps in addition to the steps described above. Other steps include, for example, the step of reducing the visible light reflectance as described in paragraph

[0172] of International Publication No. 2019 / 022089, and the step of forming a new conductive layer on the surface of the insulating film as described in paragraph

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

[0069] <Process to reduce visible light reflectance> The method of the present invention may include a step of performing a process to reduce the visible light reflectance of part or all of the conductive patterns of the laminate. One example of a treatment to reduce visible light reflectance is oxidation. When a laminate has a conductive pattern containing copper, the copper can be oxidized to copper oxide, which blackens the conductive pattern and thus reduces the visible light reflectance of the laminate. Examples of processes for reducing visible light reflectance include paragraphs

[0017] to

[0025] of Japanese Patent Publication No. 2014-150118, and paragraphs

[0041] ,

[0042] ,

[0048] , and

[0058] of Japanese Patent Publication No. 2013-206315, the contents of which are incorporated herein by reference.

[0070] <Steps for forming an insulating film, and for forming a new conductive layer on the surface of the insulating film> The method of the present invention may include the steps of forming an insulating film on the surface of a laminate having a conductive pattern, and forming a new conductive layer (such as a conductive pattern) on the surface of the insulating film. Through the above process, a first electrode pattern and an insulated second electrode pattern can be formed. Examples of the process for forming the insulating film include methods for forming known permanent films. Alternatively, an insulating film with a desired pattern may be formed by photolithography using an insulating photosensitive composition. As a step in forming a new conductive layer on the surface of an insulating film, for example, a new conductive layer with a desired pattern may be formed by photolithography using a conductive photosensitive composition.

[0071] The method of the present invention also preferably involves using a substrate having multiple conductive layers (such as metal layers) on both surfaces of the laminate, and forming a conductive pattern sequentially or simultaneously using the conductive layers formed on both surfaces of the substrate. With the above configuration, a touch panel circuit wiring can be formed in which a first conductive pattern is formed on one substrate surface and a second conductive pattern is formed on the other substrate surface. It is also preferable to form the touch panel circuit wiring with the above configuration from both sides of the substrate using a roll-to-roll method.

[0072] [Applications of the manufacturing method for laminates having conductive patterns] The manufacturing method for laminates according to the present invention can be applied to the manufacture of conductive films such as touch panels, transparent heaters, transparent antennas, electromagnetic shielding materials, and dimmable films; the manufacture of printed circuit boards and semiconductor packages; the manufacture of pillars and pins for interconnects between semiconductor chips and packages; the manufacture of metal masks; the manufacture of tape substrates such as COF (Chip on Film) and TAB (Tape Automated Bonding); and the like. Furthermore, the above-mentioned touch panel can be a capacitive touch panel. The method for manufacturing the laminate according to the present invention can be used to form conductive films and peripheral circuit wiring in the touch panel. The above-mentioned touch panel can be applied to display devices such as organic EL (electro-luminescence) display devices and liquid crystal display devices.

[0073] One embodiment of the method for manufacturing a laminate having a conductive pattern produced by the method of the present invention is, for example, in the second embodiment, a photomask including a mesh-like arrangement of light-shielding portions is used during the exposure process. The above manufacturing method is suitable as a method for manufacturing a mesh-like metal wiring pattern. The laminate having a conductive pattern obtained by the above manufacturing method can be used, for example, as a transparent conductive film. Specifically, it can be used for touch panel electrodes, transparent heaters, transparent antennas, electromagnetic wave shielding materials, and dimming films, etc. In that case, the sheet resistance value of the mesh pattern region is preferably as low as possible, preferably 100Ω / □ or less, more preferably 20Ω / □ or less, and particularly preferably 5Ω / □ or less.

[0074] Furthermore, as another embodiment of the method for manufacturing a laminate having a conductive pattern produced by the method of the present invention, for example, in the second embodiment, a photomask including light-shielding portions arranged in the shape of circular dots is used during the exposure process. The above manufacturing method can be suitably used as a method for manufacturing vias, and as a method for manufacturing pillars and pins for interconnects between semiconductor chips and packages. The diameter of the pillars and pins is preferably 1 to 20 μm, more preferably 2 to 10 μm, and even more preferably 3 to 8 μm. The length of the pillars and pins is preferably 1 to 20 μm, and even more preferably 3 to 10 μm. Another example is in the second embodiment, a photomask including openings arranged in the shape of circular dots is used during the exposure process. The above manufacturing method is suitable as a method for manufacturing through-holes, etc. The diameter of the through-holes is preferably 1 to 20 μm, more preferably 2 to 10 μm, and even more preferably 3 to 8 μm. The depth of the through-holes is preferably 1 to 20 μm, and even more preferably 3 to 10 μm.

[0075] Furthermore, as another embodiment of the method for manufacturing a laminate having a conductive pattern produced by the method of the present invention, for example, in the first embodiment, a photomask including light-shielding portions arranged in a circular dot shape is used during the exposure process. The above manufacturing method is suitable for manufacturing through-holes and the like. The diameter of the through-hole is preferably 1 to 20 μm, more preferably 2 to 10 μm, and even more preferably 3 to 8 μm. The depth of the through-hole is preferably 1 to 20 μm, and more preferably 3 to 10 μm.

[0076] The term "circular" as described above may refer to either a perfect circle or an approximate circle. Furthermore, "a photomask including light-shielding areas arranged in a circular dot pattern" may refer to a photomask with one circular dot-shaped light-shielding area, or a photomask with two or more circular dot-shaped light-shielding areas. Similarly, "a photomask including openings arranged in a circular dot pattern" may refer to a photomask with one circular dot-shaped opening, or a photomask with two or more circular dot-shaped openings.

[0077] [Transfer film] The transfer film used in the method of the present invention comprises a temporary support, an intermediate layer, and a photosensitive layer, wherein the photosensitive layer contains a crosslinkable alkali-soluble resin, an ethylenically unsaturated compound, and a photopolymerization initiator. The photosensitive layer containing the crosslinkable alkali-soluble resin, the ethylenically unsaturated compound, and the photopolymerization initiator corresponds to a so-called negative-type photosensitive layer.

[0078] The transfer film may have other layers besides the photosensitive layer described later. Furthermore, the transfer film may have other components (for example, a protective film) as described later.

[0079] From the viewpoint of suppressing the generation of air bubbles in the lamination process described above, the maximum width of the waviness of the transfer film is preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 60 μm or less. The lower limit is preferably 0 μm or more, more preferably 0.1 μm or more, and even more preferably 1 μm or more. The maximum width of the waviness in the transfer film is the value measured by the following procedure. A test sample is prepared by cutting the transfer film to a size of 20 cm x 20 cm perpendicular to the main surface. If the transfer film has a protective film, the protective film is peeled off from the transfer film. Next, the test sample is placed on a smooth and horizontal stage with the surface of the temporary support facing the stage. After placement, a 3D surface image is obtained by scanning the surface of the test sample in a 10 cm square area in the center of the sample with a laser microscope (e.g., Keyence VK-9700SP), and the minimum concave height is subtracted from the maximum convex height observed in the obtained 3D surface image. The above operation is performed for 10 test samples, and the arithmetic mean is taken as the maximum waviness width of the transfer film.

[0080] For superior adhesion, the transmittance of light at a wavelength of 365 nm in the photosensitive layer is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more. The upper limit is preferably 99.9% or less, and more preferably 99.0% or less.

[0081] An example of an embodiment of the transfer film will be described. The transfer film 10 shown in Figure 1 comprises, in this order, a temporary support 11, a composition layer 17 including an intermediate layer 13 and a photosensitive layer 15, and a protective film 19. The transfer film 10 shown in Figure 1 has a protective film 19, but it does not necessarily have to have a protective film 19. In Figure 1, each layer (for example, the photosensitive layer and the intermediate layer) other than the protective film 19 that can be placed on the temporary support 11 is also referred to as a "composition layer".

[0082] The following provides a detailed description of each component and part of the transfer film. The following description of the constituent elements may be based on a typical embodiment of the present invention, but the present invention is not limited to such embodiments.

[0083] [Temporary support] The transfer film has a temporary support. The temporary support is a component that supports the photosensitive layer and is ultimately removed in the temporary support peeling process.

[0084] The temporary support may have either a single-layer or multi-layer structure. A film is preferred as the temporary support, and a resin film is more preferred. Furthermore, a film that is flexible and does not undergo significant deformation, shrinkage, or stretching under pressure or under pressure and / or heating is also preferred as the temporary support, and a film that is free from deformation such as wrinkles and scratches is also preferred. Examples of films include polyethylene terephthalate film (e.g., biaxially oriented polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film, with polyethylene terephthalate film being preferred.

[0085] The temporary support is preferably highly transparent so that pattern exposure can be performed through it. Specifically, the transmittance of the temporary support at a wavelength of 365 nm is preferably 60% or more, and more preferably 70% or more. The upper limit is preferably less than 100%. From the viewpoint of pattern formation during pattern exposure via the temporary support and the transparency of the temporary support, it is preferable that the haze of the temporary support be small. Specifically, the haze of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less. The lower limit is preferably 0% or more.

[0086] From the standpoint of pattern formation during pattern exposure via a temporary support and the transparency of the temporary support, it is preferable to have a small number of fine particles, foreign matter, and defects in the temporary support. Specifically, the number of fine particles (e.g., fine particles with a diameter of 1 μm), foreign matter, and defects in the temporary support should be 50 per 10 mm. 2 The following is preferable: 10 pieces / 10mm 2 The following is more preferable: 3 pieces / 10mm 2 The following is even more preferable: 1 piece / 10mm 2Less is particularly preferred. The lower limit is 0 pieces / 10 mm 2 Greater than or equal to is preferred.

[0087] The thickness of the temporary support is preferably 5 to 200 μm, more preferably 5 to 150 μm, still more preferably 5 to 50 μm, and particularly preferably 5 to 25 μm from the viewpoints of ease of handling and versatility. The thickness of the temporary support is calculated as the average value of any five points measured by cross-sectional observation using SEM (Scanning Electron Microscope).

[0088] From the viewpoint of handling property, the temporary support may have a layer containing fine particles (lubricant layer) on one or both surfaces of the temporary support. The diameter of the fine 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.

[0089] From the viewpoint of improving the adhesion between the temporary support and the photosensitive layer, the surface of the temporary support that contacts the photosensitive layer may be surface-modified. Examples of the surface modification treatment include treatments using UV irradiation, corona discharge, plasma, etc. The exposure amount in UV irradiation is preferably 10 to 2000 mJ / cm 2 and more preferably 50 to 1000 mJ / cm 2 is even more preferred. If the exposure amount is within the above range, the lamp output and illuminance are not particularly limited. Examples of the light source in UV irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes (LEDs) that emit light in the wavelength band of 150 to 450 nm.

[0090] Examples of temporary supports include a biaxially oriented polyethylene terephthalate film with a thickness of 16 μm, a biaxially oriented polyethylene terephthalate film with a thickness of 12 μm, and a biaxially oriented polyethylene terephthalate film with a thickness of 9 μm. Furthermore, examples of provisional supports include paragraphs

[0017] to

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

[0019] to

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

[0041] to

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

[0029] to

[0040] of International Publication No. 2018 / 179370, the contents of which are incorporated herein by reference. Examples of commercially available temporary supports include Lumirror 16KS40 and Lumirror 16FB40 (both manufactured by Toray Industries, Inc.); Cosmoshine A4100, Cosmoshine A4300, and Cosmoshine A8300 (all manufactured by Toyobo Co., Ltd.).

[0091] [Photosensitive layer] The transfer film has a photosensitive layer. The photosensitive layer comprises a crosslinkable alkali-soluble resin, an ethylenically unsaturated compound, and a photopolymerization initiator. The above photosensitive layer corresponds to a so-called negative-type photosensitive layer, and the formed resin pattern corresponds to a cured film. The following describes the various components that the photosensitive layer may contain.

[0092] <Resin> The photosensitive layer contains resin. The photosensitive layer of the transfer film used in the method of the present invention contains a crosslinkable alkali-soluble resin as the resin. As will be described later, the photosensitive layer may further contain other resins other than the crosslinkable alkali-soluble resin.

[0093] (Crosslinkable alkali-soluble resin) The crosslinkable alkali-soluble resin is preferably an alkali-soluble resin having crosslinkable groups in its side chains, and more preferably contains structural units having crosslinkable groups in its side chains, and even more preferably contains structural units having ethylenically unsaturated groups in its side chains, in terms of achieving superior effects of the present invention. Examples of the crosslinkable groups mentioned above include polymerizable groups found in polymerizable compounds described later, with ethylenically unsaturated groups being preferred, and acryloyl groups or methacryloyl groups being more preferred. Furthermore, it is preferable that the polymerizable group is a polymerizable group that can undergo polymerization reaction with the polymerizable group of the polymerizable compound described later.

[0094] As a structural unit having a crosslinkable group in its side chain, the structural unit represented by formula (P) is preferred.

[0095] [ka]

[0096] In formula (P), R P L represents a hydrogen atom or a methyl group. P represents a divalent linking group. P represents a crosslinking group.

[0097] R P represents a hydrogen atom or a methyl group. R P A hydrogen atom is preferred as the element.

[0098] L P This represents a divalent linking group. Examples of the above-mentioned divalent linking groups include -CO-, -O-, -S-, -SO-, -SO2-, and -NR. N -, hydrocarbon groups, and groups formed by combining them are examples. N represents a hydrogen atom or substituent. Examples of the hydrocarbon groups mentioned above include alkylene groups, cycloalkylene groups, and arylene groups. The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 2 to 8, and even more preferably 3 to 5. The alkylene group may have a heteroatom, and the methylene group in the alkylene group may be replaced by a heteroatom. The heteroatom is preferably an oxygen atom, a sulfur atom, or a nitrogen atom, and more preferably an oxygen atom. The cycloalkylene group may be monocyclic or polycyclic. The number of carbon atoms in the cycloalkylene group is preferably 3 to 20, more preferably 5 to 10, and even more preferably 6 to 8. The above arylene group may be monocyclic or polycyclic. The number of carbon atoms in the above arylene group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. A phenylene group is preferred as the above arylene group. The above-mentioned cycloalkylene group and arylene group may have a heteroatom as a ring member atom. The heteroatom is preferably an oxygen atom, a sulfur atom, or a nitrogen atom, and more preferably an oxygen atom. The above hydrocarbon group may further have substituents. Examples of the substituents mentioned above include halogen atoms (e.g., fluorine atoms), hydroxyl groups, nitro groups, cyano groups, alkyl groups, alkoxy groups, alkoxycarbonyl groups, and alkenyl groups, with hydroxyl groups being preferred. L P As such, an alkylene group which may have a heteroatom is preferred.

[0099] P represents a crosslinking group. The crosslinkable groups are as described above.

[0100] Examples of structural units having crosslinking groups in their side chains include the following:

[0101] [ka]

[0102] In the crosslinkable alkali-soluble resin, the content of structural units having crosslinkable groups in their side chains is preferably 5.0 to 70.0% by mass, more preferably 10.0 to 50.0% by mass, and even more preferably 15.0 to 40.0% by mass, based on the total mass of the crosslinkable alkali-soluble resin.

[0103] The crosslinkable alkali-soluble resin preferably contains constituent units derived from monomers having aromatic hydrocarbon groups, as this suppresses line width thickening and deterioration of resolution when the focal position shifts during exposure. Examples of the above-mentioned aromatic hydrocarbon groups include optionally substituted phenyl groups and optionally substituted aralkyl groups. The content of constituent units derived from monomers having aromatic hydrocarbon groups is preferably 10.0% by mass or more, more preferably 20.0% by mass or more, and even more preferably 30.0% by mass or more, relative to the total mass of the crosslinkable alkali-soluble resin. The upper limit is preferably 80.0% by mass or less, more preferably 70.0% by mass or less, and even more preferably 65.0% by mass or less, relative to the total mass of the crosslinkable alkali-soluble resin. When the photosensitive layer contains multiple crosslinkable alkali-soluble resins, it is preferable that the average mass of the content of constituent units derived from monomers having aromatic hydrocarbon groups is within the above range.

[0104] Examples of monomers having aromatic hydrocarbon groups include monomers having aralkyl groups, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer). Monomers having aralkyl groups or styrene are preferred, and styrene is more preferred. When the monomer having an aromatic hydrocarbon group is styrene, the content of constituent units derived from styrene is preferably 10.0 to 80.0% by mass, more preferably 20.0 to 70.0% by mass, and even more preferably 30.0 to 65.0% by mass, relative to the total mass of the crosslinkable alkali-soluble resin. When the photosensitive layer contains multiple crosslinkable alkali-soluble resins, it is preferable that the average mass value of the content of constituent units having an aromatic hydrocarbon group is within the above range.

[0105] Examples of aralkyl groups include optionally substituted phenylalkyl groups (excluding benzyl groups) and optionally substituted benzyl groups, with optionally substituted benzyl groups being preferred.

[0106] Examples of monomers having a phenylalkyl group include phenylethyl (meth)acrylate.

[0107] Examples of monomers having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; and vinyl monomers having a benzyl group, such as vinyl benzyl chloride and vinylbenzyl alcohol. (meth)acrylates having a benzyl group are preferred, and benzyl (meth)acrylate is more preferred. When the monomer having an aromatic hydrocarbon group is benzyl (meth)acrylate, the content of constituent units derived from benzyl (meth)acrylate is preferably 10.0 to 90.0% by mass, more preferably 20.0 to 80.0% by mass, and even more preferably 30.0 to 70.0% by mass, based on the total mass of the crosslinkable alkali-soluble resin.

[0108] A preferred embodiment of a crosslinkable alkali-soluble resin containing structural units derived from monomers having aromatic hydrocarbon groups includes a resin comprising structural units derived from monomers having aromatic hydrocarbon groups, structural units having crosslinkable groups in their side chains, structural units derived from a first monomer described later, and optionally structural units derived from a second monomer described later.

[0109] Furthermore, another preferred embodiment of a crosslinkable alkali-soluble resin containing a constituent unit derived from a monomer having an aromatic hydrocarbon group is a resin obtained by polymerizing a monomer having an aromatic hydrocarbon group, a first monomer described later, and optionally a second monomer described later, and then reacting the carboxyl group in the constituent unit derived from the first monomer with a third monomer described later. As described later, the third monomer is a polymerizable compound having a reactive group that can react with a carboxyl group (e.g., an epoxy group) and one or more other polymerizable groups (e.g., an ethylenically unsaturated group). By reacting the third monomer with the carboxyl group in the constituent unit derived from the first monomer, a constituent unit having a crosslinkable group in its side chain can be formed in the crosslinkable alkali-soluble resin.

[0110] A preferred embodiment of a crosslinkable alkali-soluble resin that does not contain structural units derived from monomers having aromatic hydrocarbon groups includes a resin comprising structural units derived from a first monomer described later, structural units having crosslinkable groups in their side chains, and optionally structural units derived from a second monomer described later.

[0111] Furthermore, another preferred embodiment of a crosslinkable alkali-soluble resin that does not contain structural units derived from monomers having aromatic hydrocarbon groups is a resin obtained by polymerizing a first monomer (described later) and optionally a second monomer (also described later), and then reacting the carboxyl group in the structural unit derived from the first monomer with a third monomer (described later). As described later, the third monomer is a polymerizable compound having a reactive group that can react with a carboxyl group (e.g., an epoxy group) and one or more other polymerizable groups (e.g., an ethylenically unsaturated group). By reacting the third monomer with the carboxyl group in the structural unit derived from the first monomer, structural units having crosslinkable groups in their side chains can be formed in the crosslinkable alkali-soluble resin.

[0112] The first monomer is a monomer that has a carboxyl group in its molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid semiester, with (meth)acrylic acid being preferred. The content of constituent units derived from the first monomer is preferably 5.0 to 50.0% by mass, more preferably 10.0 to 40.0% by mass, and even more preferably 10.0 to 30.0% by mass, relative to the total mass of the crosslinkable alkali-soluble resin. When the above content is 5.0% by mass or more, excellent developability and edge fusing control can be achieved. When the above content is 50.0% by mass or less, high resolution of the resist pattern, further suppression of the tail shape, and high chemical resistance of the resist pattern can be achieved.

[0113] As mentioned above, in some cases, a structural unit having a crosslinkable group in its side chain is introduced into the crosslinkable alkali-soluble resin by reacting the carboxyl group in the structural unit derived from the first monomer in the crosslinkable alkali-soluble resin with the third monomer described later. The content of the structural unit derived from the first monomer mentioned above refers to the content of structural units derived from the first monomer that have not reacted with the third monomer.

[0114] The second monomer is non-acidic and has polymerizable groups in its molecule. The polymerizable group is synonymous with the polymerizable group possessed by the polymerizable compound described later, and the preferred embodiment is also the same. 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, ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or n-butyl (meth)acrylate are preferred, and methyl (meth)acrylate or ethyl (meth)acrylate are more preferred. The content of constituent units derived from the second monomer is preferably 1.0 to 60.0% by mass, more preferably 1.0 to 50.0% by mass, and even more preferably 1.0 to 30.0% by mass, relative to the total mass of the crosslinkable alkali-soluble resin.

[0115] The crosslinkable alkali-soluble resin may have a linear structure, a branched structure, or an alicyclic structure in its side chains. By using a monomer containing a group with a branched structure in its side chain, or a monomer containing a group with an alicyclic structure in its side chain, a branched structure or an alicyclic structure can be introduced into the side chain of a crosslinkable alkali-soluble resin. The group with the alicyclic structure may be monocyclic or polycyclic. A "side chain" refers to a group of atoms that branch off from the main chain. The "main chain" refers to the relatively longest bonding chain in the polymer compound that makes up a crosslinkable alkali-soluble resin. Examples of monomers containing a group with a branched structure in its side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, tert-amyl (meth)acrylate, sec-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and tert-octyl (meth)acrylate. Among these, isopropyl (meth)acrylate, isobutyl (meth)acrylate, or tert-butyl methacrylate are preferred, and isopropyl methacrylate or tert-butyl methacrylate are more preferred. Examples of monomers containing a group with an alicyclic structure in its side chain include monomers having a monocyclic aliphatic hydrocarbon group and monomers having a polycyclic aliphatic hydrocarbon group. Also, (meth)acrylates having an alicyclic hydrocarbon group with 5 to 20 carbon atoms are also examples. Specifically, (meth)acrylic acid (bicyclo[2.2.1]heptyl-2), (meth)acrylic acid-1-adamantyl, (meth)acrylic acid-2-adamantyl, (meth)acrylic acid-3-methyl-1-adamantyl, (meth)acrylic acid-3,5-dimethyl-1-adamantyl, (meth)acrylic acid-3-ethyladamantyl, (meth)acrylic acid-3-methyl-5-ethyl-1-adamantyl, (meth)acrylic acid-3,5,8-triethyl-1-adamantyl, (meth)acrylic acid-3,5-dimethyl-8-ethyl-1-adamantyl, (meth)acrylic acid-2-methyl-2-adamantyl, (meth)acrylic acid-2-ethyl-2-adamantyl, (meth)acrylic acid-3-hydroxy-1 Examples include adamantyl, octahydro-4,7-menthanoinden-5-yl (meth)acrylate, octahydro-4,7-menthanoinden-1-ylmethyl (meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl (meth)acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fentyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, and cyclohexyl (meth)acrylate. Among these, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fentyl (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecane (meth)acrylate are preferred, and cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate are more preferred.

[0116] As described above, crosslinkable alkali-soluble resins include resins obtained by reacting a resin containing constituent units derived from a first monomer with a third monomer. The third monomer is a polymerizable compound having a reactive group (preferably an epoxy group) that can react with the carboxyl group in the constituent unit derived from the first monomer, and one or more other polymerizable groups (preferably ethylenically unsaturated groups). The third monomer is preferably a compound having an epoxy group and an ethylenically unsaturated group (an ethylenically active compound having an epoxy group), and more preferably a compound having an epoxy group and an acryloyl group or a methacryloyl group.

[0117] An example of a third monomer is glycidyl (meth)acrylate.

[0118] Methods for introducing crosslinkable groups into the side chains of a resin include, for example, reacting epoxy compounds, blocked isocyanate compounds, isocyanate compounds, vinyl sulfone compounds, aldehyde compounds, methylol compounds, and carboxylic acid anhydrides with groups such as hydroxyl groups, carboxyl groups, primary amino groups, secondary amino groups, acetoacetyl groups, and sulfo groups present in the resin.

[0119] For example, as described above, one method for introducing a crosslinkable group into a resin by reacting a carboxyl group in a structural unit derived from a first monomer with a third monomer is to synthesize a first monomer and optionally another monomer by polymerization, and then react a third monomer (preferably glycidyl (meth)acrylate) with a carboxyl group (preferably a part of a carboxyl group) of a structural unit derived from the first monomer of the resulting resin to introduce a crosslinkable group (preferably a (meth)acryloxy group) into the resin. The reaction temperature for the reaction between the carboxyl group and the third monomer is preferably 80 to 110°C. Furthermore, it is preferable to use a catalyst in this reaction, and more preferably to use an ammonium salt (tetraethylammonium bromide). Furthermore, the reaction temperature for the polymerization reaction is preferably 70 to 100°C, and more preferably 80 to 90°C. The polymerization reaction is preferably carried out using a polymerization initiator, more preferably an azo-based initiator, and even more preferably V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) or V-65 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as the polymerization initiator.

[0120] Preferably, the crosslinkable alkali-soluble resin is a resin containing a structural unit having a crosslinkable group in its side chain, a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, a structural unit derived from styrene, or a structural unit derived from benzyl methacrylate, or a resin containing a structural unit having a crosslinkable group in its side chain, a structural unit derived from methacrylic acid, and a structural unit derived from styrene. In the above, it is also preferable to adjust the content of each constituent unit to the respective preferred configurations described above.

[0121] The Tg of the crosslinkable alkali-soluble resin is preferably 60 to 150°C, more preferably 80 to 150°C, and even more preferably 100 to 150°C.

[0122] The acid value of the crosslinkable alkali-soluble resin is preferably 220 mgKOH / g or less, more preferably 200 mgKOH / g or less, even more preferably 190 mgKOH / g or less, and particularly preferably 170 mgKOH / g or less, from the viewpoint of achieving superior effects of the present invention. The lower limit is preferably 10 mgKOH / g or more, more preferably 60 mgKOH / g or more, even more preferably 80 mgKOH / g or more, and particularly preferably 90 mgKOH / g or more, from the viewpoint of achieving superior effects of the present invention.

[0123] "Acid value (mgKOH / g)" refers to the mass (mg) of potassium hydroxide required to neutralize 1 g of a sample. The acid value can be determined, for example, in accordance with JIS K0070:1992. The acid value of a crosslinkable alkali-soluble resin can be adjusted by the type of constituent units and / or the content of constituent units containing acid groups in the crosslinkable alkali-soluble resin. When the photosensitive layer contains two or more crosslinkable alkali-soluble resins, the content of the crosslinkable alkali-soluble resins that satisfy the above acid value range is preferably 10 to 100% by mass, more preferably 60 to 100% by mass, and even more preferably 90 to 100% by mass, based on the total mass of the crosslinkable alkali-soluble resins.

[0124] The C=C value of the crosslinkable alkali-soluble resin is preferably 0.1 to 3.0 mmol / g. The C=C value of the crosslinkable alkali-soluble resin refers to the equivalent amount (molar amount) of double bond groups contained per gram of the crosslinkable alkali-soluble resin. The lower limit of the C=C value of the crosslinkable alkali-soluble resin is more preferably 0.4 mmol / g or higher, in terms of achieving superior effects of the present invention. The upper limit of the C=C value of the crosslinkable alkali-soluble resin is more preferably 2.0 mmol / g or lower, and even more preferably 1.0 mmol / g or lower, in terms of achieving superior effects of the present invention. Furthermore, it is also preferable that the lower limit of the C=C value of the crosslinkable alkali-soluble resin is greater than 1.0 mmol / g.

[0125] The weight-average molecular weight of the crosslinkable alkali-soluble resin is preferably 500,000 or less, more preferably 100,000 or less, even more preferably 30,000 or less, and particularly preferably 25,000 or less. The weight-average molecular weight of the crosslinkable alkali-soluble resin is preferably 3,000 or more, more preferably 4,000 or more, even more preferably 5,000 or more, and particularly preferably 10,000 or more. When the weight-average molecular weight is 500,000 or less, resolution and developability can be improved. Furthermore, when the weight-average molecular weight is 3,000 or more, the properties of the developed aggregates, as well as the properties of the unexposed film such as edge fusing and cut-tip properties of the transfer film, can be controlled. "Edge fusing" refers to the degree to which the photosensitive layer tends to protrude from the edge of the roll when the transfer film is wound into a roll. "Cut-tip properties" refers to the degree to which chips tend to fly off when the unexposed film is cut with a cutter. If these chips adhere to the upper surface of the transfer film, they can be transferred to the mask in subsequent exposure processes, causing defective products. The degree of dispersion of the crosslinkable alkali-soluble resin 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. When the photosensitive layer contains two or more crosslinkable alkali-soluble resins, the content of the crosslinkable alkali-soluble resins that satisfies the above weight-average molecular weight and / or dispersion range is preferably 10 to 100% by mass, more preferably 60 to 100% by mass, and even more preferably 90 to 100% by mass, based on the total mass of the crosslinkable alkali-soluble resins.

[0126] The crosslinkable alkali-soluble resin may be used alone or in combination of two or more types. When using two or more types of resins, it is preferable to use a mixture of two resins containing constituent units derived from monomers having aromatic hydrocarbon groups, or to use a mixture of a resin containing constituent units derived from monomers having aromatic hydrocarbon groups and a resin that does not contain constituent units derived from monomers having aromatic hydrocarbon groups. In the latter case, the content of the resin containing constituent units derived from monomers having aromatic hydrocarbon groups is preferably 50.0% by mass or more, more preferably 70.0% by mass or more, even more preferably 80.0% by mass or more, and particularly preferably 90.0% by mass or more, based on the total mass of the resin. The upper limit is preferably 100.0% by mass or less, based on the total mass of the resin.

[0127] The content of the crosslinkable alkali-soluble resin is preferably 10.0 to 90.0% by mass, more preferably 20.0 to 80.0% by mass, even more preferably 30.0 to 70.0% by mass, and particularly preferably 40.0 to 60.0% by mass, relative to the total mass of the photosensitive layer. When the content of the crosslinkable alkali-soluble resin is 90.0% by mass or less relative to the total mass of the photosensitive layer, the development time can be controlled. Furthermore, when the content of the crosslinkable alkali-soluble resin is 10.0% by mass or more relative to the total mass of the photosensitive layer, the edge fusing resistance can be improved.

[0128] One method for synthesizing crosslinkable alkali-soluble resins is to dilute the above-mentioned monomers with a solvent, add an appropriate amount of radical polymerization initiator to the solution, and heat and stir. The mixture may also be synthesized by adding a portion of it dropwise to the reaction solution. Alternatively, after the reaction is complete, the solvent may be further added to adjust the concentration to the desired level. Other methods for synthesizing crosslinkable alkali-soluble resins include, for example, bulk polymerization, suspension polymerization, and emulsion polymerization.

[0129] (Resins other than crosslinkable alkali-soluble resins) The photosensitive layer may contain other resins in addition to the crosslinkable alkali-soluble resin described above. Examples of other resins include alkali-soluble resins that do not have crosslinkable groups. Other resins include, for example, 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.

[0130] <Polymerizable compound> The photosensitive layer contains a polymerizable compound having polymerizable groups. "Polymerizable compound" refers to a compound that polymerizes through the action of a polymerization initiator, as described later, and is different from the resin mentioned above.

[0131] The polymerizable groups in a polymerizable compound can be any group that participates in the polymerization reaction, such as ethylenically unsaturated groups like vinyl groups, acryloyl groups, methacryloyl groups, styryl groups, and maleimide groups; and cationic polymerizable groups like epoxy groups and oxetane groups.

[0132] (Polymerizable compounds containing ethylenically unsaturated groups) The photosensitive layer of the transfer film used in the method of the present invention essentially contains a polymerizable compound having an ethylenically unsaturated group (hereinafter also referred to as "ethylenically unsaturated compound") as a polymerizable compound having a polymerizable group. Among the ethylenically unsaturated groups, an acryloyl group or a methacryloyl group is more preferred.

[0133] The number of ethylenically unsaturated groups in an ethylenically unsaturated compound is not particularly limited as long as there is one or more, but it is more preferable to have two or more. In other words, as an ethylenically unsaturated compound, a compound having two or more ethylenically unsaturated groups (hereinafter also referred to as a "polyfunctional ethylenically unsaturated compound") is preferred. Furthermore, in terms of superior resolution and exfoliation properties, the number of ethylenically unsaturated groups in the molecule of the ethylenically unsaturated compound is preferably 1 to 6, more preferably 1 to 3, and even more preferably 2 to 3.

[0134] Ethylene unsaturated compounds may have alkylene oxy groups. The alkylene group is preferably an ethylene oxy group or a propylene oxy group, with the ethylene oxy group being more preferred. The number of alkylene oxy groups added to the polymerizable compound is preferably 2 to 60 per molecule, more preferably 2 to 30, and even more preferably 2 to 20. The content of ethylenically unsaturated compounds having alkylene oxy groups (preferably ethylene oxy groups) is preferably 10 to 100% by mass, more preferably 60 to 100% by mass, and even more preferably 90 to 100% by mass, relative to the total polymerizable compounds in the photosensitive layer.

[0135] The content of the bifunctional ethylenically unsaturated compound in the photosensitive layer is preferably 20.0% by mass or more, more preferably 40.0% by mass or more, even more preferably 55.0% by mass or more, and particularly preferably 90.0% by mass or more, based on the total mass of the polymerizable compound. The upper limit is preferably 100.0% by mass or less, and more preferably 80.0% by mass or less. In other words, all polymerizable compounds contained in the photosensitive layer may be bifunctional ethylenically unsaturated compounds. The content of trifunctional or greater ethylenically unsaturated compounds in the photosensitive layer (preferably the content of trifunctional ethylenically unsaturated compounds) is preferably 10.0% by mass or more, and more preferably 20.0% by mass or more, relative to the total mass of polymerizable compounds. The upper limit is preferably 100.0% by mass or less, more preferably 80.0% by mass or less, and even more preferably 50.0% by mass or less. In other words, all polymerizable compounds contained in the photosensitive layer may be trifunctional or greater ethylenically unsaturated compounds (preferably trifunctional ethylenically unsaturated compounds). Furthermore, as an ethylenically unsaturated compound, a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group is preferred.

[0136] ·Polymerizable compound B1 The photosensitive layer may also preferably contain polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups. Polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in its molecule, among the polymerizable compounds described above.

[0137] Examples of aromatic rings in polymerizable compound B1 include aromatic hydrocarbon rings such as benzene rings, naphthalene rings, and anthracene rings; aromatic heterocycles such as thiophene rings, furan rings, pyrrole rings, imidazole rings, triazole rings, and pyridine rings; and fused rings thereof. Aromatic hydrocarbon rings are preferred, and benzene rings are more preferred. The above aromatic rings may have substituents. Polymerizable compound B1 may have one or more aromatic rings.

[0138] Polymerizable compound B1 is preferably a bisphenol structure because it improves resolution by suppressing swelling of the photosensitive layer due to the developer. Examples of bisphenol structures include the bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), the bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and the bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), with the bisphenol A structure being preferred.

[0139] Examples of polymerizable compounds B1 having a bisphenol structure include compounds having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. The two polymerizable groups at both ends of the bisphenol structure may be directly bonded, or they may be bonded via one or more alkylene oxy groups. The alkylene oxy groups added to both ends of the bisphenol structure are preferably ethylene oxy groups or propylene oxy groups, with ethylene oxy groups being more preferred. The number of alkylene oxy groups (preferably ethylene oxy groups) added to the bisphenol structure is preferably 2 to 60 per molecule, more preferably 2 to 30, and even more preferably 2 to 20. Examples of polymerizable compounds B1 having a bisphenol structure include paragraphs

[0072] to

[0080] of Japanese Patent Application Publication No. 2016-224162, the contents of which are incorporated herein by reference.

[0140] 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, and 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane, as well as ethoxylated bisphenol A dimethacrylates (BPE series, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), 2,2-bis(4-(methacryloxydodecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), and ethoxylated (10) bisphenol A diacrylate (NK ester A-BPE-10, manufactured by Shin Nakamura Chemical Industry Co., Ltd.).

[0141] As the polymerizable compound B1, the compound represented by formula (B1) is also preferred.

[0142] [ka]

[0143] In formula (B1), R1 and R2 each independently represent a hydrogen atom or a methyl group. A represents an ethylene group. B represents a propylene group. n1 and n3 each independently represent an integer from 1 to 39. n1 + n3 represents an integer from 2 to 40. n2 and n4 each independently represent an integer from 0 to 29. n2 + n4 represents an integer from 0 to 30. The arrangement of the constituent units of -(AO)- and -(BO)- may be random or blocky. If it is blocky, either -(AO)- or -(BO)- may be on the bisphenyl group side. For n1+n2+n3+n4, values ​​between 2 and 20 are preferred, more preferably between 2 and 16, and even more preferably between 4 and 12. Also, for n2+n4, values ​​between 0 and 10 are preferred, more preferably between 0 and 4, even more preferably between 0 and 2, and particularly preferred when 0 is used.

[0144] The content of polymerizable compound B1 is preferably 10.0% by mass or more, more preferably 20.0% by mass or more, and even more preferably 25.0% by mass or more, relative to the total mass of the photosensitive layer, from the viewpoint of superior resolution. The upper limit is preferably 70.0% by mass or less, and more preferably 60.0% by mass or less, from the viewpoint of transferability and edge fusion (the phenomenon in which the photosensitive composition seeps out from the edges of the transfer material).

[0145] The content of polymerizable compound B1 is preferably 40.0% by mass or more, more preferably 50.0% by mass or more, even more preferably 55.0% by mass or more, and particularly preferably 60.0% by mass or more, relative to the total mass of the polymerizable compound, from the viewpoint of superior resolution. The upper limit is preferably 100.0% by mass or less, more preferably 99.0% by mass or less, and even more preferably 95.0% by mass or less, relative to the total mass of the polymerizable compound, from the viewpoint of peelability.

[0146] • Other ethylenically unsaturated compounds other than polymerizable compound B1 Other ethylenically unsaturated compounds besides polymerizable compound B1 are not particularly limited and include, for example, compounds having one ethylenically unsaturated group in the molecule (monofunctional ethylenically unsaturated compounds), difunctional ethylenically unsaturated compounds without aromatic rings, and trifunctional or more ethylenically unsaturated compounds.

[0147] 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.

[0148] Examples of bifunctional ethylenically unsaturated compounds that do not have an aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate. Examples of alkylene glycol di(meth)acrylates include tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), tricyclodecanedimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate. Examples of polyalkylene glycol di(meth)acrylates include polyethylene glycol di(meth)acrylate (NK Ester 4G, etc., manufactured by Shin Nakamura Chemical Industry Co., Ltd.), dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate (Aronics M-270, etc., manufactured by Toagosei Co., Ltd.). Examples of urethane di(meth)acrylates include propylene oxide-modified urethane di(meth)acrylate, as well as ethylene oxide and propylene oxide-modified urethane di(meth)acrylate. Examples of commercially available urethane di(meth)acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., Ltd.).

[0149] Examples of ethylenically unsaturated compounds with three or more functions include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide modified products thereof. "(tri / tetra / penta / hexa)(meth)acrylate" is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate. Furthermore, "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate.

[0150] Examples of alkylene oxide modified products of ethylenically unsaturated compounds with three or more functions include caprolactone-modified (meth)acrylate compounds (KAYARAD® DPCA-20 manufactured by Nippon Kayaku Co., Ltd., and A-9300-1CL manufactured by Shin Nakamura Chemical Industry 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 Industry Co., Ltd., and EBECRYL® manufactured by Daicel Ornex Co., Ltd.). Examples include 135, ethoxylated glycerin triacrylate (such as A-GLY-9E manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Arronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Arronix M-520 (manufactured by Toagosei Co., Ltd.), Arronix M-510 (manufactured by Toagosei Co., Ltd.), and SR454 (manufactured by Tomoe Chemical Co., Ltd.).

[0151] The polymerizable compound may be a polymerizable compound having an acidic group (for example, a carboxyl group). The acidic group may form an acid anhydride group. Examples of ethylenically unsaturated compounds containing an acidic group include Arronix® TO-2349 (manufactured by Toagosei Co., Ltd.), Arronix® M-520 (manufactured by Toagosei Co., Ltd.), and Arronix® M-510 (manufactured by Toagosei Co., Ltd.). Examples of ethylenically unsaturated compounds having an acidic group include the polymerizable compounds described in paragraphs

[0025] to

[0030] of Japanese Patent Publication No. 2004-239942.

[0152] The molecular weight of the ethylenically unsaturated compound is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.

[0153] Ethylene-unsaturated compounds may be used individually or in combination of two or more. In particular, ethylenically unsaturated compounds are preferable to be used in groups of three or more, as this enhances the effects of the present invention. When using three types of ethylenically unsaturated compounds, it is preferable that at least one of the three is polymerizable compound B1, and it is more preferable that at least two of the three are polymerizable compound B1. The content of ethylenically unsaturated compounds is preferably 10.0 to 70.0% by mass, more preferably 15.0 to 70.0% by mass, and even more preferably 20.0 to 70.0% by mass, relative to the total mass of the photosensitive layer.

[0154] The mass ratio of the ethylenically unsaturated compound content to the resin content (ethylenically unsaturated compound content / resin content) is preferably 0.10 to 2.00, more preferably 0.50 to 1.50, and even more preferably 0.70 to 1.10, as this provides superior effects of the present invention.

[0155] The photosensitive layer may also preferably contain the polymerizable compound B1 and a trifunctional or more ethylenically unsaturated compound. The mass ratio of polymerizable compound B1 content to content of trifunctional or ethylenically unsaturated compound (content of polymerizable compound B1 / content of trifunctional or ethylenically unsaturated compound) is preferably 1.0 to 5.0, more preferably 1.2 to 4.0, and even more preferably 1.5 to 3.0.

[0156] (Other polymerizable compounds besides ethylenically unsaturated compounds) The photosensitive layer may contain polymerizable compounds other than ethylenically unsaturated compounds. Examples of polymerizable compounds other than ethylenically unsaturated compounds include epoxy groups and groups having cationic polymerizable groups such as oxetane groups.

[0157] <Polymerization initiator> The photosensitive layer contains a polymerization initiator. Examples of polymerization initiators include known polymerization initiators depending on the type of polymerization reaction. Specifically, these include thermal polymerization initiators and photopolymerization initiators.

[0158] The photosensitive layer of the transfer film used in the method of the present invention contains a photopolymerization initiator as a polymerization initiator. A photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound upon exposure to active light such as ultraviolet light, visible light, and X-rays. Examples of photopolymerization initiators include well-known photopolymerization initiators. Examples of photopolymerization initiators include photoradical polymerization initiators and photocationic polymerization initiators, with photoradical polymerization initiators being preferred.

[0159] Examples of photo-radical polymerization initiators include photopolymerization initiators having an oxime ester structure, photopolymerization initiators having an α-aminoalkylphenone structure, photopolymerization initiators having an α-hydroxyalkylphenone structure, photopolymerization initiators having an acylphosphine oxide structure, and photopolymerization initiators having an N-phenylglycine structure.

[0160] The photoradical polymerization initiator preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and their derivatives, from the viewpoint of photosensitivity, visibility of exposed and unexposed areas, and resolution. The two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivative may be the same or different. Examples of derivatives of the 2,4,5-triarylimidazole dimer include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0161] Examples of photoradical polymerization initiators include those described in paragraphs

[0031] to

[0042] of Japanese Patent Publication No. 2011-095716 and paragraphs

[0064] to

[0081] of Japanese Patent Publication No. 2015-014783.

[0162] Examples of photoradical polymerization initiators include ethyl dimethylaminobenzoate (DBE), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (manufactured by Midori Chemical Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (manufactured by Midori Chemical Co., Ltd.), 1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyl oxime) (IRGACURE® OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyl oxime) (IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), and IRGACURE OXE-04 (BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (Omnirad 379EG, IGM Resins BV), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (Omnirad 907, IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (Omnirad 127, IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (Omnirad 369, IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropan-1-one (Omnirad 1173 (manufactured by IGM Resins BV), 1-hydroxycyclohexyl phenyl ketone (Omnirad 184, manufactured by IGM Resins BV), 2,2-dimethoxy-1,2-diphenylethane-1-one (Omnirad 651, manufactured by IGM Resins BV), 2,4,6-trimethylbenzolyl-diphenylphosphine oxide (Omnirad TPO H, manufactured by IGM Resins BV), bis(2,4,6-trimethylbenzolyl)phenylphosphine oxide (Omnirad 819, manufactured by IGM Resins BV)(manufactured by DKSH Japan), oxime ester-based photopolymerization initiator (Lunar 6, manufactured by DKSH Japan), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (B-CIM, manufactured by Hampford), 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (TR-PBG-305, manufactured by Changzhou Strong Electronics Co., Ltd.) Examples include 1,2-propanedione,3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazole-3-yl]-,2-(O-acetyloxime) (TR-PBG-326, manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazole-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (TR-PBG-391, manufactured by Changzhou Strong Electronics New Materials Co., Ltd.).

[0163] A photocationic polymerization initiator (photoacid generator) is a compound that generates acid upon receiving active light. Preferred photocationic polymerization initiators are compounds that are sensitive to active light with a wavelength of 300 nm or higher (preferably 300-450 nm) and generate acid. Furthermore, photocationic polymerization initiators that are not directly sensitive to active light with a wavelength of 300 nm or higher can also be preferably used in combination with a sensitizer, provided they become sensitive to active light with a wavelength of 300 nm or higher and generate acid. As the photocationic polymerization initiator, a photocationic polymerization initiator that generates an acid with a pKa of 4 or less is preferred, a photocationic polymerization initiator that generates an acid with a pKa of 3 or less is more preferred, and a photocationic polymerization initiator that generates an acid with a pKa of 2 or less is even more preferred. The lower limit is preferably -10.0 or higher.

[0164] Examples of photocationic polymerization initiators include ionic photocationic polymerization initiators and nonionic photocationic polymerization initiators. Examples of ionic photocationic polymerization initiators include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, as well as quaternary ammonium salts. Examples of ionic photocationic polymerization initiators include those described in paragraphs

[0114] to

[0133] of Japanese Patent Application Publication No. 2014-085643.

[0165] Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triazines, diazomethane compounds, imidosulfonate compounds, and oximesulfonate compounds. Examples of trichloromethyl-s-triazines, diazomethane compounds, and imidosulfonate compounds include those described in paragraphs

[0083] to

[0088] of Japanese Patent Publication No. 2011-221494. Examples of oximesulfonate compounds include those described in paragraphs

[0084] to

[0088] of International Publication No. 2018 / 179640.

[0166] The photopolymerization initiator may be used alone or in combination of two or more types. The content of the photopolymerization initiator is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more, based on the total mass of the photosensitive layer. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, based on the total mass of the photosensitive layer.

[0167] <Pigments (colorants)> The photosensitive layer may contain a dye (color developer) whose maximum absorption wavelength in the wavelength range of 400-780 nm during color development is 450 nm or higher, and whose maximum absorption wavelength changes with the presence of an acid, base, or radical, in order to ensure visibility of the exposed and unexposed areas, as well as pattern visibility and resolution after development. Hereinafter, the dye (color developer) will also be referred to as "dye N". When pigment N is included, although the detailed mechanism is unknown, the adhesion to adjacent layers (e.g., intermediate layers) is improved, resulting in superior resolution.

[0168] The phrase "the maximum absorption wavelength of a pigment changes due to an acid, base, or radical" may mean any of the following: a pigment in a colored state is decolorized by an acid, base, or radical; a pigment in a decolorized state is colored by an acid, base, or radical; or a pigment in a colored state changes to a colored state of another hue. Specifically, the dye N may be either a compound that changes from a decolorized state to a colored state upon exposure, or a compound that changes from a colored state to a decolorized state upon exposure. In the above case, the dye may change its colored or decolorized state due to the generation and action of an acid, base, or radical within the photosensitive layer upon exposure, or it may be a dye that changes its colored or decolorized state due to a change in the state within the photosensitive layer (e.g., pH) caused by an acid, base, or radical. Furthermore, the dye may change its colored or decolorized state upon direct stimulation by an acid, base, or radical without the need for exposure.

[0169] In particular, from the viewpoint of visibility and resolution of the exposed and unexposed areas, the dye N is preferably a dye whose maximum absorption wavelength changes with acid or radicals, and more preferably a dye whose maximum absorption wavelength changes with radicals. The photosensitive layer preferably contains both a dye N whose maximum absorption wavelength changes with radicals and a photoradical polymerization initiator, from the viewpoint of visibility and resolution between the exposed and unexposed areas. Furthermore, from the viewpoint of visibility between the exposed and unexposed areas, the dye N is preferably a dye that develops color with an acid, base, or radical.

[0170] One example of a color development mechanism for dye N is to add a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator), or a photobase generator to the photosensitive layer, and after exposure, radicals, acids, or bases generated from the photoradical polymerization initiator, photocationic polymerization initiator, or photobase generator cause a radical-reactive dye, an acid-reactive dye, or a base-reactive dye (e.g., a leuco dye) to develop color.

[0171] From the viewpoint of visibility of the exposed and unexposed areas, the maximum absorption wavelength of the dye N in the wavelength range of 400 to 780 nm during color development is preferably 550 nm or higher, more preferably 550 to 700 nm, and even more preferably 550 to 650 nm. Furthermore, the dye N may have one or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm during color development. If the dye N has two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm during color development, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths should be 450 nm or higher.

[0172] The maximum absorption wavelength of dye N can be measured in an atmospheric environment using a UV3100 spectrophotometer (Shimadzu Corporation) to measure the transmission spectrum of a solution containing dye N (at a temperature of 25°C) in the range of 400 to 780 nm, and then detecting the wavelength at which the light intensity is minimum (maximum absorption wavelength).

[0173] Examples of dyes that develop or decolorize upon exposure include leuco compounds. Examples of dyes that decolorize upon exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes. As for the dye N, a leuco compound is preferred from the viewpoint of visibility between the exposed and unexposed areas.

[0174] Examples of leuco compounds include leuco compounds having a triarylmethane skeleton (triarylmethane dyes), leuco compounds having a spiropyran skeleton (spiropyran dyes), leuco compounds having a fluorane skeleton (fluorane dyes), leuco compounds having a diarylmethane skeleton (diarylmethane dyes), leuco compounds having a rhodamine lactam skeleton (rhodamine lactam dyes), leuco compounds having an indolylphthalide skeleton (indolylphthalide dyes), and leuco compounds having a leucoauramine skeleton (leucoauramine dyes). Among these, triarylmethane-based dyes or fluorane-based dyes are preferred, and leuco compounds having a triphenylmethane skeleton (triphenylmethane-based dyes) or fluorane-based dyes are more preferred.

[0175] From the viewpoint of visibility between the 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 radicals generated from a photoradical polymerization initiator or acids generated from a photocationic polymerization initiator, thereby changing the leuco compound to a closed state and decolorizing it, or changing the leuco compound to an open state and developing color. As the leuco compound, a compound having a lactone ring, a sultine ring, or a sultone ring that opens and develops color upon contact with a radical or acid is preferred, and a compound having a lactone ring that opens and develops color upon contact with a radical or acid is more preferred.

[0176] Examples of pigment N include dyes and leuco compounds. Examples of dyes include Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuchsine, Methyl Violet 2B, Quinaldine Red, Rose Bengal, Methanyl Yellow, Thymol Sulfophthalein, Xylenol Blue, Methyl Orange, Paramethyl Red, Congofred Red, Benzopulpurine 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Parafuchsine, Victoria Pure Blue - Naphthalene Sulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Co., Ltd.), Oil Pink #312 (manufactured by Orient Chemical Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Co., Ltd.), Oil Scarlet #308 (manufactured by Orient Chemical Co., Ltd.) Examples include (manufactured by Gaku Kogyo Co., Ltd.), Oil Red OG (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Industry Co., Ltd.), Oil Green #502 (manufactured by Orient Chemical Industry Co., Ltd.), Spiron Red BEH Special (manufactured by Hodogaya Chemical Industry Co., Ltd.), m-Cresol Purple, Cresol Red, Rhodamine B, Rhodamine 6G, Sulforhodamine B, Auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethiaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-pN,N-bis(hydroxyethyl)aminophenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0177] Examples of leuco compounds include p,p',p''-hexamethyltriaminotriphenylmethane (leucocrystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoylleucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(Np-tolyl-N-ethyl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluorane, 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, and 3-(N-cyclohexyl-N-methylamino)-6 -Methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-xylidinofluorane, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorane, 3-(N,N-diethylamino)-6-methoxy-7-aminofluorane, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluorane, 3-(N,N-diethylamino)-7-chlorofluorane, 3-(N,N-diethylamino) (Tylamino)-7-benzylaminofluorane, 3-(N,N-diethylamino)-7,8-benzofluorane, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluorane, 3-(N,N-dibutylamino)-6-methyl-7-xylidinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3,3-bis(1-ethyl-2-methylindole-3-yl)phthalide, 3,3-bis(1-n-butyl-2-methylindole-3-yl)phthalide Examples include cylindole-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-zaphthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)phthalide, and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthene-3-one.

[0178] As the dye N, a dye whose maximum absorption wavelength changes due to radicals is preferable, and a dye that develops color due to radicals is more preferable, from the viewpoints of excellent visibility of the exposed and unexposed portions, pattern visibility after development, and resolution. As the dye N, leuco crystal violet, crystal violet lactone, brilliant green, or victoria pure blue - naphthalene sulfonate is preferable.

[0179] The dye N may be used alone or in combination of two or more. The content of the dye N is preferably 0.1% by mass or more, more preferably 0.1 - 10% by mass, still more preferably 0.1 - 5% by mass, and particularly preferably 0.1 - 1% by mass, based on the total mass of the photosensitive layer, from the viewpoints of excellent visibility of the exposed and unexposed portions, and pattern visibility and resolution after development.

[0180] The content of the dye N means the content of the dye when all of the dye N contained in the total mass of the photosensitive layer is in a developed state. Hereinafter, taking the dye that develops color due to radicals as an example, the method for quantifying the content of the dye N will be described. Prepare a solution of dye N (0.001 g) and a solution of dye N (0.01 g) dissolved in 100 mL of methyl ethyl ketone. Add a photo - radical polymerization initiator (Irgacure OXE01, manufactured by BASF Japan Ltd.) to each of the obtained solutions, and irradiate with light of 365 nm to generate radicals, bringing all of the dye N into a developed state. Then, in an air atmosphere, using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), measure the absorbance of each solution at a liquid temperature of 25°C and create a calibration curve. Next, measure the absorbance of the solution in which all the dyes are developed in the same manner as above except that the photosensitive layer (3 g) is dissolved in methyl ethyl ketone instead of the dye N. Calculate the content of the dye N contained in the photosensitive layer based on the calibration curve from the absorbance of the solution containing the obtained photosensitive layer. "Photosensitive layer (3 g)" is synonymous with 3 g of the total solid content in the photosensitive composition.

[0181] <Thermally cross - linkable compound> The photosensitive layer may contain a thermally crosslinkable compound from the viewpoints of the strength of the resulting cured film and the adhesiveness of the resulting uncured film. The thermally crosslinkable compound having an ethylenically unsaturated group described later shall not be treated as a polymerizable compound but as a thermally crosslinkable compound. Examples of the thermally crosslinkable compound include a methylol compound and a blocked isocyanate compound, and from the viewpoints of the strength of the resulting cured film and the adhesiveness of the resulting uncured film, the blocked isocyanate compound is preferred. Since the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when a resin and / or a polymerizable compound has at least one of a hydroxy group and a carboxy group, the hydrophilicity of the formed film decreases, and the function when using the film obtained by curing the photosensitive layer as a protective film tends to be enhanced. The "blocked isocyanate compound" means a compound having a structure in which the isocyanate group of isocyanate is protected with a blocking agent.

[0182] The dissociation temperature of the blocked isocyanate compound is preferably 100 to 160°C, more preferably 130 to 150°C. Examples of the method for measuring the dissociation temperature of the blocked isocyanate compound include a method of measuring the temperature of the endothermic peak accompanying the deprotection reaction of the blocked isocyanate compound by DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter (for example, DSC6200, manufactured by Seiko Instruments Inc.) as the degree of dissociation.

[0183] Examples of the blocking agent having a dissociation temperature of 100 to 160°C include active methylene compounds such as malonic acid diesters, and oxime compounds. Examples of the malonic acid diester include dimethyl malonate, diethyl malonate, di-n-butyl malonate, and di-2-ethylhexyl malonate. Examples of oxime compounds include formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime, which have a structure represented by -C(=N-OH)- in their molecules. In particular, oxime compounds are preferred as blocking agents with a dissociation temperature of 100-160°C, from the viewpoint of storage stability.

[0184] Blocked isocyanate compounds are preferably configured with an isocyanurate structure, from the viewpoint of improving the brittleness of the film and enhancing adhesion to the substrate. Blocked isocyanate compounds having an isocyanurate structure can be obtained, for example, by isocyanurating and protecting hexamethylene diisocyanate. In particular, as a blocked isocyanate compound having an isocyanurate structure, a compound having an oxime structure obtained by using an oxime compound as a blocking agent is preferred because it is easier to adjust the dissociation temperature to a preferred range than compounds without an oxime structure, and development residue can be reduced.

[0185] The blocked isocyanate compound may have polymerizable groups. The polymerizable group is, for example, the same as the polymerizable group possessed by the above polymerizable compound, and the preferred embodiment is also the same.

[0186] Examples of blocked isocyanate compounds include the Karens series (registered trademark) such as AOI-BM, MOI-BM, and MOI-BP (manufactured by Showa Denko Corporation); and the blocked duranate series (registered trademark) such as TPA-B80E and WT32-B75P (manufactured by Asahi Kasei Chemicals Corporation). The following compounds are preferred as blocked isocyanate compounds.

[0187] [ka]

[0188] The thermally crosslinkable compound may be used alone or in combination of two or more types. The content of the thermally crosslinkable compound is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass, relative to the total mass of the photosensitive layer.

[0189] <Other additives> The photosensitive layer may contain other additives as needed, in addition to the components mentioned above. Other additives include, for example, radical polymerization inhibitors, benzotriazoles, carboxybenzotriazoles, sensitizers, surfactants, plasticizers, heterocyclic compounds (e.g., triazoles), pyridines (e.g., isonicotinamides), and purine bases (e.g., adenine). Other additives include, for example, metal oxide particles, chain transfer agents, antioxidants, dispersants, acid growth agents, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, crosslinking agents, organic or inorganic precipitation inhibitors, and paragraphs

[0165] to

[0184] of Japanese Patent Application Publication No. 2014-085643, the contents of which are incorporated herein by reference. Other additives may be used individually or in combination of two or more.

[0190] (Radical polymerization inhibitor) Examples of radical polymerization inhibitors (polymerization inhibitors) include the thermal polymerization inhibitors described in paragraph

[0018] of Japanese Patent No. 4502784, with phenothiazine, phenoxazine, or 4-methoxyphenol being preferred. Examples of radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. Nitrosophenylhydroxyamine aluminum salt is preferred because it does not impair the sensitivity of the photosensitive layer. The content of the radical polymerization inhibitor is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and even more preferably 0.02 to 2.0% by mass, based on the total mass of the photosensitive layer. The content of the radical polymerization inhibitor is preferably 0.005 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and even more preferably 0.01 to 1.0% by mass, based on the total mass of the polymerizable compound.

[0191] (Benzotriazoles) 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.

[0192] (Carboxybenzotriazoles) Carboxybenzotriazoles, for example, function as rust inhibitors. Examples of carboxybenzotriazoles include carboxybenzotriazoles (4-carboxy-1,2,3-benzotriazole and 5-carboxy-1,2,3-benzotriazole), N-(N,N-di-2-ethylhexyl)aminomethylene carboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylene carboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylene carboxybenzotriazole. A specific example of a carboxybenzotriazole is CBT-1 (manufactured by Johoku Chemical Industry Co., Ltd.).

[0193] The total content of radical polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles is preferably 0.01 to 3% by mass, and more preferably 0.05 to 1% by mass, relative to the total mass of the photosensitive layer. When the above content is 0.01% by mass or more, the storage stability of the photosensitive layer is better. On the other hand, when the above content is 3% by mass or less, the maintenance of sensitivity and suppression of dye decolorization are better.

[0194] (Sensitizer) Examples of the sensitizer include known sensitizers, dyes, and pigments. 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.

[0195] From the viewpoints of improving the sensitivity to the light source and improving the curing rate by the balance between the polymerization rate and the chain transfer, the content of the sensitizer is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass, based on the total mass of the photosensitive layer.

[0196] (Surfactant) Examples of the surfactant include the surfactants described in paragraph

[0017] of Japanese Patent No. 4502784 and paragraphs

[0060] to

[0071] of JP-A-2009-237362.

[0197] As the surfactant, a nonionic surfactant, a fluorine-based surfactant, or a silicone-based surfactant is preferable. Examples of fluorine-based surfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, and EXP.MF. S-330, 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, and DS-21 (all manufactured by DIC); Florard FC430, FC431, and FC171 (all manufactured by Sumitomo 3M); Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (all manufactured by AGC); PolyFox PF636, PF656, PF6320, PF6520, and PF7002 (all manufactured by OMNOVA); Futtergent Examples include 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, and 683 (all manufactured by NEOS Corporation); and U-120E (Unichem Corporation).

[0198] Furthermore, as fluorine-based surfactants, acrylic compounds having a molecular structure with a functional group containing a fluorine atom, in which the fluorine-containing functional group is cleaved when heat is applied and the fluorine atom volatilizes, are also preferred. Examples of such fluorinated surfactants include the Megafac DS series manufactured by DIC Corporation (Chemical Daily (February 22, 2016) and Nikkei Sangyo Shimbun (February 23, 2016)). Furthermore, as the fluorine-based surfactant, it is also preferable to use a copolymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group, and a hydrophilic vinyl ether compound. Block polymers can also be used as fluorine-based surfactants. As a fluorine-based surfactant, a fluorine-containing polymer compound is also preferred, which includes a structural unit derived from a (meth)acrylate compound having a fluorine atom and a structural unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkylene oxy groups (preferably ethylene oxy groups, propylene oxy groups). Furthermore, examples of fluorinated surfactants include fluorinated polymers having ethylenically unsaturated groups in their side chains, such as Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0199] As for fluorine-based surfactants, from the viewpoint of improving environmental suitability, surfactants derived from alternative materials of compounds having linear perfluoroalkyl groups with 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), are preferred.

[0200] Nonionic surfactants include, for example, glycerol, trimethylolpropane, trimethylolethane, their ethoxylates and propoxylates (e.g., glycerol propoxylate and glycerol ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters; specific examples include Pluronic® L10, L31, L61, L62, 10R5, 17R2, and 25R2 (all manufactured by BASF); Tetronic 304, 701, 704, 901, 904, 150R1, HYDROPALAT WE 3323 (all manufactured by BASF); Solspers Examples include 20000 (manufactured by Lubrizol Nippon Co., Ltd.); NCW-101, NCW-1001, and NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.); Paionin D-1105, D-6112, D-6112-W, and D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.); and Orfin E1010, Surfinol 104, 400, and 440 (manufactured by Nisshin Chemical Industry Co., Ltd.).

[0201] Examples of silicone-based surfactants include linear polymers consisting of siloxane bonds, and modified siloxane polymers in which organic groups are introduced into the side chains and / or terminals.

[0202] Specifically, silicone-based 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 Toray Dow Corning); X-22-4952, X-22-4272, X-22-6266 , KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF -6001, KF-6002, KP-101, KP-103, KP-104, KP-105, KP-106, KP-109, KP-112, KP-120, KP-121, KP-124, KP-1 25, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, and KP-652 (all manufactured by Shin-Etsu Silicone Co., Ltd.); F-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Performance Co., Ltd.) Examples include BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, and BYK323 (all manufactured by Bic Chemie).

[0203] The surfactant content is preferably 0.01 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, and even more preferably 0.05 to 0.8% by mass, relative to the total mass of the photosensitive layer.

[0204] Examples of plasticizers and heterocyclic compounds include those described in paragraphs

[0097] to

[0103] and paragraphs

[0111] to

[0118] of International Publication No. 2018 / 179640.

[0205] <Impurities> The photosensitive layer may contain impurities. Examples of impurities include metal impurities or their ions, halide ions, residual organic solvents, residual monomers, and water.

[0206] (Metal impurities and halide ions) Examples of metallic impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, and their ions, as well as halide ions. In particular, sodium ions, potassium ions, and halide ions are easily mixed in, so it is preferable to have the following concentrations. Metallic impurities are compounds different from the aforementioned particles (e.g., metal oxide particles) that may be present in the transfer film.

[0207] The content of metal impurities is preferably 80 ppm by mass or less, more preferably 10 ppm by mass or less, and even more preferably 2 ppm by mass or less, relative to the total mass of the photosensitive layer. The lower limit is preferably 1 ppb by mass or more, and more preferably 0.1 ppm by mass or more, relative to the total mass of the photosensitive layer.

[0208] Methods for adjusting the impurity content include, for example, selecting raw materials with a low impurity content for the photosensitive layer, preventing the inclusion of impurities during the formation of the photosensitive layer, and removing them by washing. The impurity content can be quantified by known methods such as ICP emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0209] (Residual organic solvent) Examples of residual organic solvents include benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane. The residual organic solvent content is preferably 100 ppm by mass or less, more preferably 20 ppm by mass or less, and even more preferably 4 ppm by mass or less, relative to the total mass of the photosensitive layer. The lower limit is preferably 10 ppb by mass or more, and more preferably 100 ppb by mass or more, relative to the total mass of the photosensitive layer. One method for adjusting the residual organic solvent content is to adjust the drying conditions in the transfer film manufacturing method described later. Furthermore, the residual organic solvent content can be quantified by known methods such as gas chromatography analysis.

[0210] (Remaining monomers) The photosensitive layer may contain monomers of each of the constituent units of the above-mentioned resin. From the viewpoint of patternability and reliability, the content of residual monomers is preferably 5000 ppm by mass or less, more preferably 2000 ppm by mass or less, and even more preferably 500 ppm by mass or less, relative to the total mass of the resin. The lower limit is preferably 1 ppm by mass or more, and more preferably 10 ppm by mass or more, relative to the total mass of the resin. The amount of residual monomers of each constituent unit of the alkali-soluble resin is preferably 3000 ppm by mass or less, more preferably 600 ppm by mass or less, and even more preferably 100 ppm by mass or less, relative to the total mass of the photosensitive layer, from the viewpoint of patternability and reliability. The lower limit is preferably 0.1 ppm by mass or more, and more preferably 1 ppm by mass or more, relative to the total mass of the photosensitive layer.

[0211] It is preferable that the amount of monomer remaining when synthesizing alkali-soluble resins by polymer reactions be within the above range. For example, when synthesizing alkali-soluble resins by reacting glycidyl acrylate with a carboxylic acid side chain, it is preferable that the content of glycidyl acrylate be within the above range. One method for adjusting the content of remaining monomers is to adjust the content of the impurities mentioned above. The amount of remaining monomer can be measured by known methods such as liquid chromatography and gas chromatography.

[0212] The water content in the photosensitive layer is preferably 0.01 to 1.0% by mass, and more preferably 0.05 to 0.5% by mass, from the viewpoint of improving reliability and lamination.

[0213] [Characteristics of the photosensitive layer] The thickness (film thickness) of the photosensitive layer is often 0.1 μm or more, preferably 0.2 μm or more, more preferably 0.5 μm or more, and particularly preferably 1.0 μm or more. The upper limit of the above film thickness is often 300 μm or less, preferably 100 μm or less, more preferably 50 μm or less, even more preferably 20 μm or less, and particularly preferably 5.0 μm or less. By keeping the film thickness of the photosensitive layer within the above range, the developability of the photosensitive layer can be improved, and the resolution can be improved.

[0214] The C=C value of the photosensitive layer is preferably 1.0 to 3.0 mmol / g. The C=C value of the photosensitive layer refers to the equivalent amount (molar amount) of double bond groups contained per gram of the photosensitive layer. For the C=C value of the photosensitive layer, 1.0 to 2.0 mmol / g is preferred in terms of superior effects of the present invention, and 1.0 mmol / g or more and less than 1.54 mmol / g is even more preferred.

[0215] [Middle class] The transfer film has an intermediate layer between the temporary support and the photosensitive layer. Examples of intermediate layers include a water-soluble resin layer and an oxygen-blocking layer with oxygen-blocking function, as described as a "separation layer" in Japanese Patent Publication No. 5-072724. As an intermediate layer, an oxygen barrier layer is also preferred because it improves sensitivity during exposure, reduces the time load on the exposure machine, and improves productivity. More preferably, the oxygen barrier layer exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (a 1% by mass aqueous solution of sodium carbonate at 22°C). The following describes the various components that the intermediate layer may contain.

[0216] <Water-soluble resin> The intermediate layer may contain a water-soluble resin. Examples of water-soluble resins include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, polyether-based resins, gelatin, and polyamide resins.

[0217] Examples of cellulose-based resins include water-soluble cellulose derivatives. Examples of water-soluble cellulose derivatives include hydroxyethylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, methylcellulose, and ethylcellulose.

[0218] Examples of polyether resins include polyethylene glycol, polypropylene glycol, and alkylene oxide adducts thereof, as well as vinyl ether resins. Examples of polyamide resins include acrylamide resins, vinylamide resins, and allylamide resins.

[0219] Examples of water-soluble resins include copolymers of (meth)acrylic acid / vinyl compounds, with copolymers of (meth)acrylic acid and (meth)acrylate being preferred, and copolymers of methacrylic acid and allyl methacrylate being more preferred. When the water-soluble resin is a copolymer of (meth)acrylic acid and a vinyl compound, the preferred composition ratio (mol% of (meth)acrylic acid / mol% of vinyl compound) is 90 / 10 to 20 / 80, and more preferably 80 / 20 to 30 / 70.

[0220] The weight-average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and even more preferably 10,000 or more. The upper limit is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less. The degree of dispersion of the water-soluble resin is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.

[0221] Water-soluble resins may be used individually or in combination of two or more types. The water-soluble resin content is preferably 50% by mass or more, and more preferably 70% by mass or more, relative to the total mass of the intermediate layer. The upper limit is preferably 100% by mass or less, more preferably 99.99% by mass or less, and even more preferably 99.9% by mass or less, relative to the total mass of the intermediate layer.

[0222] <Other ingredients> The intermediate layer may contain other components in addition to the resin mentioned above.

[0223] Other preferred components include polyhydric alcohols, alkylene oxide adducts of polyhydric alcohols, phenol derivatives, or amide compounds, with polyhydric alcohols, phenol derivatives, or amide compounds being more preferred.

[0224] Examples of polyhydric alcohols include glycerin, diglycerin, and diethylene glycol. The number of hydroxyl groups in polyhydric alcohols is preferably 2 to 10. Examples of alkylene oxide adducts of polyhydric alcohols include compounds obtained by adding ethyleneoxy groups and propyleneoxy groups to the above-mentioned polyhydric alcohols. The average number of alkylene oxy groups added is preferably 1 to 100, preferably 2 to 50, and more preferably 2 to 20. Examples of phenol derivatives include bisphenol A and bisphenol S. An example of an amide compound is N-methylpyrrolidone.

[0225] The intermediate layer preferably contains one or more selected from the group consisting of water-soluble cellulose derivatives, polyhydric alcohols, alkylene oxide adducts of polyhydric alcohols, polyether resins, polyamide resins, polyvinylamide resins, polyallylamide resins, phenol derivatives, and amide compounds.

[0226] The molecular weight of the other components is preferably less than 5,000, more preferably 4,000 or less, even more preferably 3,000 or less, particularly preferably 2,000 or less, and most preferably 1,500 or less. The lower limit is preferably 60 or more.

[0227] Other ingredients may be used individually or in combination of two or more. The content of other components 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 10% by mass or less, and even more preferably 5% by mass or less.

[0228] <Impurities> The intermediate layer may contain impurities. Examples of impurities include those contained in the photosensitive layer mentioned above.

[0229] The thickness of the intermediate layer is preferably 3.0 μm or less, and more preferably 2.0 μm or less. The lower limit is preferably 0.3 μm or more, and more preferably 1.0 μm or more.

[0230] [Other components] The transfer film may have other components in addition to the components described above. Other components include, for example, protective films.

[0231] Examples of protective films include resin films having heat resistance and solvent resistance. Specifically, these include polyolefin films such as polypropylene film and polyethylene film, polyester films such as polyethylene terephthalate film, polycarbonate film, and polystyrene film. Alternatively, a resin film made of the same material as the temporary support may be used as the protective film. Among these, polyolefin film is preferred as the protective film, and polypropylene film or polyethylene film is more preferred.

[0232] The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, even more preferably 5 to 40 μm, and particularly preferably 15 to 30 μm. The thickness of the protective film is preferably 1 μm or more for superior mechanical strength, and preferably 100 μm or less for relatively low cost.

[0233] The number of fisheyes with a diameter of 80 μm or more included in the protective film is 5 per square meter. 2 The following is preferable. The lower limit is 0 pieces / m 2 The above is preferable. "Fish eye" refers to a phenomenon where foreign matter, undissolved material, and oxidatively degraded materials are incorporated into the film during the manufacturing process, such as by thermal melting, kneading, extrusion, biaxial stretching, and casting.

[0234] The number of particles with a diameter of 3 μm or larger contained in the protective film is 30 particles / mm². 2 The following is preferable: 10 pieces / mm 2 The following is more preferable: 5 pieces / mm 2 The following is even more preferable. The lower limit is 0 pieces / mm 2 The above is preferable. When within the above range, defects caused by irregularities resulting from particles contained in the protective film being transferred to the photosensitive layer or conductive layer can be suppressed.

[0235] From the standpoint of providing windability, the arithmetic mean roughness Ra of the surface of the protective film opposite to the surface in contact with the photosensitive layer, or the surface in contact with the layer, is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. The upper limit is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0236] [Method for manufacturing transfer film] Examples of methods for manufacturing transfer films include known methods. A method for manufacturing the transfer film 10 includes, for example, the steps of: applying an intermediate layer forming composition to the surface of a temporary support 11 to form a coating film, and further drying this coating film to form an intermediate layer 13; and applying a photosensitive composition to the surface of the intermediate layer 13 to form a coating film, and further drying this coating film to form a photosensitive layer 15.

[0237] A transfer film 10 is manufactured by pressing a protective film 19 onto the photosensitive layer 15 of the laminate manufactured by the above manufacturing method. As a method for manufacturing the transfer film, it is preferable to manufacture a transfer film 10 comprising a temporary support 11, an intermediate layer 13, a photosensitive layer 15, and a protective film 19 by including a step of providing a protective film 19 so as to contact the side of the photosensitive layer 15 opposite to the temporary support 11 side. The transfer film 10 manufactured by the above manufacturing method may be wound up to produce and store a transfer film in roll form. The transfer film in roll form can be provided in its original form for the lamination process with a substrate (substrate with a metal layer) using the roll-to-roll method described later.

[0238] [Photosensitive composition and method for forming a photosensitive layer] A preferred method for forming the photosensitive layer is to apply it using a photosensitive composition containing components included in the photosensitive layer (e.g., resin, polymerizable compound, polymerization initiator, etc.) and a solvent. A preferred method for forming the photosensitive layer is, for example, to apply a photosensitive composition onto an intermediate layer to form a coating film, and if necessary, to dry the coating film at a predetermined temperature to form the photosensitive layer.

[0239] The photosensitive composition preferably contains the components included in the photosensitive layer and a solvent. The content of each component included in the photosensitive layer is as described above. The solvent is not particularly limited as long as it can dissolve or disperse the components contained in the photosensitive layer other than the solvent. Examples of solvents include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (e.g., methanol and ethanol), ketone solvents (e.g., acetone and methyl ethyl ketone), aromatic hydrocarbon solvents (e.g., toluene), aprotic polar solvents (e.g., N,N-dimethylformamide), cyclic ether solvents (e.g., tetrahydrofuran), ester solvents (e.g., n-propyl acetate), amide solvents, lactone solvents, and mixed solvents combining these.

[0240] The solvent preferably comprises at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. Among these, a mixed solvent comprising at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, and at least one selected from the group consisting of ketone solvents and cyclic ether solvents is more preferred, and a mixed solvent comprising at least 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.

[0241] Examples of alkylene glycol ether solvents include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether (e.g., propylene glycol monomethyl ether acetate), propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether. Examples of alkylene glycol ether acetate solvents include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate. Examples of solvents include those described in paragraphs

[0092] to

[0094] of International Publication No. 2018 / 179640 and those described in paragraph

[0014] of Japanese Patent Application Publication No. 2018-177889, the details of which are incorporated herein by reference.

[0242] The solvent may be used individually or in combination of two or more types. The solvent content is preferably 50 to 1900 parts by mass, more preferably 100 to 1200 parts by mass, and even more preferably 100 to 900 parts by mass, per 100 parts by mass of the total solids content of the photosensitive composition.

[0243] Examples of methods for applying the photosensitive composition include known application methods. Specifically, these include printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (slit coating).

[0244] For drying the photosensitive composition coating, heat drying or reduced-pressure drying is preferred. The drying temperature is preferably 60°C or higher, preferably 70°C or higher, and more preferably 80°C or higher. The upper limit is preferably 130°C or lower, and more preferably 120°C or lower. Alternatively, the drying method may involve continuously changing the drying temperature. The drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. The upper limit is preferably 600 seconds or less, more preferably 450 seconds or less, and even more preferably 300 seconds or less.

[0245] Furthermore, a transfer film may be manufactured by laminating a protective film onto a photosensitive layer. Methods for laminating a protective film onto a photosensitive layer include, for example, known methods. Apparatus for laminating a protective film onto a photosensitive layer include, for example, known laminators such as vacuum laminators and auto-cut laminators. A laminator is preferably equipped with a heat-sensitive roller, such as a rubber roller, and capable of applying pressure and heating.

[0246] [Composition for forming an intermediate layer and method for forming an intermediate layer] A preferred method for forming the intermediate layer is to apply it using an intermediate layer forming composition that includes components contained in the intermediate layer (for example, a water-soluble resin) and a solvent. As a method for forming the intermediate layer, for example, it is preferable to apply an intermediate layer forming composition onto a temporary support to form a coating film, and if necessary, to dry this coating film at a predetermined temperature to form the intermediate layer.

[0247] The composition for forming the intermediate layer preferably contains the components included in the intermediate layer and a solvent. The content of the components in the middle layer is as described above. The solvent is not particularly limited as long as it can dissolve or disperse the components contained in the intermediate layer. The solvent is preferably at least one selected from the group consisting of water and water-miscible organic solvents, and more preferably water or a mixed solvent of water and a water-miscible organic solvent. Examples of water-miscible organic solvents include C1-C3 alcohols, acetone, ethylene glycol, glycerin, and mixed solvents of these, with C1-C3 alcohols being preferred, and methanol or ethanol being more preferred.

[0248] The solvent may be used individually or in combination of two or more types. The solvent content is preferably 50 to 2500 parts by mass, more preferably 50 to 1900 parts by mass, and even more preferably 100 to 900 parts by mass, per 100 parts by mass of the total solids content of the intermediate layer forming composition.

[0249] Examples of methods for forming the intermediate layer include known coating methods. Specifically, these include slit coating, spin coating, curtain coating, and inkjet coating.

[0250] For drying the coating film of the intermediate layer-forming composition, heat drying or reduced-pressure drying is preferred. The drying temperature is preferably 80°C or higher, more preferably 90°C or higher, and even more preferably 100°C or higher. The upper limit is preferably 130°C or lower, and more preferably 120°C or lower. Alternatively, the drying method may involve continuously changing the drying temperature. The drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. The upper limit is preferably 600 seconds or less, more preferably 450 seconds or less, and even more preferably 300 seconds or less. [Examples]

[0251] The present invention will be described in more detail below based on examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the examples shown below. Unless otherwise specified, "parts" and "%" are based on mass. Furthermore, in the following examples, the weight-average molecular weight of the resin is the weight-average molecular weight obtained by gel permeation chromatography (GPC) on a polystyrene basis.

[0252] [Materials used to prepare the transfer film] The materials (intermediate layer-forming composition and photosensitive composition) used in the preparation of the transfer films used in the examples and comparative examples will be described below.

[0253] [Components of the intermediate layer forming composition] The intermediate layer of the transfer film was formed using an intermediate layer forming composition. The components used to prepare the intermediate layer-forming compositions are as follows. Each of the components listed below was mixed in the proportions shown in Table 2 below to obtain each intermediate layer-forming composition. Note that PVA, PVP, and HPMC, as shown below, all correspond to water-soluble resins.

[0254] <Resin> • PVA: Polyvinyl alcohol, product name "Kuraray Poval PVA-205", manufactured by Kuraray Co., Ltd. • PVP: Polypyrrolidone, product name "Polyvinylpyrrolidone K-30", manufactured by Nippon Shokubai Co., Ltd. • HPMC: Hydroxypropyl methylcellulose, product name "Metrolose 60SH-03", manufactured by Shin-Etsu Chemical Co., Ltd.

[0255] <Surfactants> • F444: Megafac F444, fluorine-based surfactant, manufactured by DIC Corporation.

[0256] <Solvent> ·methanol ·water

[0257] [Components of photosensitive composition] The photosensitive layer of the transfer film was formed using a photosensitive composition. The components used to prepare the photosensitive compositions are as follows. Each of the components listed below was mixed in the proportions shown in Table 2 below to obtain each photosensitive composition.

[0258] <Alkali-soluble resin> (Synthesis of crosslinkable alkali-soluble resins (compounds 1-3) and non-crosslinkable alkali-soluble resin (compound 4 (comparative compound))) The abbreviations used in the synthesis examples described later are as follows: St: Styrene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) MMA: Methyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) MAA: Methacrylic acid (manufactured by Fujifilm Wako Pure Chemical Corporation) BzMA: Benzyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) PGMEA: Propylene glycol monomethyl ether acetate (manufactured by Showa Denko Corporation) PGME: Propylene glycol monomethyl ether (manufactured by Showa Denko Corporation) MEK: Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.) V-601: Dimethyl-2,2'-azobis(2-methylpropionate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0259] • Synthesis of Compound 1 PGME (66.7 parts) was placed in a flask and heated to 90°C under a nitrogen stream. To this solution, a solution of St (42.6 parts), MMA (1.2 parts), and MAA (33.5 parts) dissolved in PGME (33.3 parts), and a solution of polymerization initiator V-601 (3.1 parts) dissolved in PGMEA (30.0 parts) were simultaneously added dropwise over 3 hours. After the dropwise addition was complete, V-601 (1.0 part) was added three times at 1-hour intervals. The solution was then allowed to react for a further 3 hours. Under an air stream, the solution was heated to 100°C, and tetraethylammonium bromide (1.0 part, Fujifilm Wako Pure Chemical Industries, Ltd.) and p-methoxyphenol (1.0 part, Fujifilm Wako Pure Chemical Industries, Ltd.) were added. To the obtained solution, a solution of glycidyl methacrylate (13.0 parts, NOF Corporation, Bremmer GH) dissolved in PGMEA (16.6 parts) was added dropwise over 20 minutes. The resulting solution was reacted at 100°C for 7 hours, and then diluted with PGMEA (20.0 parts) to obtain a solution of compound 1. The solid content concentration of the obtained solution was 60% by mass. The weight-average molecular weight in terms of standard polystyrene in GPC was 18,000. The amount of residual monomer measured by gas chromatography was less than 0.1% by mass relative to the polymer solid content for all monomers.

[0260] • Synthesis of Compound 2 PGME (66.7 parts) was placed in a flask and heated to 90°C under a nitrogen stream. To this solution, a solution of St (37.7 parts), MMA (24.5 parts), and MAA (28.6 parts) dissolved in PGME (33.3 parts), and a solution of polymerization initiator V-601 (4.2 parts) dissolved in PGMEA (30.0 parts) were simultaneously added dropwise over 3 hours. After the dropwise addition was complete, V-601 (1.0 part) was added three times at 1-hour intervals. The solution was then allowed to react for a further 3 hours. Under an air stream, the solution was heated to 100°C, and tetraethylammonium bromide (1.0 part, Fujifilm Wako Pure Chemical Industries, Ltd.) and p-methoxyphenol (1.0 part, Fujifilm Wako Pure Chemical Industries, Ltd.) were added. To the obtained solution, a solution of glycidyl methacrylate (6.9 parts, NOF Corporation, Bremmer GH) dissolved in PGMEA (16.6 parts) was added dropwise over 20 minutes. The resulting solution was reacted at 100°C for 7 hours, and then diluted with PGMEA (20.0 parts) to obtain a solution of compound 2. The solid content concentration of the obtained solution was 60% by mass. The weight-average molecular weight in terms of standard polystyrene in GPC was 12,500. The amount of residual monomer measured by gas chromatography was less than 0.1% by mass relative to the polymer solid content for all monomers.

[0261] • Synthesis of compound 3 PGME (66.7 parts) was placed in a flask and heated to 90°C under a nitrogen stream. To this solution, a solution of St (56.6 parts), MMA (2.5 parts), and MAA (31.4 parts) dissolved in PGME (33.3 parts), and a solution of polymerization initiator V-601 (3.1 parts) dissolved in PGMEA (30.0 parts) were simultaneously added dropwise over 3 hours. After the dropwise addition was complete, V-601 (1.0 part) was added three times at 1-hour intervals. The solution was then allowed to react for a further 3 hours. Under an air stream, the solution was heated to 100°C, and tetraethylammonium bromide (1.0 part, Fujifilm Wako Pure Chemical Industries, Ltd.) and p-methoxyphenol (1.0 part, Fujifilm Wako Pure Chemical Industries, Ltd.) were added. To the obtained solution, a solution of glycidyl methacrylate (6.9 parts, NOF Corporation, Bremmer GH) dissolved in PGMEA (16.6 parts) was added dropwise over 20 minutes. The resulting solution was reacted at 100°C for 7 hours, and then diluted with PGMEA (20.0 parts) to obtain a solution of compound 3. The solid content concentration of the obtained solution was 60% by mass. The weight-average molecular weight in terms of standard polystyrene in GPC was 14,000. The amount of residual monomer measured by gas chromatography was less than 0.1% by mass relative to the polymer solid content for all monomers.

[0262] • Synthesis of compound 4 PGMEA (66.7 parts) was placed in a flask and heated to 90°C under a nitrogen stream. To this solution, solutions of MMA (20 parts) and BzMA (80 parts) dissolved in PGMEA (33.3 parts), and a solution of polymerization initiator V-601 (1.8 parts) dissolved in PGMEA (20.0 parts) were simultaneously added dropwise over 3 hours. After the dropwise addition was complete, V-601 (1.0 part) was added three times at 1-hour intervals. The solution was then reacted for a further 3 hours. The resulting solution was then diluted with PGMEA (46.6 parts) to obtain a solution of compound 4. The solid content concentration of the obtained solution was 60% by mass. The weight-average molecular weight in terms of standard polystyrene in GPC was 60,000.

[0263] Table 1 below shows the compositions of the obtained compounds 1 to 4. The physical properties of compounds 1 to 4 [acid value (mgKOH / g), C=C value (mmol / g), and glass transition temperature Tg (°C)] are also shown. Note that "meq / g" in the "C=C value (meq / g)" column of the table is synonymous with "mmol / g".

[0264] Compounds 1-4 shown in Table 1 all correspond to alkali-soluble resins. The acid values ​​(mgKOH / g) of compounds 1-4 in Table 1 were determined in accordance with JIS K0070:1992. Furthermore, the glass transition temperatures Tg (°C) of compounds 1-4 in Table 1 were measured using differential scanning calorimetry (DSC) analysis with a differential scanning calorimeter.

[0265] [Table 1]

[0266] The abbreviations in Table 1 are as follows: St: Repeating unit derived from styrene MMA: Repeating units derived from methyl methacrylate MAA: Repeating unit derived from methacrylic acid BzMA: Repeating unit derived from benzyl methacrylate MAA-GMA: A repeating unit derived from methacrylic acid, in which glycidyl methacrylate is attached to the carboxyl group within the repeating unit.

[0267] <Polymerizable compound> • Ethoxylated (10) bisphenol A dimethacrylate (BPE-500, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) • Ethoxylated (4) bisphenol A dimethacrylate (BPE-200, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) • Ethoxylated (2,6) bisphenol A dimethacrylate (BPE-100, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) • Propylene glycol (12) diacrylate (Aronix M-270, manufactured by Toagosei Co., Ltd.)

[0268] <Photopolymerization initiator> • 2,2'-Bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0269] <Sensitizer> • 4,4′-Bis(diethylamino)benzophenone (Sanyo Trading Co., Ltd. "SB-PI 701")

[0270] <Coloring agent> • Leucocrystal violet: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0271] <Solvent> ·acetone ·toluene ·methanol

[0272] [Preparation of transfer film] Transfer films 1 to 7 were prepared using the above-mentioned photosensitive composition and intermediate layer forming composition according to the following procedure. Note that transfer films 5 and 6 did not form an intermediate layer, and the photosensitive layer was placed on a temporary support.

[0273] First, an intermediate layer-forming composition was applied to a temporary support made of 16 μm thick polyethylene terephthalate film (product name "16KS40," manufactured by Toray Industries, Inc.) using a bar coater, so that the thickness after drying would be 1.0 μm. The intermediate layer was then formed by drying it in an oven at 90°C. Furthermore, a photosensitive composition was applied to the intermediate layer using a bar coater so that the thickness after drying was as shown in Table 2 (μm), and then dried in an oven at 80°C to form a photosensitive layer. A 16 μm thick polyethylene terephthalate (product name "16KS40," manufactured by Toray Industries, Inc.) was pressed onto the surface of the obtained photosensitive layer as a protective film to create a transfer film.

[0274] Table 2 is shown below. In Table 2 below, the unit for the content of each component in the composition is "parts by mass". Furthermore, "M / B" represents the ratio of the polymerizable compound content to the alkali-soluble resin content (binder content) (polymerizable compound content / alkali-soluble resin content).

[0275] [Table 2]

[0276] [Manufacturing of laminates with conductive patterns] [Fabrication of resist patterns (resin patterns)] A PET substrate with a copper layer was used, in which a 500 nm thick copper layer was fabricated on a 188 μm thick PET film (polyethylene terephthalate film) using the sputtering method. The protective film of the fabricated transfer film was peeled off, and the exposed photosensitive layer was laminated onto a PET substrate with a copper layer under lamination conditions of roll temperature 90°C, linear pressure 0.8 MPa, and linear speed 3.0 m / min, so that the surface of the photosensitive layer was in contact with the copper layer on the surface of the PET substrate, thereby obtaining a laminate.

[0277] Next, the temporary support was peeled off, and the photomask was placed in close contact with the exposed surface (the intermediate layer for transfer films 1-4 and 7, and the photosensitive layer for transfer films 5 and 6) that was exposed by the peeling off of the temporary support. Then, light was irradiated using a high-pressure mercury lamp exposure machine (MAP-1200L, manufactured by Dainippon Kaken Co., Ltd., main wavelength: 365 nm) to expose the photosensitive layer at 100 mJ / cm². 2 It was exposed to light. Subsequently, a resist pattern (resin pattern) was formed by shower development for 30 seconds using an aqueous sodium carbonate solution at a liquid temperature of 25°C.

[0278] [Fabrication of conductor patterns] Next, the resulting laminate (substrate with resist pattern formed on it) was etched with a copper etching solution (Cu-02: manufactured by Kanto Chemical Co., Ltd.) at 23°C for 30 seconds. Furthermore, the resist pattern was removed using PGMEA to obtain a substrate with copper wiring patterned on it (laminated substrate with conductive pattern).

[0279] 〔evaluation〕 <Resolution> Using the transfer films shown in Table 2, resin patterns were formed by following the steps up to "Preparation of resist patterns (resin patterns)" in the "Manufacturing of laminates with conductive patterns" described above. Exposure and subsequent development were performed using a photomask with a 1:1 line-to-space ratio. The minimum line width at which the resulting resin pattern could be resolved was defined as the resolution, and evaluation was conducted according to the following criteria. The results are shown in Table 3. ≪Evaluation Criteria≫ "A": Minimum line width is 3.0 μm or less. "B": Minimum line width is greater than 3.0 μm and less than or equal to 4.0 μm. "C": Minimum line width is greater than 4.0 μm and less than or equal to 5.0 μm. "D": Minimum line width is greater than 5.0 μm

[0280] <Shape properties of resin patterns> Using each transfer film shown in Table 2, resin patterns were formed by following the steps up to "Preparation of resist patterns (resin patterns)" in the above-described "Manufacturing of laminates with conductive patterns." At this time, a photomask with a line (μm) / space (μm) pattern of 1 (μm) / 1 (μm) was used. Next, the cross-sectional shape of the obtained resin patterns was observed using a scanning electron microscope, and evaluation was performed based on the following evaluation criteria. Figure 2 shows a schematic cross-sectional view of a pattern with a hemline. "Hemline length (one side)" refers to the distance L between the intersection point Q of a perpendicular line drawn from the edge ET of the upper surface FT of the pattern to the lower surface FB of the pattern, and the edge EB of the lower surface FB of the pattern. The hemline length was measured for each of the two sides of the pattern's cross-sectional shape (indicated by the white arrows in Figure 2). For each side, the hemline length was measured at 10 arbitrary locations, and the average value was calculated. The larger of the two average values ​​obtained was evaluated based on the evaluation criteria below. The results are shown in Table 3.

[0281] ≪Evaluation Criteria≫ "A": Hem length (one side) 0.3 μm or less "B": Hem length (one side) greater than 0.3 μm and less than or equal to 0.5 μm "C": Hem length (one side) greater than 0.5 μm and less than or equal to 0.7 μm "D": Hem length (one side) is greater than 0.7 μm.

[0282] <Development residue suppression property> Similar to the above-mentioned resolution, patterns were formed, and the resulting line / space patterns were observed with a scanning electron microscope to measure the thickness of the residue in the spaced areas. Visual inspection was also performed, and the development residue suppression performance was evaluated according to the following criteria. "A": The residue thickness in the space is 50 nm or less, and no residue is visible to the naked eye. "B": The residue thickness in the space is 50 nm or less, and the residue is visible to the naked eye. "C": Residual thickness in the space area exceeds 50nm

[0283] <Shape of Conductor Patterns> Using the transfer films shown in Table 2, the procedures up to "Fabrication of Conductor Pattern" in the above-described "Manufacturing of Laminates Having Conductor Patterns" were carried out to form a conductor pattern. At this time, a photomask with a line (μm) / space (μm) pattern of 1 (μm) / 1 (μm) was used. Next, five arbitrary locations of the obtained conductor pattern were observed using a scanning electron microscope, and the absolute value of the difference between the most bulging point (peak) and the most constricted point (valley) among the edge positions in the field of view was determined, and the average value of the five observed locations was calculated and defined as the shape of the conductor pattern. The results are shown in Table 3. ≪Evaluation Criteria≫ "A": The difference between the mountaintop and the valley floor is 0.1 μm or less. "B": The difference between the mountaintop and the valley floor is greater than 0.1 μm and less than or equal to 0.2 μm. "C": The difference between the mountaintop and the valley floor is greater than 0.2 μm and less than or equal to 0.4 μm. "D": The difference between the mountaintop and the valley floor is greater than 0.4 μm.

[0284] Table 3 is shown below. In Table 3, "Presence or absence of temporary support removal during exposure" refers to whether or not temporary support removal was performed during exposure for resin pattern fabrication. "Yes" indicates that temporary support removal was performed, and "No" indicates that temporary support removal was not performed. In Table 3, "Presence or absence of mask contact during exposure" refers to whether or not the photomask and the intermediate layer (or the photosensitive layer in the case of transfer films without an intermediate layer) were in close contact during exposure for the creation of the resin pattern. "Yes" indicates that mask contact exposure was performed, and "No" indicates that mask contact exposure was not performed. Note that in the table, "meq / g" in the "C=C value (meq / g)" column is synonymous with "mmol / g".

[0285] [Table 3]

[0286] The results in Table 3 clearly show that the conductor patterns produced by the manufacturing method of the laminate having the conductor pattern of the example exhibit excellent shape characteristics.

[0287] Furthermore, the following is clear from comparing Example 1 and Example 2. When the C=C value of the alkali-soluble resin binder is higher (preferably above 1.0 mmol / g; Example 1 falls under this category), the transfer film has high resolution and the shape of the formed resin pattern is good. However, the formed resin pattern is prone to generating development residue, and the shape performance of the conductive pattern formed using the resin pattern as a resist pattern is somewhat inferior. In contrast, when the C=C value of the alkali-soluble resin binder is lower (preferably 1.0 mmol / g or less; Example 2 falls under this category), the transfer film tends to have lower resolution, and the shape of the formed resin pattern is somewhat inferior. However, the formed resin pattern is less prone to generating development residue, and the shape performance of the conductive pattern formed using the resin pattern as a resist pattern is superior.

[0288] Furthermore, a comparison of Example 2 and Example 3 revealed that by using a polymerizable compound with a lower C=C value in the configuration of Example 2, the C=C value of the photosensitive layer was set to a predetermined range (preferably less than 1.54 mmol / g, more preferably 1.50 mmol / g or less), resulting in an improved resin pattern shape.

[0289] Furthermore, a comparison of Example 3 and Example 4 revealed that in the configuration of Example 3, when the glass transition temperature of the alkali-soluble resin binder is set within a predetermined range (preferably 100°C or higher), the resolution of the transfer film is superior.

[0290] In the manufacturing methods for laminates having conductive patterns in Comparative Examples 1 and 2, the desired results could not be obtained because the transfer film did not have an intermediate layer. Specifically, it is presumed that during mask contact exposure after temporary support removal, the photosensitive layer and the mask adhered excessively, causing the resin pattern to peel off when the mask was removed, and / or that the surface of the photosensitive layer became roughened during temporary support removal, resulting in a deterioration of resolution and the shape of the resin pattern. As a result, it is presumed that the shape of the conductive pattern formed using the resin pattern as a resist pattern deteriorated. Furthermore, comparing Comparative Example 1 and Comparative Example 2, it is presumed that because Comparative Example 1 uses a crosslinkable alkali-soluble resin, the penetration of the developer solution during alkali development after exposure treatment was suppressed, resulting in a shorter tail length of the resin pattern and suppressed fluctuations in the shape of the tail (improved shape quality of the resin pattern) compared to Comparative Example 2. In addition, mask contamination also occurred in Comparative Examples 1 and 2. In the manufacturing method of the laminate having a conductive pattern in Comparative Example 3, although the transfer film had an intermediate layer, a crosslinkable alkali-soluble resin was not used, and therefore the desired results could not be obtained. [Explanation of symbols]

[0291] 10 Transfer film 11 Temporary support 13. Middle Class 15 Photosensitive composition layer 17 Composition layer 19 Protective film FT pattern top surface ET pattern upper surface FT edge ET FB pattern bottom surface Q intersection EB pattern bottom surface FB edge L distance

Claims

1. A bonding step is performed in which a transfer film having a temporary support, an intermediate layer, and a photosensitive layer in this order is bonded to a substrate such that the photosensitive layer side is in contact with the metal layer of the substrate having a metal layer on its surface. An exposure step of pattern-exposing the photosensitive layer from the side opposite to the side having the substrate, A developing step involves performing a developing process on the exposed photosensitive layer using an alkaline developer to form a resist pattern, An etching process or a plating process is performed on the metal layer in the region where the resist pattern is not placed. A resist peeling step for peeling off the resist pattern, Furthermore, if the plating process is included, the method for manufacturing a laminate having a conductive pattern comprises a removal step of removing the metal layer exposed by the resist stripping step and forming a conductive pattern on the substrate, Between the bonding step and the exposure step, or between the exposure step and the development step, there is further a temporary support peeling step for peeling off the temporary support, The photosensitive layer comprises a crosslinkable alkali-soluble resin, an ethylenically unsaturated compound, and a photopolymerization initiator. The C=C value of the aforementioned crosslinkable alkali-soluble resin is 0.1 to 1.0 mmol / g. A method for producing a laminate having a conductive pattern, wherein the photopolymerization initiator is a 2,4,5-triarylimidazole dimer or a derivative thereof.

2. A method for manufacturing a laminate having a conductive pattern according to claim 1, wherein the intermediate layer contains a water-soluble resin.

3. A method for producing a laminate having a conductive pattern according to claim 1 or 2, wherein the intermediate layer comprises one or more selected from the group consisting of water-soluble cellulose derivatives, polyhydric alcohols, alkylene oxide adducts of polyhydric alcohols, polyether resins, polyamide resins, polyvinylamide resins, polyallylamide resins, phenol derivatives, and amide compounds.

4. The method for manufacturing a laminate having a conductive pattern according to any one of claims 1 to 3, wherein the crosslinkable alkali-soluble resin has ethylenically unsaturated groups in its side chains.

5. A method for producing a laminate having a conductive pattern according to any one of claims 1 to 4, wherein the C=C value of the crosslinkable alkali-soluble resin is 0.4 to 1.0 mmol / g.

6. A method for manufacturing a laminate having a conductive pattern according to any one of claims 1 to 5, wherein the C=C value of the photosensitive layer is 1.0 to 3.0 mmol / g.

7. A method for manufacturing a laminate having a conductive pattern according to any one of claims 1 to 6, wherein the glass transition temperature of the crosslinkable alkali-soluble resin is 60 to 150°C.

8. A method for producing a laminate having a conductive pattern according to any one of claims 1 to 7, wherein the acid value of the crosslinkable alkali-soluble resin is 60 to 200 mg KOH / g.

9. A method for manufacturing a laminate having a conductive pattern according to any one of claims 1 to 8, comprising the step of peeling off the temporary support between the lamination step and the exposure step.

10. Between the lamination step and the exposure step, there is a temporary support peeling step, A method for manufacturing a laminate having a conductive pattern according to any one of claims 1 to 9, wherein the exposure step is a step of performing pattern exposure through a photomask.

11. Between the lamination step and the exposure step, there is a temporary support peeling step, A method for manufacturing a laminate having a conductive pattern according to any one of claims 1 to 10, wherein the exposure step is a step of performing pattern exposure by bringing the surface of the exposed intermediate layer into contact with a photomask.

12. Between the exposure step and the development step, there is a temporary support peeling step, A method for manufacturing a laminate having a conductive pattern according to any one of claims 1 to 8, wherein the exposure step is a step of performing pattern exposure through a photomask.

13. Between the exposure step and the development step, there is a temporary support peeling step, A method for manufacturing a laminate having a conductive pattern according to any one of claims 1 to 8, wherein the exposure step is a step of bringing the surface of the transfer film opposite to the side having the substrate into contact with a photomask to perform pattern exposure.

14. A method for manufacturing a laminate having a conductive pattern according to any one of claims 10 to 13, wherein the photomask includes light-shielding portions arranged in a mesh-like manner.

15. A method for manufacturing a laminate having a conductive pattern according to any one of claims 10 to 13, wherein the photomask includes light-shielding portions arranged in a circular dot pattern.

16. A method for manufacturing a laminate having a conductive pattern according to any one of claims 10 to 13, wherein the photomask includes openings arranged in a circular dot shape.

Images