Manufacturing method for laminates, manufacturing method for circuit wiring

Abstract

The present invention provides a method for manufacturing a laminate including a pattern having an excellent pattern shape, and a method for manufacturing circuit wiring. This method for manufacturing a laminate comprises: a bonding step for bringing a surface of a photosensitive composition layer of a transfer film having a temporary support and the photosensitive composition layer, the surface being on the opposite side to the temporary support side, into contact with a substrate, and bonding the transfer film and the substrate; an exposure step for subjecting the photosensitive composition layer to pattern exposure; and a developing step for developing the exposed photosensitive composition layer using a developer and forming a pattern. A glass-transition temperature X of the photosensitive composition layer is 110°C or lower, and a glass-transition temperature Y obtained by measurement Y is 125°C or higher.

Description

[Technical Field]

[0001] This invention relates to a method for manufacturing a laminate and a method for manufacturing circuit wiring. [Background technology]

[0002] Because it requires fewer steps to obtain a predetermined pattern, a widely used method involves placing a photosensitive composition layer on any substrate using a transfer film, exposing this photosensitive composition layer through a photomask, and then developing it.

[0003] For example, Patent Document 1 discloses a photosensitive transfer material having a temporary support, a thermoplastic resin layer, an intermediate layer, and a negative-type photosensitive layer in that order. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] International Publication No. 2020 / 203502 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] The present inventors investigated a conventional method for manufacturing laminates using transfer films, such as those described in Patent Document 1, and found that the resulting pattern shape tends to be defective. Specifically, the transfer film is bonded to the object to be transferred, the pattern is exposed, and then developed to obtain the desired pattern. When observing the cross-sectional shape of the resulting pattern, it was found that the pattern shape tends to become a flared shape, where the width of the pattern widens as it approaches the substrate side from the opposite side. In other words, a flared shape refers to a pattern shape in which the length of the bottom base (substrate side) is longer than the length of the top base (opposite side from the substrate). More specifically, as shown in Figure 1, in the pattern 2 placed on the substrate 1, there was a problem in which a flared portion 3, as shown by the dashed line, occurred. The resulting pattern is less likely to have a flared shape, which is also referred to as having superior pattern shape.

[0006] Therefore, the object of the present invention is to provide a method for manufacturing a laminate containing a pattern, which has excellent pattern shape. Another object of the present invention is to provide a method for manufacturing circuit wiring. [Means for solving the problem]

[0007] As a result of diligent research into the above problems, the inventors have found that the above problems can be solved by the following configuration.

[0008] [1] A bonding step is performed by bringing the surface of the photosensitive composition layer of the transfer film, which has a temporary support and a photosensitive composition layer, on the side opposite to the temporary support, into contact with the substrate, thereby bonding the transfer film and the substrate. An exposure step of pattern exposure of the above photosensitive composition layer, The process includes a developing step in which the exposed photosensitive composition layer is developed using a developing solution to form a pattern, A method for manufacturing a laminate, wherein the glass transition temperature X of the above-mentioned photosensitive composition layer is 110°C or lower, and the glass transition temperature Y determined by measurement Y is 125°C or higher. Measurement Y: The surface of the photosensitive composition layer of the transfer film opposite to the temporary support side is brought into contact with the substrate, the transfer film and the substrate are bonded together, the temporary support is peeled off from the resulting laminate, the photosensitive composition layer in the laminate from which the temporary support was peeled off is fully exposed under the same exposure conditions as in the exposure step, and then the glass transition temperature of the resulting cured film is measured and defined as the glass transition temperature Y. [2] The method for manufacturing a laminate according to [1], wherein the difference between the above glass transition temperature X and the above glass transition temperature Y is 35 to 50°C. [3] A method for producing a laminate according to [1] or [2], wherein the photosensitive composition layer comprises a resin and a polymerizable compound. [4] The method for producing a laminate according to [3], wherein the glass transition temperature of the resin is 70 to 115 °C. [5] The method for producing a laminate according to [3] or [4], wherein the resin has a polymerizable group. [6] The method for producing a laminate according to any one of [3] to [5], wherein the content of the polymerizable group in the polymerizable compound is 2.4 mmol / g or more. [7] The method for producing a laminate according to any one of [3] to [6], wherein the polymerizable compound has an ethyleneoxy group. [8] The method for producing a laminate according to any one of [3] to [7], wherein the photosensitive composition layer contains three or more polymerizable compounds. [9] The method for producing a laminate according to any one of [3] to [8], wherein the mass ratio of the content of the polymerizable compound to the content of the resin is 0.70 to 1.10.

[10] The method for producing a laminate according to any one of [1] to [9], wherein the transfer film further has an intermediate layer between the temporary support and the photosensitive composition layer.

[11] The method for producing a laminate according to

[10] , wherein the intermediate layer contains a water-soluble resin.

[12] The method for producing a laminate according to

[10] or

[11] , wherein the intermediate layer contains at least one selected from the group consisting of a water-soluble cellulose derivative, polyhydric alcohols, an oxide adduct of polyhydric alcohols, a polyether resin, a phenol derivative, and an amide compound.

[13] Between the laminating step and the exposure step, there is further a peeling step of peeling the temporary support from the laminate of the transfer film and the substrate, The method for producing a laminate according to any one of [1] to

[12] , wherein the exposure step is an exposure step of pattern-exposing the photosensitive composition layer of the laminate from which the temporary support has been peeled in the peeling step through a photomask.

[14] Between the above bonding step and the above exposure step, there is further a peeling step of peeling the temporary support from the laminate of the transfer film and the substrate, A method for manufacturing a laminate according to any one of [1] to

[12] , wherein the exposure step is an exposure step in which the surface of the laminate from which the temporary support obtained in the peeling step has been peeled off is brought into contact with a photomask and the photosensitive composition layer is pattern-exposed.

[15] Between the exposure step and the development step, there is further a peeling step of peeling the temporary support from the laminate of the transfer film and the substrate. A method for manufacturing a laminate according to any one of [1] to

[12] , wherein the exposure step is an exposure step of pattern-exposing the photosensitive composition layer of the laminate through a photomask.

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

[13] to

[15] , wherein the above-mentioned photomask includes light-shielding portions arranged in a mesh-like manner.

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

[13] to

[15] , wherein the above photomask includes light-shielding portions arranged in a circular dot pattern.

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

[13] to

[15] , wherein the above photomask includes openings arranged in a circular dot pattern.

[19] A seed layer formation step in which a seed layer is formed on a substrate to form a substrate with a seed layer, A lamination step in which the surface of the photosensitive composition layer opposite to the temporary support side is brought into contact with the seed layer of the substrate with the seed layer, and the transfer film and the substrate with the seed layer are bonded together to obtain a substrate with a photosensitive composition layer having the substrate, the seed layer, the photosensitive composition layer and the temporary support in this order, A peeling step of peeling the temporary support from the substrate with the photosensitive composition layer, An exposure step in which the photosensitive composition layer is pattern-exposed by bringing the surface of the substrate with the photosensitive composition layer, from which the temporary support has been peeled off, on the side opposite to the substrate side, into contact with a photomask, A developing step in which the exposed photosensitive composition layer is developed using a developer to form a pattern, A metal plating layer formation step is performed to form a metal plating layer on the seed layer in an area where the above pattern is not arranged by a plating process, A protective layer formation step in which a protective layer is formed on the above metal plating layer, A removal process to remove the above pattern, The process includes a seed layer removal step of removing the exposed seed layer to obtain a conductive nanowire, A method for manufacturing circuit wiring, wherein the glass transition temperature X of the above-mentioned photosensitive composition layer is 110°C or lower, and the glass transition temperature Y determined by measurement Y is 125°C or higher. Measurement Y: The surface of the photosensitive composition layer of the transfer film opposite to the temporary support side is brought into contact with the substrate, the transfer film and the substrate are bonded together, the temporary support is peeled off from the resulting laminate, the photosensitive composition layer in the laminate from which the temporary support was peeled off is fully exposed under the same exposure conditions as in the exposure step, and then the glass transition temperature of the resulting cured film is measured and defined as the glass transition temperature Y. [Effects of the Invention]

[0009] According to the present invention, a method for manufacturing a laminate containing a pattern, which has excellent pattern shape, can be provided. Furthermore, according to the present invention, a method for manufacturing circuit wiring can also be provided. [Brief explanation of the drawing]

[0010] [Figure 1] This is a schematic diagram showing an example of a flared base shape. [Figure 2] This is a schematic diagram showing an example of the structure of a transfer film. [Figure 3] This is a schematic diagram illustrating a method for evaluating line width variation. [Modes for carrying out the invention]

[0011] The present invention will be described in detail below. The following terms used in this specification are explained below. A numerical range represented using "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. In numerical ranges described in stages, the upper or lower limit described 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 herein, the upper or lower limit described in one numerical range may be replaced with the values ​​shown in the examples. The term "process" includes not only independent processes, but also cases where it is not clearly distinguishable from other processes, as long as the intended purpose of that process is achieved. Unless otherwise specified, "transparent" means that the average transmittance of visible light with wavelengths of 400-700 nm is 80% or higher, and preferably 90% or higher. The average transmittance of visible light is a value measured using a spectrophotometer, for example, the Hitachi U-3310 spectrophotometer. Unless otherwise specified, the refractive index is the value measured using an ellipsometer at a wavelength of 550 nm. Unless otherwise specified, the hue values ​​were measured using a colorimeter (CR-221, manufactured by Minolta).

[0012] Unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are calculated using a gel permeation chromatography (GPC) analyzer, with TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all product names from Tosoh Corporation) as columns, THF (tetrahydrofuran) as the eluent, a differential refractometer as the detector, and polystyrene as the standard material. The values ​​are converted using the polystyrene standard material. Unless otherwise specified, the molecular weight of a compound with a molecular weight distribution is the weight-average molecular weight (Mw). Unless otherwise specified, the metallic element content is measured using an inductively coupled plasma (ICP) spectrometer. "(meth)acrylic" is a concept that encompasses both acrylic and methacrylic, and "(meth)acryloxy group" is a concept that encompasses both acryloxy group and methacryloxy group. "Alkali-soluble" means that the solubility of a material in 100g of a 1% by mass aqueous solution of sodium carbonate at 22°C is 0.1g or more. In other words, "alkali-soluble resin" means a resin that satisfies the above solubility requirement. "Water-soluble" means that the solubility of a substance in 100g of water at a temperature of 22°C and pH 7.0 is 0.1g or more. In other words, a "water-soluble resin" is a resin that satisfies the above solubility requirement.

[0013] The "solid content" of a composition refers to the components that form the composition layers (e.g., photosensitive composition layer, intermediate layer, and thermoplastic resin layer) using the composition. If the composition contains a solvent (e.g., organic solvent and water), it refers to all components excluding the solvent. Furthermore, any liquid components that form a composition layer are also considered to be solid content.

[0014] [Method for manufacturing laminates] A method for manufacturing a laminate includes a bonding step in which a transfer film having a temporary support and a photosensitive composition layer is brought into contact with a substrate on the surface of the photosensitive composition layer opposite to the temporary support, thereby bonding the transfer film and the substrate. An exposure step in which a photosensitive composition layer is pattern-exposed, The process includes a developing step in which an exposed photosensitive composition layer is developed using a developer to form a pattern, A method for manufacturing a laminate, wherein the glass transition temperature X (hereinafter also referred to as "TgX") of the photosensitive composition layer is 110°C or lower, and the glass transition temperature Y (hereinafter also referred to as "TgY") determined by measurement Y is 125°C or higher. Measurement Y: The surface of the photosensitive composition layer of the transfer film opposite to the temporary support is brought into contact with the substrate, the transfer film and the substrate are bonded together, the temporary support is peeled off from the resulting laminate, and the photosensitive composition layer in the laminate from which the temporary support has been peeled off is fully exposed under the same exposure conditions as in the exposure process. Then, the glass transition temperature of the resulting cured film is measured and defined as the glass transition temperature Y. A preferred embodiment of the method for manufacturing the laminate is, for example, an embodiment that includes the lamination step, the exposure step, and the development step in this order.

[0015] A key feature of the present invention's method for producing a laminate is that TgX is 110°C or lower, and TgY, determined by measurement Y, is 125°C or higher. Although the detailed mechanism by which the method for manufacturing the laminate of the present invention achieves the desired effect is not clear, the inventors speculate as follows. When TgX is above 110°C, the diffusion of radicals generated during exposure treatment is suppressed in the photosensitive composition layer, so the resulting pattern (cured film) tends to have a flared shape. Furthermore, the inventors have found that when TgY is below 125°C, the crosslinking density of the pattern (cured film) obtained by exposure to the photosensitive composition layer is low, and when developed with a developer, the pattern tends to swell and dissolve, resulting in a flared shape. In view of the above, the inventors of the present invention predict that by adjusting the TgX and TgY to predetermined values, the pattern shape will be superior. Hereinafter, the superiority of the pattern shape is also referred to as the superior effect of the present invention.

[0016] The manufacturing method for the laminate of the present invention will be described in detail below, step by step. 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.

[0017] [Glass transition temperature] <tgx> TgX is 110°C or lower, preferably 105°C or lower, and more preferably 100°C or lower. The lower limit is preferably 70°C or higher, more preferably 80°C or higher, and even more preferably 90°C or higher.

[0018] TgX can be measured using, for example, the following method. First, a temperature-modulated differential scanning calorimetry (T.A. Instruments) was performed using 5-6 mg of the sample (instrument: DSC2500). A Tzero aluminum pan was used to encase the sample. The measurement conditions were a nitrogen atmosphere, a temperature range of -70°C to 200°C (5°C / min), and a temperature modulation condition of ±1°C / min (N=2). In the obtained measurement data, the temperature at which the baseline shifts in the reversing heat flow (Rev. Heat Flow) (midpoint) was defined as the glass transition temperature (average value for N=2).

[0019] The following measurement X may also be used as a method for measuring TgX. Measurement X involves bringing the surface of the photosensitive composition layer of the transfer film, opposite to the temporary support side, into contact with the substrate, bonding the transfer film and the substrate together, peeling the temporary support from the resulting laminate between the temporary support and the photosensitive composition layer, and then measuring the glass transition temperature of the exposed photosensitive composition layer. The obtained glass transition temperature is defined as glass transition temperature X. Unlike TgY, which will be discussed later, TgX is the glass transition temperature of the photosensitive composition layer that has not undergone exposure treatment. In other words, TgX is the glass transition temperature of the unexposed portion of the photosensitive composition layer. The substrate used in measurement X is synonymous with the substrate described later, and the preferred embodiment is also the same. As for the method of removing the temporary support, for example, known removal methods can be used, and a method of removal using the same method as the removal process described later is preferred. The substrate used in measurement X is the same as the substrate used in the manufacturing method of the laminate described later. If the transfer film has a protective film as described later, measurement X is performed after peeling the protective film off the transfer film.

[0020] <tgy> TgY is 125°C or higher, preferably 130°C or higher, more preferably 135°C or higher, and even more preferably 140°C or higher. The upper limit is preferably 160°C or lower, more preferably 150°C or lower, and even more preferably 145°C or lower.

[0021] TgY is a value obtained from the following measurement Y. Measurement Y is performed by bringing the surface of the photosensitive composition layer of the transfer film opposite to the temporary support side into contact with the substrate, bonding the transfer film and the substrate, peeling off the temporary support from the resulting laminate, and fully exposing the photosensitive composition layer in the laminate from which the temporary support has been peeled off under the same exposure conditions as the exposure process. Subsequently, the glass transition temperature of the resulting cured film is measured and defined as the glass transition temperature Y. The exposure conditions (e.g., type of light source and exposure amount) for the full-surface exposure described above are the same as those used in the exposure process described later. In other words, the full-surface exposure performed in measurement Y corresponds to the exposure performed in the exposure process described later, but with the exposure range changed to the entire photosensitive composition layer. TgY is the glass transition temperature of the cured film formed by exposing a photosensitive composition layer to light. The method for measuring the glass transition temperature, the method for removing the temporary support, and the substrate used in measurement Y are the same as the measurement methods and substrates listed in TgX above, and the preferred embodiments are also the same. If the transfer film has a protective film as described later, measurement Y is performed after peeling the protective film off the transfer film.

[0022] The difference between TgX and TgY is preferably 35-50°C, and more preferably 40-50°C. The "difference" mentioned above is the value obtained by subtracting the smaller of TgY from the larger of TgX. For example, if TgY is greater than TgX, the difference is the value obtained by "TgY - TgX". If TgX and TgY are the same value, the difference is 0.

[0023] Methods for adjusting TgX and TgY include, for example, changing the type and content of the resin and polymerizable compound described later that are contained in the photosensitive composition layer of the transfer film. Specifically, these include methods for adjusting the Tg of the resin, the types and content of monomers that can constitute the constituent units of the resin to the preferred embodiments described later, methods for adjusting the number of types of polymerizable compounds, the content of polymerizable groups in the polymerizable compounds, the types and content of predetermined functional groups (e.g., ethyleneoxy groups) in the polymerizable compounds to the preferred embodiments described later, and methods combining these.

[0024] [Lamination process] The lamination process involves bringing the surface of the photosensitive composition layer of the transfer film, which has a temporary support and a photosensitive composition layer, on the side opposite to the temporary support, into contact with the substrate, thereby laminating the transfer film and the substrate. 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.

[0025] The surface of the photosensitive composition layer of the transfer film, opposite to the temporary support side, is brought into contact with the substrate and pressed down. Examples of bonding methods include known transfer methods and lamination methods, and a preferred method involves placing the surface of the photosensitive composition 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 conductive substrate is preferred, which includes a support substrate and a conductive layer disposed on the support substrate. The conductive substrate may have any layer other than the conductive layer formed on the support substrate as needed. In other words, it is preferable that the substrate is a conductive substrate having at least a support substrate and a conductive layer disposed on the support substrate. Examples of support substrates include resin substrates, glass substrates, and semiconductor substrates, with the support substrate described in paragraph

[0140] of International Publication No. 2018 / 155193 being preferred. As the material for the resin substrate, cycloolefin polymers or polyimides 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 areas 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 at the exposure wavelength is 50% or higher. The transmittance of the transparent substrate is preferably 80% or higher, more preferably 90% or higher, and even more preferably 95% or higher. The upper limit is preferably less than 100%. 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. Among the transparent substrates mentioned above, polyamide film, polyethylene terephthalate film, cycloolefin polymer, polyethylene naphthalate film, polyimide film, or polycarbonate film are preferred, with polyethylene terephthalate film being more preferred. 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 of the measured values.

[0027] Furthermore, when using a photomask that includes light-shielding areas or openings arranged in a circular dot pattern, a silicon substrate, a glass substrate, or an organic substrate such as FR4 (Flame Retardant Type 4) is preferred as the substrate. In that case, the thickness of the substrate is not particularly limited. Furthermore, wiring patterns may be formed on the surface of the substrate, and wiring layers may be stacked. Photomasks that include light-shielding areas or openings arranged in a circular dot pattern will be explained in a later section.

[0028] As the conductive layer, at least one selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer is preferred from the viewpoint of conductivity and fine wire formation. One or more conductive layers may be placed on the support substrate. When two or more conductive layers are arranged, the conductive layers may be the same or different, but it is preferable that they be conductive layers made of different materials. Examples of conductive layers include paragraph

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

[0029] A conductive substrate is preferably one having at least one of transparent electrodes and routing wiring, and such a substrate can be used as a substrate for a touch panel. 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.

[0030] 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 metals. Copper, molybdenum, aluminum, or titanium are preferred, with copper being more preferred.

[0031] [Peeling process] The method for manufacturing the laminate preferably includes a peeling step, and more preferably includes a peeling step between the bonding step and the exposure step, or between the exposure step and the development step. The peeling process is the process of peeling the temporary support from the laminate of the transfer film and the substrate. 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.

[0032] [Exposure process] The exposure process involves pattern exposure of the photosensitive composition layer. "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 direction may be from the side of the photosensitive composition layer or from the side opposite to the photosensitive composition layer (the substrate side).

[0033] As an exposure step, it is also preferable to pattern-expose the photosensitive composition layer of the laminate from which the temporary support obtained in the peeling step has been peeled off, using a photomask. Furthermore, as an exposure process, it is preferable to bring the photomask into contact with the surface of the laminate from which the temporary support obtained in the peeling process has been removed (opposite the substrate side) and to perform pattern exposure on the photosensitive composition layer, in order to obtain a high-resolution pattern. In other words, it is preferable to bring the photomask into contact with the surface of the laminate from which the temporary support has been removed (exposed by the peeling of the temporary support) and to perform pattern exposure on the photosensitive composition layer. In addition, the exposed surface refers to the surface of the photosensitive composition layer when the transfer film has a two-layer structure consisting of a temporary support and a photosensitive composition layer, and to 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 composition layer. In the exposure process described above, when a pattern is exposed, a curing reaction of the components contained in the photosensitive composition layer may occur in the exposed region of the photosensitive composition layer (the region corresponding to the opening of the photomask). After exposure, alkaline development is performed to remove the unexposed region of the photosensitive composition layer, and the pattern is formed.

[0034] As the above-mentioned photomask, a photomask including light-shielding parts arranged in a mesh pattern or a photomask including light-shielding parts arranged in a circular dot pattern, as described later, is preferred.

[0035] The manufacturing method for the laminate preferably includes 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.

[0036] The light source for pattern exposure can be any light capable of irradiating with light in a wavelength range that can cure the photosensitive composition layer (e.g., 365 nm and 405 nm), with 365 nm being preferred. "Main wavelength" refers to the wavelength with the highest intensity.

[0037] 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.

[0038] Furthermore, it is preferable that the object to be exposed has a substrate on which a cushioning material is placed on a support substrate. If the object to be exposed has a cushioning material, it is preferable that the object to be exposed further has an intermediate layer. An example of such an intermediate layer is an intermediate layer that a transfer film may have. The cushioning material may be placed on the support substrate before the bonding process described above, or it may be placed on the support substrate after the bonding process described above. A known method can be used to place the cushioning material. Specifically, it is preferable to include a bonding step of bonding the transfer film and the substrate by bringing the surface of the photosensitive composition layer of the transfer film having a temporary support and a photosensitive composition layer, opposite to the temporary support side, into contact with the surface of the substrate having a cushioning material, opposite to the cushioning material, and bonding the transfer film and the substrate; and an exposure step of pattern-exposing the photosensitive composition layer. It is also preferable to include a bonding step of bonding the transfer film and the substrate by bringing the surface of the photosensitive composition layer of the transfer film having a temporary support and a photosensitive composition layer, opposite to the temporary support side, into contact with the substrate; a forming step of forming a cushioning material on the surface of the substrate opposite to the photosensitive composition layer; and an exposure step of pattern-exposing the photosensitive composition layer. Examples of cushioning materials include those made of silicone, urethane, nitrile, and chloroprene. The cushioning material may be in the form of a sheet. The hardness of the cushioning material is preferably 30 or higher, more preferably 50 or higher, and even more preferably 70 or higher. The upper limit is preferably 100 or lower, and more preferably 90 or lower. The above hardness values ​​are Type A durometer hardness.

[0039] [Development process] The developing process involves developing the exposed photosensitive composition layer using a developer solution to form a pattern. By developing with a developing solution, the unexposed areas of the photosensitive composition layer are removed, and a pattern is formed in which the openings of the photomask are convex.

[0040] An alkaline aqueous solution is preferred as the developing solution. Examples of alkaline compounds contained in alkaline aqueous solutions (compounds that dissolve in water and exhibit alkalinity) include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0041] 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.

[0042] [Post-exposure process and post-bake process] The method for manufacturing the laminate may further include a step of exposing the pattern obtained in the development step to light (hereinafter also referred to as the "post-exposure step") and / or a step of heating (hereinafter also referred to as the "post-bake step"). If the method for manufacturing the laminate 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 / cm² 2 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.

[0043] The position and size of the pattern formed on the substrate obtained by the manufacturing method of the laminate are not particularly limited, but a fine linear shape is preferred. Specifically, the line width of the 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 preferably 1.0 μm or more.

[0044] [Applications of laminates] Laminates manufactured by the lamination manufacturing method can be applied to various devices. Examples of devices equipped with the above-mentioned laminate include input devices, with touch panels being preferred and capacitive touch panels being more preferred. The above-mentioned input device can be applied to display devices such as organic EL (organic electroluminescent) displays and liquid crystal displays.

[0045] Furthermore, the method for manufacturing laminates according to the present invention can be applied to, for example, the manufacture of conductive films such as transparent heaters, transparent antennas, electromagnetic wave 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.

[0046] [Method of manufacturing circuit wiring] <<First Embodiment>> A first embodiment of a method for manufacturing circuit wiring includes a bonding step in which a transfer film having a temporary support and a photosensitive composition layer is brought into contact with a conductive substrate on the surface of the photosensitive composition layer opposite to the temporary support, thereby bonding the transfer film and the conductive substrate. An exposure step in which a photosensitive composition layer is pattern-exposed, A developing step involves developing an exposed photosensitive composition layer using a developer to form a pattern, The process includes an etching step for etching the conductive layer in areas where no pattern is placed, TgX is below 110°C, and TgY is above 125°C. A preferred embodiment of the method for manufacturing circuit wiring is one in which the bonding step, the exposure step, the developing step, and the etching step are performed in this order. The terms TgX, TgY, bonding step, exposure step, and developing step described above have the same meaning as the terms used in the manufacturing method of the laminate, and the preferred embodiments are also the same.

[0047] The following describes in detail each step of an embodiment of the circuit wiring manufacturing method. Note that steps included in the circuit wiring manufacturing method that are the same as those already described above will be omitted. Specifically, the lamination step, exposure step, and development step will be omitted. 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.

[0048] [Etching process] The etching process is a process in which, when a conductive substrate is used as the substrate, the conductive layer in areas where no pattern is placed in a laminate having a pattern manufactured by the above-mentioned method for manufacturing the laminate is etched. Specifically, the etching process involves using a pattern obtained from the photosensitive composition layer by the development process in the manufacturing method of the laminate as an etching resist to etch the conductive layer. The substrate is the same as the substrate in the manufacturing method of the laminate described above, and the preferred embodiment is also the same.

[0049] 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, and dry etching such as wet etching and plasma etching, which involve immersion in an etching solution.

[0050] 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).

[0051] [Removal process] A method for manufacturing circuit wiring may include a removal step to remove any remaining patterns. The removal process is preferably carried out after the etching process described above. Methods for removing remaining patterns include, for example, removal by chemical treatment, and a method using a removal solution is preferred. Methods for removing remaining patterns include, for example, using a removal solution and removing them by known methods such as the spray method, shower method, and paddle method.

[0052] Examples of removal solutions include those 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. The temperature of the removal solution is preferably 30 to 80°C, and more preferably 50 to 80°C. A preferred method of removal involves immersing a substrate having the pattern to be removed in a removal solution that is being stirred and has a liquid temperature of 50 to 80°C for 1 to 30 minutes.

[0053] The first embodiment of the method for manufacturing circuit wiring may further include a peeling step, a post-exposure step, and / or a post-bake step in the method for manufacturing a laminate.

[0054] <<Second Embodiment>> A seed layer formation step in which a seed layer is formed on a substrate to form a substrate with a seed layer, A lamination step in which the surface of the photosensitive composition layer opposite to the temporary support side is brought into contact with the seed layer of the substrate with the seed layer, and the transfer film and the substrate with the seed layer are laminated to obtain a substrate with a photosensitive composition layer having the substrate, seed layer, photosensitive composition layer and temporary support in this order, A peeling step in which a temporary support is peeled off from a substrate with a photosensitive composition layer, An exposure step in which the photosensitive composition layer is pattern-exposed by bringing the surface of the substrate with the photosensitive composition layer, from which the temporary support has been peeled off, on the side opposite to the substrate side, into contact with a photomask, A developing step involves developing an exposed photosensitive composition layer using a developer to form a pattern, A metal plating layer formation process in which a metal plating layer is formed on a seed layer in an area where no pattern is placed by a plating process, A protective layer formation process in which a protective layer is formed on a metal plating layer, A removal process to remove the pattern, The process includes a seed layer removal step to remove the exposed seed layer and obtain a conductive nanowire, A method for manufacturing circuit wiring, wherein the glass transition temperature X of the photosensitive composition layer is 110°C or lower, and the glass transition temperature Y determined by measurement Y is 125°C or higher. Except for changing the substrate to a substrate with a seed layer in the above TgX, TgY, bonding step, peeling step, exposure step, developing step, and removal step, the terms used in the above manufacturing method of the laminate are the same as those used in the above manufacturing method of the laminate, and the preferred embodiments are also the same.

[0055] [Seed layer formation process] The seed layer formation process is the process of forming a seed layer on a substrate. Examples of the above-mentioned substrate include the substrate used in the bonding step of the manufacturing method of the above-mentioned laminate.

[0056] The seed layer may contain metal. Examples of the above-mentioned metals include, for example, all metals of the world. Examples of the main metal components in the seed layer include copper, chromium, lead, nickel, gold, silver, tin, and zinc. "Main component" refers to the metal present in the largest quantity among the metals contained in the seed layer.

[0057] The seed layer thickness is preferably 50 nm or more, and more preferably 100 nm or more. The upper limit is preferably 2 μm or less.

[0058] Methods for forming the seed layer include, for example, known methods such as applying a dispersion of metal nanoparticles and sintering the coating film, sputtering, and vapor deposition.

[0059] [Metal plating layer formation process] The metal plating layer formation process is a process in which a metal plating layer is formed on a seed layer in an area where no pattern is placed, by a plating treatment. Examples of plating methods include electrolytic plating and electroless plating, and electrolytic plating is preferred from the viewpoint of productivity.

[0060] Examples of metals included in the metal 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 metal plating layer preferably contains copper or an alloy thereof, as this provides superior conductivity for the conductive nanowires. Furthermore, the metal plating layer preferably contains copper as its main component, as this provides superior conductivity for the conductive nanowires.

[0061] The thickness of the metal plating layer is preferably 0.1 μm or more, and more preferably 1 μm or more. The upper limit is preferably 20 μm or less.

[0062] [Protective layer formation process] The protective layer formation process is the process of forming a protective layer on the metal plating layer. As the material for the protective layer, a material that has resistance to the removal solution or etching solution in the removal process or the conductive fine wire formation process is preferred. Examples include metals such as nickel, chromium, tin, zinc, magnesium, gold, and silver, their alloys, and resins, with nickel or chromium being preferred.

[0063] Methods for forming the protective layer include, for example, electroless plating and electroplating, with electroplating being preferred.

[0064] The thickness of the protective layer is preferably 0.3 μm or more, and more preferably 0.5 μm or more. The upper limit is preferably 3.0 μm or less, and more preferably 2.0 μm or less.

[0065] [Seed layer removal process] The seed layer removal process is a process of removing the exposed seed layer to obtain a conductive nanowire. In the seed layer removal process, the metal plating layer formed in the metal plating layer formation process is used as an etching resist to etch the seed layer located in the non-pattern formation region (the region not protected by the metal plating layer).

[0066] One method for removing the seed layer is to use a known etching solution. Examples of known etching solutions include ferric chloride solution, cupric chloride solution, ammonia-alkali solution, a mixture of sulfuric acid and hydrogen peroxide, and a mixture of phosphoric acid and hydrogen peroxide.

[0067] The wire width of the formed conductive nanowire is preferably 8 μm or less, and more preferably 6 μm or less. The lower limit is preferably 1 μm or more.

[0068] [Other processes] The method for manufacturing circuit wiring may include other steps in addition to the steps described above. Other processes include, for example, a post-exposure process, a post-bake process, a process to reduce the visible light reflectance as described in paragraph

[0172] of International Publication No. 2019 / 022089, and a process to form 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> A method for manufacturing circuit wiring may include a step of performing a treatment to reduce the visible light reflectance of some or all of the multiple conductive layers on the substrate. One example of a treatment to reduce visible light reflectivity is oxidation. If the substrate has a conductive layer containing copper, the copper can be oxidized to copper oxide, which blackens the conductive layer and reduces its visible light reflectivity. 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> A method for manufacturing circuit wiring may include the steps of forming an insulating film on the surface of the circuit wiring and forming a new conductive layer on the surface of the insulating film. Through the above process, a 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] In the method for manufacturing circuit wiring, it is also preferable to use a substrate having multiple conductive layers on both surfaces of the substrate, and to form circuit wiring sequentially or simultaneously on 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 circuit wiring] Circuit wiring manufactured by the circuit wiring manufacturing method can be applied to various devices. Examples of devices equipped with the above-mentioned circuit wiring include input devices, touch panels are preferred, and capacitive touch panels are more preferred. The above-mentioned input device can be applied to display devices such as organic EL displays and liquid crystal displays. One embodiment of the present invention for manufacturing circuit wiring is, for example, using a photomask that includes a mesh-like arrangement of light-shielding portions when exposing the material. The above manufacturing method is suitable for manufacturing mesh-like metal wiring patterns. The wiring circuit 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. In this case, a lower sheet resistance value in the mesh pattern region is preferable. Specifically, 100Ω / □ or less is preferred, 20Ω / □ or less is more preferred, and 5Ω / □ or less is particularly preferred. The lower limit is preferably greater than 0Ω / □.

[0073] Another embodiment of the manufacturing method for circuit wiring according to the present invention is, for example, the use of a photomask that includes light-shielding areas arranged in a circular dot pattern during exposure. The above manufacturing method can be suitably used as a method for manufacturing vias, semiconductor chips, and pillars and pins for interconnects between 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 more preferably 3 to 10 μm. Another example involves using a photomask that includes circular dot-shaped openings 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.

[0074] The above manufacturing method, which uses a photomask including light-shielding areas arranged in a circular dot pattern, is also suitable as a manufacturing method for 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 or less. Although the above describes a method for manufacturing circuit wiring according to the present invention, the above may also refer to a method for manufacturing laminates according to the present invention.

[0075] The term "circular" as used above may refer to either a perfect circle or an approximate circle. If the circular shape is an approximate circle, its diameter refers to the longest diameter within the approximate circle. Furthermore, "a photomask including light-shielding areas arranged in a circular dot pattern" may refer to a photomask having one circular dot-shaped light-shielding area, or a photomask having two or more circular dot-shaped light-shielding areas. Furthermore, "a photomask containing openings arranged in a circular dot pattern" may be a photomask with one circular dot-shaped opening, or a photomask with two or more circular dot-shaped openings.

[0076] Furthermore, a photomask including light-shielding sections arranged in a mesh pattern may also include light-shielding sections arranged in a pattern different from that of the mesh-like light-shielding sections. Furthermore, a photomask containing light-shielding areas arranged in a circular dot pattern may also include light-shielding areas arranged in a pattern different from that of the circular dot pattern.

[0077] [Transfer film] The transfer film comprises a temporary support and a photosensitive composition layer, and is subjected to an exposure process in which the photosensitive composition layer is pattern-exposed, wherein TgX is 110°C or less and TgY is 125°C or more. The above TgX and TgY have the same meanings as those described in the above-mentioned method for manufacturing the laminate, and the preferred embodiments are also the same.

[0078] The transfer film may have other layers in addition to the photosensitive composition layer described later. Other layers include, for example, the intermediate layer and the thermoplastic resin layer described later. The transfer film may also have other components (for example, a protective film) described later.

[0079] Examples of the transfer film include the following configurations (1) to (3). In particular, the transfer film preferably has an intermediate layer, and the following configuration (2) or configuration (3) is more preferable, with configuration (2) being even more preferable. (1) "Temporary support / photosensitive composition layer / protective film" (2) "Temporary support / intermediate layer / photosensitive composition layer / protective film" (3) "Temporary support / thermoplastic resin layer / intermediate layer / photosensitive composition layer / protective film" In each of the above configurations, the photosensitive composition layer is preferably a negative-type photosensitive composition layer or a colored resin layer, as described later.

[0080] 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 transfer film's waviness is measured using 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.

[0081] In the photosensitive composition layer of the transfer film, if there are other composition layers (for example, a photosensitive composition layer, an intermediate layer, and a thermoplastic resin layer, etc.) on the side opposite to the temporary support side of the photosensitive composition layer, the total thickness of the other composition layers is preferably 0.1 to 30%, and more preferably 0.1 to 20%, of the thickness of the photosensitive composition layer.

[0082] For superior adhesion, the transmittance of the photosensitive composition layer at a wavelength of 365 nm is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more. The upper limit is preferably 99.9% or less, and more preferably 99.0% or less.

[0083] 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 composition layer 15, and a protective film 19. The transfer film 10 shown in Figure 1 has an intermediate layer 13 and a protective film 19, but it does not necessarily have to have an intermediate layer 13 and a protective film 19. In Figure 1, each layer (for example, the photosensitive composition layer, the intermediate layer, and the thermoplastic resin layer) other than the protective film 19 that can be placed on the temporary support 11 is also referred to as a "composition layer". The transfer film may have a thermoplastic resin layer in addition to the above-mentioned layer. Preferably, the thermoplastic resin layer is placed between the temporary support 11 and the intermediate layer 13.

[0084] 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.

[0085] [Temporary support] The transfer film has a temporary support. The temporary support is a component that supports the photosensitive composition layer and is ultimately removed by a peeling process.

[0086] The temporary support may have either a single-layer structure or a multilayer structure. As the temporary support, a film is preferred, and a resin film is more preferred. Also, as the temporary support, a film having flexibility and not undergoing significant deformation, shrinkage or elongation under pressure or under pressure and heat is preferred, and a film without deformation such as wrinkles and scratches is also preferred. Examples of the film include a polyethylene terephthalate film (e.g., a biaxially stretched polyethylene terephthalate film), a polymethyl methacrylate film, a triacetate cellulose film, a polystyrene film, a polyimide film, and a polycarbonate film, and a polyethylene terephthalate film is preferred.

[0087] From the viewpoint of being able to perform pattern exposure through the temporary support, it is preferred that the temporary support has high transparency. Specifically, the transmittance of the temporary support at a wavelength of 365 nm is preferably 60% or more, more preferably 70% or more. The upper limit is preferably less than 100%. From the viewpoints of pattern formation property during pattern exposure through the temporary support and transparency of the temporary support, it is preferred that the haze of the temporary support is 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.

[0088] From the viewpoints of pattern formation property during pattern exposure through the temporary support and transparency of the temporary support, the number of fine particles, foreign matters and defects in the temporary support is preferably small. Specifically, the number of fine particles (e.g., fine particles with a diameter of 1 μm), foreign matters and defects in the temporary support is preferably 50 pieces / 10 mm 2 or less, more preferably 10 pieces / 10 mm 2 or less, even more preferably 3 pieces / 10 mm 2 or less, particularly preferably less than 1 piece / 10 mm 2 The lower limit is preferably 0 pieces / 10 mm 2 or more.

[0089] The thickness of the temporary support is preferably 5 to 200 μm, more preferably 5 to 150 μm, even more preferably 5 to 50 μm, and particularly preferably 5 to 25 μm, from the viewpoint of ease of handling and versatility. The thickness of the temporary support is calculated as the average value of five arbitrary points measured by cross-sectional observation using a Scanning Electron Microscope (SEM).

[0090] For ease of handling, the temporary support may have a layer containing fine particles (lubricant layer) on one or both sides 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.

[0091] To improve adhesion between the temporary support and the photosensitive composition layer, the surface of the temporary support that comes into contact with the photosensitive composition layer may be surface-modified. Examples of surface modification treatments include those using UV irradiation, corona discharge, and plasma. The exposure dose during UV irradiation is 10-2000 mJ / cm². 2 Preferably, 50-1000 mJ / cm² 2 This is preferable. If the exposure is within the above range, the lamp output and illuminance are not particularly limited. Examples of light sources for 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), all of which emit light in the 150-450 nm wavelength range.

[0092] 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 the registered trademarks Lumirror 16KS40 and Lumirror 16FB40 (both manufactured by Toray Industries, Inc.); and Cosmoshine A4100, Cosmoshine A4300, and Cosmoshine A8300 (all manufactured by Toyobo Co., Ltd.).

[0093] [Photosensitive composition layer] The transfer film has a photosensitive composition layer. In display devices equipped with touch panels, such as capacitive input devices (e.g., organic EL display devices and liquid crystal display devices), conductive layer patterns, including electrode patterns corresponding to the sensor in the viewing area, peripheral wiring sections, and output wiring sections, are provided inside the touch panel. Generally, a widely used method for forming patterned layers involves providing a photosensitive composition layer on a substrate using a transfer film, exposing the photosensitive composition layer through a photomask having a desired pattern, and then developing it. Therefore, a negative-type photosensitive composition layer is preferred as the photosensitive composition layer. When the photosensitive composition layer is a negative-type photosensitive composition layer, the formed pattern corresponds to a cured film.

[0094] The photosensitive composition layer preferably contains a resin and a polymerizable compound, as described later, and more preferably contains a resin, a polymerizable compound, and a polymerization initiator, as described later. Furthermore, the photosensitive composition layer preferably contains an alkali-soluble resin. In other words, the photosensitive composition layer preferably contains a resin including an alkali-soluble resin and a polymerizable compound. The photosensitive composition layer preferably contains 10.0 to 90.0% by mass of resin, 5.0 to 70.0% by mass of polymerizable compound, and 0.01 to 20.0% by mass of polymerization initiator, based on the total mass of the photosensitive composition layer. The following describes the components that the photosensitive composition layer may contain.

[0095] <Resin> The photosensitive composition layer may contain a resin. Alkali-soluble resins are preferred as the resin. As the resin, an alkali-soluble resin contained in the thermoplastic resin layer described later may be used.

[0096] To suppress line width thickening and resolution deterioration that occur when the focal position shifts during exposure, it is preferable that the resin contains constituent units derived from monomers having aromatic hydrocarbon groups. 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 resin. The upper limit is preferably 80.0% by mass or less, more preferably 60.0% by mass or less, and even more preferably 55.0% by mass or less, relative to the total mass of the resin. When the photosensitive composition layer contains multiple resins, it is preferable that the average mass value of the content of constituent units derived from monomers having aromatic hydrocarbon groups is within the above range.

[0097] 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 dimers, and styrene trimers). 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 60.0% by mass, and even more preferably 30.0 to 55.0% by mass, relative to the total mass of the resin. When the photosensitive composition layer contains multiple resins, it is preferable that the average mass value of the content of constituent units having aromatic hydrocarbon groups is within the above range.

[0098] Examples of aralkyl groups include optionally substituted phenylalkyl groups (excluding benzyl groups) and optionally substituted benzyl groups, with optionally substituted benzyl groups being preferred.

[0099] Examples of monomers having a phenylalkyl group include phenylethyl (meth)acrylate.

[0100] 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, relative to the total mass of the resin.

[0101] A resin containing constituent units derived from a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing a monomer having an aromatic hydrocarbon group with at least one of the first monomers described later and / or at least one of the second monomers described later.

[0102] Resins that do not contain constituent units derived from monomers having aromatic hydrocarbon groups are preferably obtained by polymerizing at least one of the first monomers described later, and more preferably by polymerizing at least one of the first monomers and at least one of the second monomers described later.

[0103] 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 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, control of the tail shape, and high chemical resistance of the resist pattern can be achieved.

[0104] The second monomer is non-acidic (does not have acidic groups) 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 80.0% by mass, more preferably 1.0 to 60.0% by mass, and even more preferably 1.0 to 50.0% by mass, relative to the total mass of the resin.

[0105] The 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 the 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 within the polymer compound that makes up the 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- Examples include 1-adamantyl, octahydro-4,7-menthanoinden-5-yl (meth)acrylate, octahydro-4,7-menthanoinden-1-ylmethyl (meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl (meth)acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fentyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, and cyclohexyl (meth)acrylate. Among these, 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.

[0106] The resin preferably has polymerizable groups, more preferably contains structural units having polymerizable groups, and even more preferably contains structural units having ethylenically unsaturated groups in their side chains, in order to achieve superior effects of the present invention. Examples of polymerizable groups include those found in polymerizable compounds described later, with ethylenically unsaturated groups being preferred, and acryloyl groups or methacryloyl groups being more preferred. Furthermore, the polymerizable group described above is preferably a polymerizable group that can undergo polymerization reaction with the polymerizable group of a polymerizable compound.

[0107] It is preferable that the resin containing polymerizable structural units be obtained by reacting a resin containing structural units derived from a first monomer with a third monomer.

[0108] The third monomer is a monomer having two or more polymerizable groups in its molecule, and it is preferable that it is a monomer having two polymerizable groups in its molecule. Examples of the polymerizable groups mentioned above include the polymerizable groups found in polymerizable compounds described later. In particular, the third monomer preferably has two types of polymerizable groups, more preferably an ethylenically unsaturated group and a cationic polymerizable group, and even more preferably an acryloyl group or a methacryloyl group and an epoxy group.

[0109] An example of a third monomer is glycidyl (meth)acrylate.

[0110] As a constituent unit having polymerizable groups, the constituent unit represented by formula (P) is preferred.

[0111] [ka]

[0112] In formula (P), R P L represents a hydrogen atom or a methyl group. P represents a divalent linking group. P represents a polymerizable group.

[0113] R P represents a hydrogen atom or a methyl group. R P A hydrogen atom is preferred as the element.

[0114] 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 - Examples include hydrocarbon groups and groups formed by combining them. N represents a 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-mentioned arylene group may be monocyclic or polycyclic. The number of carbon atoms in the above-mentioned 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-mentioned 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.

[0115] P represents a polymerizable group. The polymerizable groups are as described above.

[0116] Examples of constituent units having polymerizable groups include the following:

[0117] [ka]

[0118] When the resin contains polymerizable structural units, the content of polymerizable structural units is preferably 5.0 to 70.0% by mass, more preferably 10.0 to 50.0% by mass, even more preferably 15.0 to 40.0% by mass, and particularly preferably 20.0 to 40.0% by mass, based on the total mass of the resin.

[0119] Methods for introducing polymerizable groups into 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 present in the resin, such as hydroxyl groups, carboxyl groups, primary amino groups, secondary amino groups, acetoacetyl groups, and sulfo groups. A preferred embodiment of the method for introducing polymerizable groups into a resin is, for example, a method in which a first monomer is synthesized by polymerization, and then a third monomer (preferably glycidyl (meth)acrylate) is polymerized to some of the carboxyl groups of the constituent units derived from the first monomer of the resulting resin by polymer reaction to introduce polymerizable groups (preferably (meth)acryloxy groups) into the resin. The reaction temperature for the polymer reaction is preferably 80 to 110°C. The polymer reaction is preferably carried out using a catalyst, and more preferably using an ammonium salt (tetraethylammonium bromide). The reaction temperature for the above polymerization reaction is preferably 70 to 100°C, and more preferably 80 to 90°C. The above 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 resin is a resin containing constituent units derived from methacrylic acid, constituent units derived from methyl methacrylate, and constituent units derived from styrene or benzyl methacrylate, and a resin containing constituent units derived from methacrylic acid and constituent units derived from styrene, and more preferably a resin containing constituent units having polymerizable groups. In the above, it is also preferable to adjust the content of each constituent unit to the respective preferred embodiments described above.

[0121] The Tg of the resin is preferably 60 to 135°C, more preferably 70 to 115°C, even more preferably 75 to 105°C, and particularly preferably 80 to 100°C.

[0122] The acid value of the resin is preferably 220 mgKOH / g or less, more preferably less than 200 mgKOH / g, even more preferably less than 190 mgKOH / g, and particularly preferably less than 170 mgKOH / g, from the viewpoint of achieving superior effects of the present invention. The lower limit is preferably 10 mgKOH / g or more, more preferably 50 mgKOH / g or more, even more preferably 70 mgKOH / g or more, and particularly preferably 90 mgKOH / g or more, from the viewpoint of achieving superior effects of the present invention. "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 resin can be adjusted by the type of constituent units the resin possesses and / or the content of constituent units containing acid groups.

[0123] The weight-average molecular weight of the resin is preferably 5,000 to 500,000, more preferably 10,000 to 100,000, even more preferably 10,000 to 60,000, and particularly preferably 20,000 to 50,000. 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 5,000 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 composition 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 photomask in subsequent exposure processes, causing defective products. The degree of dispersion of the 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.

[0124] The photosensitive composition layer may contain other resins in addition to the resins mentioned above. 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.

[0125] The resin may be used individually 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. As an upper limit, it is preferable to use 100.0% by mass or less, based on the total mass of the resin.

[0126] The resin content 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 composition layer. When the resin content is 90.0% by mass or less relative to the total mass of the photosensitive composition layer, the development time can be controlled. Furthermore, when the resin content is 10.0% by mass or more relative to the total mass of the photosensitive composition layer, the edge fusing resistance can be improved.

[0127] One method for synthesizing the resin is to dilute the above-mentioned monomers with solvents such as acetone, methyl ethyl ketone, and isopropanol, add appropriate amounts of radical polymerization initiators such as benzoyl peroxide and azoisobutyronitrile to the solution, and then heat and stir. The mixture may also be synthesized by adding a portion of it dropwise to the reaction solution. After the reaction is complete, the solvent may be further added to adjust the concentration to the desired level. Other methods for synthesizing resins include, for example, bulk polymerization, suspension polymerization, and emulsion polymerization.

[0128] <Polymerizable compound> The photosensitive composition layer may contain a polymerizable compound having a polymerizable group. "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.

[0129] The polymerizable groups in a polymerizable compound can be any groups that participate 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. In particular, polymerizable groups are preferably groups having an ethylenically unsaturated group, and acryloyl groups or methacryloyl groups are more preferred.

[0130] As polymerizable compounds, compounds having one or more ethylenically unsaturated groups (hereinafter also referred to as "ethylenically unsaturated compounds") are preferred, and compounds having two or more ethylenically unsaturated groups in the molecule (hereinafter also referred to as "polyfunctional ethylenically unsaturated compounds") are more preferred, in that they provide superior photosensitivity to the photosensitive composition layer. 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, even more preferably 2 to 3, and particularly preferably 3.

[0131] Polymerizable compounds may have alkylene oxy groups. The alkylene group described above is preferably an ethyleneoxy group or a propyleneoxy group, and the ethyleneoxy group is more preferred in terms of superior effects of the present invention. The number of alkyleneoxy groups added to the polymerizable compound is preferably 2 to 30 per molecule, and more preferably 2 to 20.

[0132] From the viewpoint of achieving a better balance between photosensitivity, resolution, and peelability of the photosensitive composition layer, the polymerizable compound preferably contains a bifunctional or trifunctional ethylenically unsaturated compound having two or three ethylenically unsaturated groups in the molecule, and more preferably contains a trifunctional ethylenically unsaturated compound having three ethylenically unsaturated groups in one molecule.

[0133] The content of the difunctional ethylenically unsaturated compound 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, relative to the total mass of the polymerizable compound, from the viewpoint of excellent peelability. 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 composition layer may be difunctional ethylenically unsaturated compounds. The content of the trifunctional ethylenically unsaturated compound is preferably 10.0% by mass or more, and more preferably 20.0% by mass or more, relative to the total mass of the polymerizable compound. 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 composition layer may be 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.

[0134] (Polymerizable compound B1) The photosensitive composition 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.

[0135] 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.

[0136] Polymerizable compound B1 is preferably a bisphenol structure because it suppresses swelling of the photosensitive composition layer by the developer, thereby improving resolution. 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.

[0137] 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 30 per molecule, and 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.

[0138] 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.), ethoxylated bisphenol A dimethacrylates such as 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane and 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (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.).

[0139] As the polymerizable compound B1, the compound represented by formula (B1) is also preferred.

[0140] [ka]

[0141] 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.

[0142] 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 composition 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 member).

[0143] 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. As an upper limit, relative to the total mass of the polymerizable compound, it is preferably 100.0% by mass or less, more preferably 99.0% by mass or less, even more preferably 95.0% by mass or less, particularly preferably 90.0% by mass or less, and most preferably 85.0% by mass or less, relative to the total mass of the polymerizable compound, from the viewpoint of peelability.

[0144] (Other polymerizable compounds) The photosensitive composition layer may contain other polymerizable compounds in addition to those mentioned above. Other polymerizable compounds include, for example, well-known polymerizable compounds. Specifically, these include compounds having one ethylenically unsaturated group in the molecule (monofunctional ethylenically unsaturated compounds), difunctional ethylenically unsaturated compounds without an aromatic ring, and trifunctional or more ethylenically unsaturated compounds.

[0145] 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.

[0146] Examples of bifunctional ethylenically unsaturated compounds that do not have an aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate. Examples of alkylene glycol di(meth)acrylates include tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), tricyclodecanedimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate. Examples of polyalkylene glycol di(meth)acrylates include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate. Examples of urethane di(meth)acrylates include propylene oxide-modified urethane di(meth)acrylates, and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates. Examples of commercially available 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.).

[0147] 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, ditrimethylolpropanetetra(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.

[0148] Examples of alkylene oxide modified products of ethylenically unsaturated compounds with three or more functions include caprolactone-modified (meth)acrylate compounds (such as KAYARAD® DPCA-20 manufactured by Nippon Kayaku Co., Ltd. and A-9300-1CL manufactured by Shin Nakamura Chemical Industry Co., Ltd.), alkylene oxide-modified (meth)acrylate compounds (such as KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin Nakamura Chemical Industry Co., Ltd., and EBECRYL® 135 manufactured by Daicel Ornex Co., Ltd.), ethoxylated glycerin triacrylate (such as A-GLY-9E manufactured by Shin Nakamura Chemical Industry Co., Ltd.), Arronix® TO-2349 (manufactured by Toagosei Co., Ltd.), Arronix M-520 (manufactured by Toagosei Co., Ltd.), and Arronix M-510 (manufactured by Toagosei Co., Ltd.).

[0149] 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 polymerizable compounds having an acidic group include Arronix® TO-2349 (manufactured by Toagosei Co., Ltd.), Arronix® M-520 (manufactured by Toagosei Co., Ltd.), and Arronix® M-510 (manufactured by Toagosei Co., Ltd.). Examples of polymerizable compounds having an acidic group include the polymerizable compounds having an acidic group described in paragraphs

[0025] to

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

[0150] The molecular weight of the polymerizable compound is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.

[0151] The viscosity of the polymerizable compound at 25°C is preferably 1 to 10,000 mPa·s, more preferably 5 to 3,000 mPa·s, and even more preferably 10 to 1,500 mPa·s. Furthermore, when two or more polymerizable compounds are used, the difference (absolute value) between the viscosity of polymerizable compound A, which has the highest viscosity, at 25°C and the viscosity of polymerizable compound B, which has the lowest viscosity, at 25°C is preferably 250 to 5000 mPa·s, more preferably 500 to 2500 Pa·s, and even more preferably 900 to 1000 Pa·s. Examples of methods for measuring the viscosity mentioned above include the following: The viscosity will be measured using a vibrating viscometer (SEKONIC VM-10A). Specifically, 20 mL of polymerizable compound will be transferred to a container and allowed to stand at room temperature (25±2°C) for 30 minutes. After that, the detection terminal will be inserted into the container of polymerizable compound, and the power will be turned on. The viscosity value will be read after 30 seconds.

[0152] The polymerizable group content of the polymerizable compound is preferably 1.0 mmol / g or more, more preferably 2.0 mmol / g or more, and even more preferably 2.4 mmol / g or more, as this provides superior effects for the present invention. The upper limit is preferably 10.0 mmol / g or less. The above polymerizable content may also be interpreted as the double bond content. When the photosensitive composition layer contains multiple polymerizable compounds, it is preferable that the content of polymerizable groups in all of the polymerizable compounds is as described above. For example, it is preferable that all of the polymerizable compounds have 2.4 mmol / g or more of polymerizable groups. "Polymerizable group content" refers to the equivalent amount (moles) of polymerizable groups contained per gram of polymerizable compound.

[0153] Polymerizable compounds may be used individually or in combination of two or more. In particular, polymerizable compounds are preferably used in groups of three or more, and more preferably in groups of three, as this enhances the effects of the present invention. When using three polymerizable 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 polymerizable compound content 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, based on the total mass of the photosensitive composition layer.

[0154] The mass ratio of the polymerizable compound content to the resin content (polymerizable 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 yields superior effects of the present invention.

[0155] The photosensitive composition layer may also preferably contain the polymerizable compound B1 and a trifunctional or higher 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] <Polymerization initiator> The photosensitive composition layer may contain 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. The polymerization initiator may be either a radical polymerization initiator or a cationic polymerization initiator.

[0157] The photosensitive composition layer preferably contains a photopolymerization initiator. A photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound upon exposure to active light such as ultraviolet light, visible light, and X-rays. 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.

[0158] 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.

[0159] 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.

[0160] 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.

[0161] 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-benzoyl oxime) (TR-PBG-305, manufactured by Changzhou Strong Power 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 Electronic New Materials Co., Ltd.) and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazole-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (TR-PBG-391, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.).

[0162] 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.

[0163] Examples of photocationic polymerization initiators include ionic photocationic polymerization initiators and nonionic photocationic polymerization initiators. Examples of the ionic photo cationic polymerization initiators include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts. Examples of the ionic photo cationic polymerization initiators include the ionic photo cationic polymerization initiators described in paragraphs

[0114] to

[0133] of JP-A-2014-085643.

[0164] Examples of the nonionic photo cationic polymerization initiators include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Examples of the trichloromethyl-s-triazines, diazomethane compounds, and imide sulfonate compounds include the compounds described in paragraphs

[0083] to

[0088] of JP-A-2011-221494. Examples of the oxime sulfonate compounds include the compounds described in paragraphs

[0084] to

[0088] of WO 2018 / 179640.

[0165] The polymerization initiator may be used alone or in combination of two or more. The content of the polymerization initiator (preferably a photo polymerization initiator) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total mass of the photosensitive composition layer. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, based on the total mass of the photosensitive composition layer.

[0166] <Dye> From the viewpoints of the visibility of the exposed portion and the unexposed portion, and the pattern visibility and resolution after development, the photosensitive composition layer may contain a dye (hereinafter also referred to as "dye N") having a maximum absorption wavelength in the wavelength range of 400 to 780 nm during color development of 450 nm or more, and the maximum absorption wavelength is changed by an acid, a base, or a radical. When the dye N is contained, although the detailed mechanism is unknown, the adhesion to an adjacent layer (for example, an intermediate layer) is improved and the resolution is more excellent.

[0167] The statement that the pigment "has a maximum absorption wavelength that changes due to an acid, a base, or a radical" may mean any of the following modes: a mode in which the pigment in the colored state is decolorized by an acid, a base, or a radical; a mode in which the pigment in the decolorized state is colored by an acid, a base, or a radical; and a mode in which the pigment in the colored state changes to a colored state of another hue. Specifically, the pigment N may be either a compound that changes from the decolorized state to the colored state upon exposure or a compound that changes from the colored state to the decolorized state upon exposure. In the above cases, it may be a pigment whose coloring or decoloring state changes due to the generation and action of an acid, a base, or a radical in the photosensitive composition layer upon exposure, or it may be a pigment whose coloring or decoloring state changes due to a change in the state (e.g., pH) in the photosensitive composition layer by an acid, a base, or a radical. Also, it may be a pigment whose coloring or decoloring state changes directly upon receiving an acid, a base, or a radical as a stimulus without going through exposure.

[0168] Among them, from the viewpoints of visibility and resolution of the exposed part and the non-exposed part, the pigment N is preferably a pigment whose maximum absorption wavelength changes due to an acid or a radical, and more preferably a pigment whose maximum absorption wavelength changes due to a radical. From the viewpoints of visibility and resolution of the exposed part and the non-exposed part, the photosensitive composition layer preferably contains both a pigment whose maximum absorption wavelength changes due to a radical as the pigment N and a photo radical polymerization initiator. Also, from the viewpoint of visibility of the exposed part and the non-exposed part, the pigment N is preferably a pigment that is colored by an acid, a base, or a radical.

[0169] Examples of the coloring mechanism of the pigment N include adding a photo radical polymerization initiator, a photo cationic polymerization initiator (photo acid generator), or a photo base generator to the photosensitive composition layer, and coloring a radical-reactive pigment, an acid-reactive pigment, or a base-reactive pigment (e.g., a leuco pigment) by a radical, an acid, or a base generated from the photo radical polymerization initiator, the photo cationic polymerization initiator, or the photo base generator after exposure.

[0170] 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.

[0171] 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).

[0172] 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.

[0173] 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.

[0174] 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 develops color when the lactone ring, sultine ring, or sultone ring opens in response to radicals or acids is preferred, and a compound having a lactone ring that develops color when the lactone ring opens in response to radicals or acids is more preferred.

[0175] 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, Congo 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: 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.

[0176] 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-di Ethylamino)-7-benzylaminofluorane, 3-(N,N-diethylamino)-7,8-benzofluorane, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluorane, 3-(N,N-dibutylamino)-6-methyl-7-xylidinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3,3-bis(1-ethyl-2-methylindole-3-yl)phthalide, 3,3-bis(1-n-butyl-2 Examples include methylindole-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-zaphthalide, 3'-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)phthalide, and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthene-3-one.

[0177] As for the dye N, a dye whose maximum absorption wavelength changes due to radicals is preferred, and a dye that develops color due to radicals is more preferred, in terms of excellent visibility of exposed and unexposed areas, pattern visibility after development, and resolution. As the dye N, leucocrystal violet, crystal violet lactone, brilliant green, or Victoria Pure Blue naphthalene sulfonate are preferred.

[0178] Dye N may be used alone or in combination of two or more types. The content of dye N is preferably 0.1% by mass or more, more preferably 0.1 to 10% by mass, even more preferably 0.1 to 5% by mass, and particularly preferably 0.1 to 1% by mass, based on the total mass of the photosensitive composition layer, in order to provide excellent visibility of the exposed and unexposed areas, as well as pattern visibility and resolution after development.

[0179] The content of dye N refers to the amount of dye N present in the total mass of the photosensitive composition layer when all of the dye N is in a color-developed state. Below, the method for quantifying the content of dye N will be explained using a dye that develops color via radicals as an example. Prepare two solutions: one in which 0.001 g of dye N is dissolved in 100 mL of methyl ethyl ketone, and the other in which 0.01 g of dye N is dissolved in 100 mL of methyl ethyl ketone. Add a photoradical polymerization initiator (Irgacure OXE01, BASF Japan) to each of the obtained solutions, and irradiate with 365 nm light to generate radicals, causing all of the dye N to develop color. Then, under an atmospheric environment, measure the absorbance of each solution at a liquid temperature of 25°C using a spectrophotometer (UV3100, Shimadzu Corporation), and create a calibration curve. Next, the absorbance of the solution in which all the dye has developed is measured using the same method as above, except that the photosensitive composition layer (3g) is dissolved in methyl ethyl ketone instead of dye N. From the absorbance of the obtained solution containing the photosensitive composition layer, the amount of dye N contained in the photosensitive composition layer is calculated based on the calibration curve. "Photosensitive composition layer (3g)" is synonymous with 3g of total solids in the photosensitive composition.

[0180] <Thermal crosslinkable compound> The photosensitive composition layer may contain a thermally crosslinkable compound in terms 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 methylol compounds and blocked isocyanate compounds. In terms of the strength of the resulting cured film and the adhesiveness of the resulting uncured film, blocked isocyanate compounds are 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 composition 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.

[0181] 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, by DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter (for example, DSC6200, manufactured by Seiko Instruments Inc.), the temperature of the endothermic peak accompanying the deprotection reaction of the blocked isocyanate compound as the degree of dissociation.

[0182] 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.

[0183] 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.

[0184] 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.

[0185] 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.

[0186] [ka]

[0187] 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 composition layer.

[0188] <Pigments> The photosensitive composition layer may contain a pigment. When the photosensitive composition layer contains a pigment, it corresponds to a colored resin layer. In recent electronic devices, liquid crystal display windows may have a cover glass attached to the back edge of a transparent glass substrate or similar material to protect the liquid crystal display window. This cover glass has a black, frame-shaped light-shielding layer formed on the back edge. A colored resin layer may be used to form such a light-shielding layer. The pigment can be appropriately selected according to the desired hue, and examples include black pigment, white pigment, and pigments of other chromatic colors besides black and white. When forming a black-based pattern, black pigment is preferred as the pigment.

[0189] (Black pigment) Examples of black pigments include known black pigments (e.g., organic pigments and inorganic pigments). In particular, from the viewpoint of optical density, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, or graphite are preferred as black pigments, with carbon black being more preferred. As for carbon black, from the viewpoint of surface resistance, surface-modified carbon black in which at least a portion of the surface is coated with resin is preferred.

[0190] The particle size (number-average particle size) of the black pigment is preferably 0.001 to 0.1 μm, and more preferably 0.01 to 0.08 μm, from the viewpoint of dispersion stability. "Particle size" refers to the diameter of a circle with the same area as the pigment particle, calculated from a photograph of the pigment particle taken with an electron microscope. "Number-average particle size" refers to the average value obtained by calculating the particle size for any 100 particles and averaging the calculated particle sizes of those 100 particles.

[0191] Examples of white pigments include inorganic pigments and the white pigments described in paragraphs

[0015] and

[0114] of Japanese Patent Publication No. 2005-007765. As inorganic pigments, titanium dioxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate are preferred, titanium dioxide or zinc oxide is more preferred, titanium dioxide is even more preferred, rutile-type or anatase-type titanium dioxide is particularly preferred, and rutile-type titanium dioxide is most preferred. Furthermore, the surface of titanium dioxide may be treated with silica, alumina, titania, zirconia, or organic substances, or two or more of these treatments may be applied. This suppresses the catalytic activity of titanium dioxide and improves its heat resistance and fading properties. From the viewpoint of reducing the thickness of the photosensitive composition layer after heating, it is preferable to apply at least one of alumina treatment and zirconia treatment as a surface treatment to the surface of titanium oxide, and more preferably both alumina treatment and zirconia treatment.

[0192] When the photosensitive composition layer is a colored resin layer, it is preferable, from the viewpoint of transferability, that the photosensitive composition layer also contains chromatic pigments other than black and white pigments. For chromatic pigments, the particle size (number-average particle size) is preferably 0.1 μm or less, and more preferably 0.08 μm or less, from the standpoint of superior dispersibility. The lower limit is preferably 10 nm or more. Examples of chromatic pigments include Victoria Pure Blue BO (Color Index (hereinafter also referred to as "CI") 42595), Auramine (CI 41000), Fat Black HB (CI 26150), Monolight Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11), Fastel Pink B Spray (CI Pigment Red 81), and Monastral First Blue (CI Pigment Blue Examples include -15), Monolight First Black B (CI Pigment Black 1) and Carbon, CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red 215, CI Pigment Green 7, CI Pigment Blue 15:1, CI Pigment Blue 15:4, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64 and CI Pigment Violet 23, with CI Pigment Red 177 being preferred.

[0193] Pigments may be used individually or in combination of two or more types. The pigment content is preferably more than 3% by mass and 40% by mass or less, more preferably more than 3% by mass and 35% by mass or less, even more preferably more than 5% by mass and 35% by mass or less, and particularly preferably 10 to 35% by mass, based on the total mass of the photosensitive composition layer.

[0194] When the photosensitive composition layer contains pigments other than black pigment (for example, white pigment and chromatic pigment), the content of pigments other than black pigment is preferably 30% by mass or less, more preferably 1 to 20% by mass, and even more preferably 3 to 15% by mass, relative to the total mass of black pigment.

[0195] If the photosensitive composition layer contains a black pigment, it is preferable that the black pigment (preferably carbon black) be introduced into the photosensitive composition in the form of a pigment dispersion. The dispersion may be prepared by pre-mixing a black pigment and a pigment dispersant, obtaining a mixture, and then adding it to an organic solvent (or vehicle) and dispersing it in a disperser. The pigment dispersant can be selected according to the pigment and solvent; for example, commercially available dispersants can be used. "Vehicle" refers to the medium that disperses the pigment in a pigment dispersion. The above vehicle is liquid and contains a binder component that holds the black pigment in a dispersed state, and a solvent component (organic solvent) that dissolves and dilutes the binder component.

[0196] Examples of known dispersers include kneaders, roll mills, attritors, super mills, dissolvers, homomixers, and sand mills. Alternatively, the material may be finely ground using frictional force through mechanical grinding. Examples of dispersers and fine grinders can be found in, for example, the "Dictionary of Pigments" (by Kunizo Asakura, 1st edition, Asakura Shoten, 2000, pp. 438, 310).

[0197] <Other additives> The photosensitive composition layer may contain other additives as needed, in addition to the above-mentioned components. 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 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.

[0198] (Radical polymerization inhibitor) Examples of radical polymerization inhibitors include the thermal polymerization inhibitors described in paragraph

[0018] of Japanese Patent Publication 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 composition 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 composition 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.

[0199] (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.

[0200] (Carboxybenzotriazoles) Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole. A specific example of a carboxybenzotriazole is CBT-1 (manufactured by Johoku Chemical Industry Co., Ltd.).

[0201] 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 composition layer. When the above content is 0.01% by mass or more, the storage stability of the photosensitive composition 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.

[0202] (Sensitizer) Examples of sensitizers include known sensitizers, dyes, and pigments. Examples of sensitizers include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

[0203] The sensitizer content is preferably 0.01 to 5% by mass, and more preferably 0.05 to 1% by mass, relative to the total mass of the photosensitive composition layer, from the viewpoint of improving sensitivity to light sources and improving curing speed by balancing polymerization rate and chain transfer.

[0204] (Surfactants) Examples of surfactants include those described in paragraph

[0017] of Japanese Patent No. 4502784 and paragraphs

[0060] to

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

[0205] As the surfactant, nonionic surfactants, fluorinated surfactants, or silicone surfactants are preferred. 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, and F-780. EXP.MFS-330, 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).

[0206] 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).

[0207] 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.

[0208] 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 and 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.).

[0209] 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.

[0210] Specifically, silicone-based surfactants include EXP.S-309-2, EXP.S-315, EXP.S-503-2, EXP.S-505-2 (all manufactured by DIC Corporation), DOWSIL 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, K F-6001, KF-6002, KP-101, KP-103, KP-104, KP-105, KP-106, KP-109, KP-112, KP-120, KP-121, KP-124, KP -125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, KP-652 (all manufactured by Shin-Etsu Silicone Co., Ltd.); F-4440, TSF-4300, TSF-4445, TSF-4460 and TSF-4452 (all manufactured by Momentive Performance Examples include BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, and BYK323 (all manufactured by Bic Chemie).

[0211] 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, based on the total mass of the photosensitive composition layer.

[0212] 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.

[0213] <Impurities> The photosensitive composition layer may contain impurities. Examples of impurities include metal impurities or their ions, halide ions, residual organic solvents, residual monomers, and water.

[0214] (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.

[0215] 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 composition 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 composition layer.

[0216] Methods for adjusting the impurity content include, for example, selecting raw materials with a low impurity content for the photosensitive composition layer, as well as methods for preventing the inclusion of impurities during the formation of the photosensitive composition layer and methods for removing them by washing. The impurity content can be quantified by known methods such as ICP emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0217] (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 composition 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 composition 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.

[0218] (Remaining monomers) The photosensitive composition 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 composition 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 composition layer.

[0219] 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.

[0220] The water content in the photosensitive composition 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.

[0221] [Characteristics of the photosensitive composition layer] The thickness (film thickness) of the photosensitive composition layer is often 0.1 to 300 μm, preferably 0.2 to 100 μm, more preferably 0.5 to 50 μm, even more preferably 0.5 to 30 μm, and particularly preferably 1 to 20 μm. This improves the developability of the photosensitive composition layer and enhances resolution.

[0222] The polymerizable group content in the photosensitive composition layer is preferably 1.0 mmol / g or more, more preferably 2.0 mmol / g or more, and even more preferably 3.0 mmol / g or more, from the viewpoint of superior effects of the present invention. The upper limit is preferably 10.0 mmol / g or less. The above polymerizable group content may also be interpreted as the double bond content.

[0223] The acid value of the photosensitive composition layer is preferably 10 to 150 mg KOH / g, more preferably 40 to 120 mg KOH / g, even more preferably 50 to 120 mg KOH / g, particularly preferably 50 to 100 mg KOH / g, and most preferably 60 to 100 mg KOH / g. Examples of methods for measuring the acid value include methods for measuring the acid value of the resin and methods for calculating the acid value from the content of a resin whose acid value is known.

[0224] [Middle class] The transfer film may have an intermediate layer between the temporary support and the photosensitive composition layer. For example, the intermediate layer is preferably placed between the temporary support and the photosensitive composition layer if there is no thermoplastic resin layer, or between the thermoplastic resin layer and the photosensitive composition layer if there is a thermoplastic resin 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 preferred because it improves sensitivity during exposure, reduces the time load on the exposure machine, and improves productivity. More preferably, an oxygen barrier layer exhibiting low oxygen permeability 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.

[0225] <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.

[0226] Examples of cellulose-based resins include water-soluble cellulose derivatives. Examples of water-soluble cellulose derivatives include hydroxyethylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, methylcellulose, and ethylcellulose.

[0227] 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.

[0228] 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.

[0229] 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.

[0230] 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 99.9% by mass or less, even more preferably 99.8% by mass or less, and particularly preferably 99% by mass or less, relative to the total mass of the intermediate layer.

[0231] <Other ingredients> The intermediate layer may contain other components in addition to the resin mentioned above.

[0232] 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.

[0233] 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.

[0234] The intermediate layer preferably contains at least one selected from the group consisting of water-soluble cellulose derivatives, polyhydric alcohols, oxide adducts of polyhydric alcohols, polyether resins, phenol derivatives, and amide compounds.

[0235] 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.

[0236] 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.

[0237] <Impurities> The intermediate layer may contain impurities. Examples of impurities include those contained in the above-mentioned photosensitive composition layer.

[0238] 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 1.0 μm or more.

[0239] [Thermoplastic resin layer] The transfer film may have a thermoplastic resin layer. The thermoplastic resin layer is preferably placed between the temporary support and the photosensitive composition layer if there is no intermediate layer, and between the temporary support and the intermediate layer if there is an intermediate layer. When the transfer film has a thermoplastic resin layer, its conformability to the transfer object during the lamination process is improved, and the inclusion of air bubbles between the transfer film and the transfer object can be suppressed. As a result, the adhesion between the thermoplastic resin layer and adjacent layers (e.g., temporary support) is improved. Examples of thermoplastic resin layers include paragraphs

[0189] to

[0193] of Japanese Patent Publication No. 2014-085643, the contents of which are incorporated herein by reference. The following describes the various components that the thermoplastic resin layer may contain.

[0240] <Thermoplastic resin> The thermoplastic resin layer may contain thermoplastic resin. Alkali-soluble resins are preferred as thermoplastic resins. Examples of alkali-soluble resins include acrylic resins, polystyrene 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 glycol. As the alkali-soluble resin, the alkali-soluble resin contained in the photosensitive composition layer described above may be used.

[0241] As the alkali-soluble resin, acrylic resin is preferred from the viewpoint of developability and adhesion to adjacent layers. "Acrylic resin" means a resin containing at least one constituent unit selected from the group consisting of constituent units derived from (meth)acrylic acid, constituent units derived from (meth)acrylic acid esters, and constituent units derived from (meth)acrylamide. In acrylic resins, the total content of constituent units derived from (meth)acrylic acid, (meth)acrylic acid ester, and (meth)acrylamide is preferably 30% by mass or more, and more preferably 50% by mass or more, relative to the total mass of the acrylic resin. The upper limit is preferably 100% by mass or less, relative to the total mass of the acrylic resin. In particular, the total content of constituent units derived from (meth)acrylic acid and constituent units derived from (meth)acrylic acid esters is preferably 30 to 100% by mass, and more preferably 50 to 100% by mass, relative to the total mass of the acrylic resin.

[0242] As the alkali-soluble resin, a resin having an acidic group is preferred. Examples of acidic groups include carboxyl groups, sulfol groups, phosphate groups, and phosphonic acid groups, with carboxyl groups being preferred. Furthermore, the alkali-soluble resin preferably contains constituent units having acidic groups, more preferably contains constituent units having carboxyl groups, and even more preferably, an acrylic resin having constituent units derived from (meth)acrylic acid is preferred from the viewpoint of developability and adhesion to adjacent layers.

[0243] For alkali-soluble resins, the acid value is preferably 60 mg KOH / g or higher from the viewpoint of developability. The upper limit is preferably 300 mg KOH / g or less, more preferably 250 mg KOH / g or less, even more preferably 200 mg KOH / g or less, and particularly preferably 150 mg KOH / g or less. Among these, alkali-soluble resins with an acid value of 60 mgKOH / g or higher are preferred, and acrylic resins having carboxyl groups with an acid value of 60 mgKOH / g or higher are more preferred.

[0244] As an acrylic resin having a carboxyl group with an acid value of 60 mgKOH / g or more, for example, it can be appropriately selected from known resins and used. Specifically, examples include paragraph

[0025] of Japanese Patent Publication No. 2011-095716, paragraphs

[0033] to

[0052] of Japanese Patent Publication No. 2010-237589, and paragraphs

[0053] to

[0068] of Japanese Patent Publication No. 2016-224162.

[0245] The content of the constituent units having a carboxyl group is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 12 to 30% by mass, based on the total mass of the acrylic resin.

[0246] Alkali-soluble resins may have polymerizable groups. The polymerizable group can be any group that participates in the polymerization reaction, and examples include groups having ethylenically unsaturated groups such as vinyl groups, acryloyl groups, methacryloyl groups, styryl groups, and maleimide groups; and groups having cationic polymerizable groups such as epoxy groups and oxetane groups. In particular, polymerizable groups are preferably groups having an ethylenically unsaturated group, and acryloyl groups or methacryloyl groups are more preferred.

[0247] The weight-average molecular weight of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and even more preferably 20,000 to 50,000.

[0248] Thermoplastic resins may be used individually or in combination of two or more types. From the viewpoint of developability and adhesion to adjacent layers, the thermoplastic resin content is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, even more preferably 40 to 80% by mass, and particularly preferably 50 to 75% by mass, relative to the total mass of the thermoplastic resin layer.

[0249] <Dye> The thermoplastic resin layer may contain a dye (hereinafter also simply referred to as "dye B") whose maximum absorption wavelength in the wavelength range of 400 to 780 nm at the time of color development is 450 nm or higher, and whose maximum absorption wavelength changes due to an acid, base, or radical. The preferred embodiment of dye B is the same as that of dye N, except for the points described later, and the preferred embodiment is also the same.

[0250] As for dye B, a dye whose maximum absorption wavelength changes with acid or radicals is preferred, and a dye whose maximum absorption wavelength changes with acid is more preferred, from the viewpoint of visibility of the exposed and unexposed areas, as well as resolution. The thermoplastic resin layer preferably contains both a dye whose maximum absorption wavelength changes with an acid as dye B, and a compound that generates an acid when exposed to light, as described later, from the viewpoint of visibility of the exposed and unexposed areas, as well as resolution.

[0251] Pigment B may be used alone or in combination of two or more types. From the viewpoint of visibility between the exposed and unexposed areas, the content of dye B is preferably 0.2% by mass or more, more preferably 0.2 to 6.0% by mass, even more preferably 0.2 to 5.0% by mass, and particularly preferably 0.25 to 3.0% by mass, relative to the total mass of the thermoplastic resin layer. "Pigment B content" refers to the amount of pigment B present in the thermoplastic resin layer when all of it is in a colored state. The following explains how to quantify the pigment B content, using a pigment that develops color through radicals as an example. Prepare two solutions: one in which 0.001 g of dye B is dissolved in 100 mL of methyl ethyl ketone, and another in which 0.01 g of dye B is dissolved in 100 mL of methyl ethyl ketone. Add a photoradical polymerization initiator (Irgacure OXE01, BASF Japan) to each of the obtained solutions, and irradiate with 365 nm light to generate radicals, causing all of the dye B to develop color. Then, under an atmospheric environment, measure the absorbance of each solution at a liquid temperature of 25°C using a spectrophotometer (UV3100, Shimadzu Corporation) and create a calibration curve. Next, the absorbance of the solution in which all the dyes have developed is measured, using the same method as above, except that a thermoplastic resin layer (3g) is dissolved in methyl ethyl ketone instead of dye B. From the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of dye B contained in the thermoplastic resin layer is calculated based on the calibration curve. "Thermoplastic resin layer (3g)" is synonymous with 3g of total solids in the thermoplastic resin composition.

[0252] <Compounds that generate acids, bases, or radicals upon exposure to light> The thermoplastic resin layer may contain a compound that generates an acid, base, or radical upon exposure to light (hereinafter also simply referred to as "compound C"). As compound C, a compound that generates an acid, base, or radical upon exposure to active light such as ultraviolet light and visible light is preferred. Examples of compound C include known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators).

[0253] (Photoacid generator) The thermoplastic resin layer may contain a photoacid generator for the sake of resolution. Examples of photoacid generators include photocationic polymerization initiators that may be included in the above-mentioned photosensitive composition layer, and the preferred embodiments are the same except for the points described later.

[0254] As a photoacid generator, it is preferable that it contains at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds, from the viewpoint of sensitivity and resolution, and it is more preferable that it contains an oxime sulfonate compound, from the viewpoint of sensitivity, resolution and adhesion. As a photoacid generator, a photoacid generator having the following structure is also preferred.

[0255] [ka]

[0256] (Photoradical polymerization initiator) The thermoplastic resin layer may contain a photoradical polymerization initiator. Examples of photoradical polymerization initiators include photoradical polymerization initiators that can be contained in the above-mentioned photosensitive composition layer, and the preferred embodiments are the same.

[0257] (Photobase Generator) The thermoplastic resin composition may contain a photobase generator. Examples of photobase generators include well-known photobase generators. Specifically, 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)-1-benzyl-1-dimethyl Examples include minopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt(III)tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2,6-dimethyl-3,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine, and 2,6-dimethyl-3,5-diacetyl-4-(2,4-dinitrophenyl)-1,4-dihydropyridine.

[0258] Compound C may be used alone or in combination of two or more compounds. The content of compound C is preferably 0.1 to 10% by mass, and more preferably 0.5 to 5% by mass, relative to the total mass of the thermoplastic resin layer, from the viewpoint of visibility of the exposed and unexposed areas, as well as resolution.

[0259] <Plasticizer> The thermoplastic resin layer may contain a plasticizer, in terms of resolution, adhesion to adjacent layers, and developability. The plasticizer is preferably smaller in molecular weight (or weight-average molecular weight if it is an oligomer or polymer with a molecular weight distribution) than the thermoplastic resin (preferably an alkali-soluble resin). Specifically, the molecular weight (weight-average molecular weight) of the plasticizer is preferably 200 to 2,000. The plasticizer is not particularly limited as long as it is a compound that is compatible with the alkali-soluble resin and exhibits plasticity. From the viewpoint of imparting plasticity, plasticizers are preferably found to have alkylene oxy groups in their molecules, and more preferably to have a polyethylene oxy structure or a polypropylene oxy structure. Polyalkylene glycol compounds are preferred as plasticizers.

[0260] From the viewpoint of resolution and storage stability, the plasticizer preferably contains a (meth)acrylate compound. From the viewpoint of compatibility, resolution, and adhesion to adjacent layers, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound. Examples of (meth)acrylate compounds include polymerizable (meth)acrylate compounds that can be included in the above-mentioned photosensitive composition layer. In transfer films, when a thermoplastic resin layer and a photosensitive composition layer are laminated in direct contact (without an intermediate layer), it is preferable that both the thermoplastic resin layer and the photosensitive composition layer contain the same (meth)acrylate compound. By having the thermoplastic resin layer and the photosensitive composition layer each contain the same (meth)acrylate compound, interlayer diffusion of components is suppressed, and storage stability is improved.

[0261] When the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, it is preferable that the (meth)acrylate compound does not polymerize in the exposed area after exposure, from the viewpoint of adhesion between the thermoplastic resin layer and the adjacent layer. Furthermore, as the (meth)acrylate compound, a polyfunctional (meth)acrylate compound having two or more (meth)acryloyl groups in one molecule is preferred from the viewpoint of resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability. Furthermore, as the (meth)acrylate compound, (meth)acrylate compounds having an acid group or urethane (meth)acrylate compounds are also preferred.

[0262] The plasticizer may be used alone or in combination of two or more types. The plasticizer content is preferably 1 to 70% by mass, more preferably 10 to 60% by mass, and even more preferably 20 to 50% by mass, relative to the total mass of the thermoplastic resin layer, from the viewpoint of resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability.

[0263] <Sensitizer> The thermoplastic resin layer may contain a sensitizer. Examples of sensitizers include those that may be included in the above-mentioned photosensitive composition layer.

[0264] The sensitizer may be used alone or in combination of two or more types. The sensitizer content is preferably 0.01 to 5% by mass, and more preferably 0.05 to 1% by mass, relative to the total mass of the thermoplastic resin layer, from the viewpoint of improving sensitivity to the light source and visibility of the exposed and unexposed areas.

[0265] <Other additives> The thermoplastic resin layer may contain other additives in addition to the components mentioned above. Other additives include, for example, other additives that may be included in the above-mentioned photosensitive composition layer.

[0266] <Impurities> The thermoplastic resin layer may contain impurities. Examples of impurities include those contained in the above-mentioned photosensitive composition layer.

[0267] The thickness of the thermoplastic resin layer is preferably 1 μm or more, and more preferably 2 μm or more, from the viewpoint of adhesion with adjacent layers. The upper limit is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 8 μm or less, from the viewpoint of developability and resolution.

[0268] [Other components] The transfer film may have other components in addition to the components described above. Other components include, for example, protective films.

[0269] 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.

[0270] 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.

[0271] 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 condition where foreign matter, undissolved material, or oxidatively degraded material is incorporated into the film during the manufacturing process, such as by thermal melting, kneading, extrusion, biaxial stretching, and casting.

[0272] 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 composition layer or conductive layer can be suppressed.

[0273] From the standpoint of providing windability, the arithmetic mean roughness Ra of the surface opposite to the surface in contact with the photosensitive composition layer of the protective film, or the surface in contact with it, 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.

[0274] [Method for manufacturing transfer film] Examples of methods for manufacturing transfer films include known methods. Examples of methods for manufacturing the transfer film 10 include the steps of: applying an intermediate layer forming composition to the surface of a temporary support 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 composition layer 15. Furthermore, the process may include a step of applying a thermoplastic resin layer-forming composition to the surface of the temporary support 11 to form a coating film before the step of forming the intermediate layer 13, and then drying this coating film to form a thermoplastic resin layer.

[0275] A transfer film 10 is manufactured by pressing a protective film 19 onto the photosensitive composition 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 composition layer 15, and a protective film 19 by including a step of providing a protective film 19 so as to be in contact with the side of the photosensitive composition layer 15 opposite to the temporary support 11 side. Furthermore, as a method for manufacturing the transfer film, it is also preferable to include a step of providing a protective film 19 so as to contact the side of the photosensitive composition layer 15 opposite to the side of the temporary support 11, thereby manufacturing a transfer film 10 comprising a temporary support 11, a thermoplastic resin layer, an intermediate layer 13, a photosensitive composition layer 15, and a protective film 19. 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 the substrate using the roll-to-roll method described later. Furthermore, as a method for manufacturing the transfer film 10, a photosensitive composition layer 15 and an intermediate layer 13 may be formed on the protective film 19, and then a thermoplastic resin layer may be formed so as to be in contact with the surface of the intermediate layer 13 opposite to the photosensitive composition layer.

[0276] [Photosensitive composition and method for forming a photosensitive composition layer] A preferred method for forming the photosensitive composition layer is to apply it using a photosensitive composition containing components (e.g., resin, polymerizable compound, polymerization initiator, etc.) and a solvent. A preferred method for forming the photosensitive composition layer is, for example, to apply a photosensitive composition onto an intermediate layer to form a coating film, and if necessary, to dry this coating film at a predetermined temperature to form the photosensitive composition layer. The amount of residual solvent is adjusted by the drying treatment of the coating film.

[0277] The photosensitive composition preferably contains the components included in the photosensitive composition layer and a solvent. The content of each component included in the photosensitive composition 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 composition 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.

[0278] 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.

[0279] 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.

[0280] 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.

[0281] 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).

[0282] For drying the photosensitive composition coating, heat drying or reduced-pressure drying is preferred. The drying temperature is preferably 90°C or higher, more preferably 100°C or higher, and even more preferably 110°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.

[0283] Furthermore, a transfer film may be manufactured by laminating a protective film onto a photosensitive composition layer. Methods for laminating a protective film onto a photosensitive composition layer include, for example, known methods. Apparatus for laminating a protective film onto a photosensitive composition 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.

[0284] [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 (e.g., water-soluble resin, etc.) and a solvent. A preferred method for forming the intermediate layer is, for example, to apply an intermediate layer-forming composition onto a temporary support to form a coating film, and then, if necessary, to dry the coating film at a predetermined temperature to form the intermediate layer. The amount of residual solvent is adjusted by the drying process of the coating film.

[0285] 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. C1-C3 alcohols are preferred, and methanol or ethanol are more preferred.

[0286] 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.

[0287] Examples of methods for forming the intermediate layer include known coating methods. Specifically, these include slit coating, spin coating, curtain coating, and inkjet coating.

[0288] For drying the coating film of the intermediate layer-forming composition, heat drying or reduced-pressure drying is preferred. The drying temperature is preferably 90°C or higher, more preferably 100°C or higher, and even more preferably 110°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.

[0289] [Composition for forming a thermoplastic resin layer and method for forming a thermoplastic resin layer] A preferred method for forming a thermoplastic resin layer is to apply it using a thermoplastic resin layer-forming composition that includes components contained in the thermoplastic resin layer (e.g., thermoplastic resin, etc.) and a solvent. A preferred method for forming the thermoplastic resin layer is, for example, 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 thermoplastic resin layer. The amount of residual solvent is adjusted by the drying process of the coating film.

[0290] The composition for forming a thermoplastic resin layer preferably contains components included in the thermoplastic resin layer and a solvent. The content of the components in the thermoplastic resin layer is as described above. The solvent is not particularly limited as long as it can dissolve or disperse the components contained in the thermoplastic resin layer. The solvent is the same as the solvent included in the photosensitive composition described above, and the preferred embodiment is also the same.

[0291] 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, and more preferably 100 to 900 parts by mass, per 100 parts by mass of the total solids content of the thermoplastic resin layer forming composition.

[0292] Examples of methods for forming a thermoplastic resin layer include known coating methods. Specifically, these include slit coating, spin coating, curtain coating, and inkjet coating.

[0293] For drying the coating film of the thermoplastic resin layer-forming composition, heat drying or vacuum drying is preferred. The drying temperature is preferably 90°C or higher, more preferably 100°C or higher, and even more preferably 110°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]

[0294] The present invention will be described in more detail below based on examples. The materials, quantities, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples. Unless otherwise specified, "parts" and "%" are based on mass. Furthermore, in the following examples, the weight-average molecular weight of the resin is the weight-average molecular weight (Mw) obtained by the above-mentioned gel permeation chromatography (GPC) on a polystyrene basis. The glass transition temperature was measured by the method described above.

[0295] 〔resin〕 <Synthesis of resin A1> 85 parts by mass of propylene glycol monomethyl ether was placed in a flask, and the flask was heated to 90°C under a nitrogen stream. To this solution, a solution of styrene (46 parts by mass), methacrylic acid (20 parts by mass), and methyl methacrylate (2 parts by mass) dissolved in propylene glycol monomethyl ether (20 parts by mass), and a solution of polymerization initiator V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (7 parts by mass) dissolved in propylene glycol monomethyl ether (45 parts by mass) were simultaneously added dropwise over 3 hours. After the dropwise addition was complete, 1.0 part by mass of V-601 was added three times at 1-hour intervals. The reaction was then allowed to continue for another 3 hours. After that, the solution was diluted with propylene glycol monomethyl ether acetate (60 parts by mass) and propylene glycol monomethyl ether (12 parts by mass). Under an airflow, the reaction solution was heated to 100°C, and tetraethylammonium bromide (0.7 parts by mass) and p-methoxyphenol (0.3 parts by mass) were added. Glycidyl methacrylate (Bremmer G, manufactured by NOF Corporation) (32 parts by mass) was added dropwise over 20 minutes. This was reacted at 100°C for 7 hours to obtain a solution containing resin A1. The solid content concentration of the obtained solution was 30.0% by mass. Using the synthesis method of resin A1 described above as a reference, a solution containing any of resins A2 to A4 was obtained. The solid content concentration of each obtained solution was 30.0% by mass.

[0296] <Synthesis of resin A5> 116.5 parts by mass of propylene glycol monomethyl ether acetate was placed in a three-necked flask and heated to 90°C under a nitrogen atmosphere. A solution containing 52.0 parts by mass of St, 29.0 parts by mass of MAA, 19.0 parts by mass of MMA, 10.0 parts by mass of V-601, and 116.5 parts by mass of propylene glycol monomethyl ether acetate was added dropwise to the flask solution, maintained at 90°C ± 2°C, over 2 hours. After the dropwise addition was complete, the solution in the flask was stirred at 90°C ± 2°C for 2 hours to obtain a solution containing resin A5. The solid content concentration of the obtained solution was 30.0% by mass.

[0297] <Synthesis of resin A6> 116.5 parts by mass of propylene glycol monomethyl ether acetate was placed in a three-necked flask and heated to 90°C under a nitrogen atmosphere. A solution containing 52.0 parts by mass of St, 29.0 parts by mass of MAA, 19.0 parts by mass of MMA, 4.0 parts by mass of V-601, and 116.5 parts by mass of propylene glycol monomethyl ether acetate was added dropwise to the flask solution, maintained at 95°C ± 2°C, over 6 hours. After the dropwise addition was complete, the solution in the flask was stirred at 95°C ± 2°C for 2 hours to obtain a solution containing resin A6. The solid content concentration of the obtained solution was 30.0% by mass.

[0298] The following shows resins A1 to A6.

[0299] [Table 1]

[0300] In Table 1, each entry has the following meaning: The constituent units other than GMA-MMA represent the monomers required to form each constituent unit. "GMA-MAA" represents a constituent unit in which glycidyl methacrylate is added to a constituent unit derived from methacrylic acid. Resins A1 to A6 are alkali-soluble resins. MAA: Methacrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) St: Styrene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) MMA: Methyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) BzMA: Benzyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) GMA-MMA: A structural unit in which glycidyl methacrylate is added to a structural unit derived from methacrylic acid. IBMA: Isobornyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) In the table, the "Polymerizable Groups" column indicates that if it is "A", the resin has polymerizable groups, and if it is "B", the resin does not have polymerizable groups. The "Tg[°C]" column indicates the glass transition temperature of the resin. The "Mw" column indicates the weight-average molecular weight of the resin. The numerical values ​​for the constituent units in the table indicate the mass ratio.

[0301] [Photosensitive composition] Each photosensitive composition was prepared using the components and formulations shown in Table 2 below. In Table 2, the values ​​listed in each component column represent the content (parts by mass) of each component. Note that, for resins, the content shown in the table refers to the content of the resin itself, and not the amount added to the solution containing each resin.

[0302] [Table 2]

[0303] <Resin> Resins A1 to A6 are as described above.

[0304] <Polymerizable compound> B1: BPE-900 (Ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) B2: BPE-500 (Ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) B3: BPE-100 (Ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) B4: Aronics M-270 (Polypropylene glycol diacrylate, manufactured by Toagosei Co., Ltd.) B5: A-NOD-N (1,9-nonanediol diacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) B6: A-DOD-N (1,10-decanediol diacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) The properties of polymerizable compounds are shown in the table below. In the table, the "Ethylene Oxy Group" column indicates that if it is "A", the polymerizable compound has an ethylene oxy group, and if it is "B", the polymerizable compound does not have an ethylene oxy group. The "Number of Functional Groups [units / molecule]" column indicates the number of functional groups contained per molecule of polymerizable compound. For example, polymerizable compound B1, which has 2 functional groups per molecule, is classified as a difunctional ethylenically unsaturated compound. The "Polymerizable Group Content [mmol / g]" column indicates the amount of polymerizable groups (mmol) contained per gram of polymerizable compound.

[0305] [Table 3]

[0306] <Polymerization initiator> B-CIM: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (manufactured by Hampford)

[0307] <Sensitizer> SB-PI 701: 4,4'-Bis(diethylamino)benzophenone (manufactured by Sanyo Trading Co., Ltd.)

[0308] <Dye> Leucocrystal violet (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0309] <Other additives> N-phenylcarbamoylmethyl-N-carboxymethylaniline (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) TDP-G: Phenothiazine (manufactured by Kawaguchi Chemical Industry Co., Ltd.) CBT-1: Carboxybenzotriazole (manufactured by Johoku Chemical Industry Co., Ltd.) 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone (manufactured by Fujifilm Wako Pure Chemical Industries) Megafuck F-552 (manufactured by DIC Corporation)

[0310] <Solvent> PGMEA: Propylene glycol monomethyl ether acetate (manufactured by Showa Denko Corporation) MEK: Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.) MFG: Propylene glycol monomethyl ether (manufactured by Nippon Emulsifier Co., Ltd.) MeOH: Methanol (manufactured by Mitsubishi Gas Chemical Company)

[0311] [Composition for forming intermediate layer] Intermediate layer-forming composition 1 was prepared using the following components. The various components of composition 1 for forming the intermediate layer are shown below. PVA: Polyvinyl alcohol, product name "Kuraray Poval PVA-205" (manufactured by Kuraray Co., Ltd.) PVP: Polypyrrolidone, product name "Polyvinylpyrrolidone K-30" (manufactured by Nippon Shokubai Co., Ltd.) HPMC: Hydroxypropyl methylcellulose, product name "Metrol 60SH-03" (manufactured by Shin-Etsu Chemical Co., Ltd.) Composition 1 for forming an intermediate layer was prepared by mixing PVA, PVP, and HPMC in a mixing ratio (mass ratio) of 67.5 / 31.5 / 1, and then adding a solvent (a mixed solvent prepared by mixing ion-exchanged water and methanol (manufactured by Mitsubishi Gas Chemical Co., Ltd.) in a mixing ratio (mass ratio) of 40 / 60).

[0312] [Transfer film] <Examples 1-11, Comparative Examples 1-2> Transfer films for Examples 1-11 and Comparative Examples 1-2 were prepared, consisting of a temporary support and a photosensitive composition layer, as shown in Table 4. Specifically, they were prepared as follows. First, the photosensitive compositions shown in Table 4 were applied to a temporary support (a 16 μm thick polyethylene terephthalate film (registered trademark Lumirror 16KS40, manufactured by Toray Industries, Inc.)) using a bar coater to a thickness of 3 μm after drying, and then dried in an oven at 80°C to form a negative-type photosensitive composition layer. A 16 μm thick layer of polyethylene terephthalate (registered trademark Lumirror 16KS40, manufactured by Toray Industries, Inc.) was pressed onto the obtained negative-type photosensitive composition layer to produce transfer films for Examples 1-11 and Comparative Examples 1-2.

[0313] <Examples 12-14> Transfer films were prepared, each consisting of a temporary support, an intermediate layer, and a photosensitive composition layer, to have the configuration shown in Table 4. Specifically, they were as follows: First, the intermediate layer-forming composition 1 for forming the intermediate layer was applied to a temporary support (a polyethylene terephthalate film (registered trademark Lumirror 16KS40, manufactured by Toray Industries, Inc.) with a thickness of 16 μm) using a bar coater so that the thickness after drying was 1.0 μm, and the intermediate layer was formed by drying it in an oven at 90°C. Furthermore, a photosensitive composition for forming the photosensitive composition layer shown in Table 4 was applied to the intermediate layer using a bar coater to a thickness of 3 μm after drying, and then dried in an oven at 80°C to form a negative-type photosensitive composition layer. A 16 μm thick layer of polyethylene terephthalate (registered trademark 16KS40, manufactured by Toray Industries, Inc.) was pressed onto the obtained negative-type photosensitive composition layer to produce the transfer films of Examples 12 to 14.

[0314] [Measurement and Evaluation] <Glass transition temperature> TgX and TgY were measured using the measurement method described above.

[0315] <Pattern shape (flared hem)> The protective film of the transfer film prepared as described above was peeled off, and the surface of the photosensitive composition layer opposite to the temporary support side was laminated onto a substrate having a conductive layer with Ni plating (thickness 100 nm) on glass (lamination conditions: substrate temperature 80°C, rubber roller temperature 110°C, linear pressure 3 N / cm, transport speed 2 m / min) to obtain a laminate. Next, the temporary support was peeled off the resulting laminate, and a photomask having a line (μm) / space (μm) pattern of 1 / 1 was brought into close contact with the surface of the photosensitive composition layer in the resulting laminate that was opposite the substrate side. 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 composition layer to 100 mJ / cm². 2 The images were exposed to light. Subsequently, a pattern was formed by shower development for 30 seconds using a sodium carbonate aqueous solution at a liquid temperature of 25°C. The cross-sectional shape of the obtained patterns was observed using a scanning electron microscope, and the length of the portion that extended beyond the top surface of the pattern (the side opposite to the substrate side) (the flared base portion 3 in Figure 1) was defined as the base length. The longest base length was used to evaluate the pattern shape according to the following evaluation criteria. A: Hem length is less than 0.20 μm B: Hem length is 0.20 μm or more, and less than 0.30 μm. C: Hem length is 0.30 μm or more and 0.40 μm or less. D: Hem length exceeds 0.40 μm

[0316] Table 4 shows the evaluation results. In Table 4, each entry is as follows: In the "Polymerizable Groups" column, if "A" indicates that the resin has polymerizable groups and the content of polymerizable structural units is 20.0% by mass or more of the total mass of the resin. If "B" indicates that the resin has polymerizable groups and the content of polymerizable structural units is greater than 0% by mass and less than 20.0% by mass of the total mass of the resin. If "C" indicates that the resin is not polymerizable. In the "Polymerizable group content of 2.4 mmol / g or more" column, "A" indicates that the polymerizable group content in the polymerizable compound is 2.4 mmol / g or more. "B" indicates that the polymerizable group content in the polymerizable compound is less than 2.4 mmol / g. Note that if multiple polymerizable compounds are present, "A" is used only if all polymerizable compounds contain 2.4 mmol / g or more. In the "Ethylene Oxy Group" column, "A" indicates that the polymerizable compound has an ethylene oxy group. "B" indicates that the polymerizable compound does not have an ethylene oxy group. Note that if multiple polymerizable compounds are included, "A" is used only if all polymerizable compounds have an ethylene oxy group. The "TgY-TgX" column shows the value obtained by subtracting the value of TgX (°C) from the value of TgY (°C). The "m / b" column indicates the mass ratio of the polymerizable compound content to the resin content (polymerizable compound content / resin content). The "Intermediate Layer" column indicates that if it is "A", the transfer film has an intermediate layer between the temporary support and the photosensitive composition layer. If it is "B", it indicates that the transfer film does not have an intermediate layer between the temporary support and the photosensitive composition layer.

[0317] [Table 4]

[0318] The results in Table 4 confirm that the manufacturing method for the laminate of the present invention results in superior pattern shape. It was confirmed that the effects of the present invention are superior when the difference between the glass transition temperature X and the glass transition temperature Y is 35 to 50°C (comparison of Example 1 and Example 2). It was confirmed that the effects of the present invention are superior when the glass transition temperature of the resin is 70-115°C (comparison of Example 1 and Examples 3-4). It was confirmed that the effects of the present invention are superior when the polymerizable group content in the polymerizable compound is 2.4 mmol / g or more (comparison of Example 1 and Example 5). It was confirmed that the effects of the present invention are superior when the polymerizable compound has an ethyleneoxy group (comparison of Example 1 and Example 6). It was confirmed that the effects of the present invention are superior when the photosensitive composition layer contains three or more polymerizable compounds (comparison of Example 1 and Example 7). It was confirmed that the effects of the present invention are superior when the resin has polymerizable groups, and that the effects of the present invention are even superior when the content of polymerizable structural units is 20.0 to 40.0% by mass relative to the total mass of the resin (comparison of Examples 1, 8 and 9). It was confirmed that the effects of the present invention are superior when the mass ratio of the polymerizable compound content to the resin content is 0.70 to 1.10 (comparison of Example 1 and Examples 10-11).

[0319] [Example 101] A copper-layered PET substrate was obtained by fabricating a 500 nm thick copper layer on a 50 μm thick PET film (polyethylene terephthalate film) using the sputtering method. The transfer film 1 prepared above was cut into 10 cm squares, the protective film was peeled off, and the removed transfer film 1 was laminated onto the copper-layered PET substrate under lamination conditions of roll temperature 90°C, linear pressure 0.8 MPa, and linear speed 3.0 m / min, so that the exposed photosensitive composition layer was in contact with the copper layer on the surface of the copper-layered PET substrate, thereby obtaining a laminate. At this point, the laminate has the following components in order: "PET film - copper layer - photosensitive composition layer - intermediate layer - temporary support". Next, the temporary support was peeled off the resulting laminate to expose the intermediate layer. A photomask having one of the following line (μm) / space (μm) patterns covering its entire surface was brought into close contact with the exposed intermediate layer. At this point, the laminate had the following components in the order of "PET film - copper layer - photosensitive composition layer - intermediate layer - photomask". The resulting laminate was irradiated with light from the photomask side using a high-pressure mercury lamp exposure machine (MA-1200A model, manufactured by Dainippon Kaken Co., Ltd., main wavelength: 365 nm, vacuum during exposure: -50 kPa). The exposure amount was set so that the resist pattern obtained after development reproduced the line and space shape of the photomask. Subsequently, development was performed using a 1.0% by mass aqueous solution of sodium carbonate at 28°C as the developer. Specifically, the development process involved showering for 30 seconds, then using an AirKnife to remove the developer, followed by showering with pure water for 30 seconds, and finally another AirKnife treatment. This resulted in a laminate having a line-and-space resist pattern with a line width:space width ratio of 1:1. At this point, the laminate had the following components in order: PET film - copper layer - resist pattern.

[0320] <Variation in line width> In the obtained laminate, the pattern at a total of 25 locations, namely the 20 intersections of the solid vertical lines and solid horizontal lines shown in Figure 3, was cut perpendicular to the length of the lines. The cross-sections of the pattern with a line (μm) / space (μm) of 2 μm / 2 μm were observed using a scanning optical microscope, and the width of each space was measured. The standard deviation of the measured space widths at the 25 points was calculated, and the variation in line width was evaluated according to the following criteria. A: Standard deviation is less than 0.20 μm B: Standard deviation is 0.20 μm or greater, and less than 0.50 μm. C: Standard deviation is 0.50 μm or greater.

[0321] [Examples 102-104] In Example 101, the line width variation was evaluated in the same manner as in Example 101, except that the exposure method of the laminate was changed as described below. Referring to the procedure for preparing the evaluation sample of the pattern shape described above, a laminate was prepared having the following components in the order of "cushion material - PET film - copper layer - photosensitive composition layer - intermediate layer - temporary support". The temporary support was peeled off the obtained laminate to expose the intermediate layer. A photomask having one of the following patterns with line (μm) / space (μm) values: 1 / 1, 2 / 2, 3 / 3, 4 / 4, 5 / 5, 6 / 6, 7 / 7, 8 / 8, 9 / 9, and 10 / 10 was brought into close contact with the exposed intermediate layer. At this point, the laminate had the following components in the order of "cushion material - PET film - copper layer - photosensitive composition layer - intermediate layer - photomask". Next, light was irradiated from the photomask side using a high-pressure mercury lamp exposure machine (MA-1200A model, manufactured by Dainippon Kaken Co., Ltd., main wavelength: 365 nm, vacuum during exposure: -50 kPa).

[0322] <Cushioning material> • Cushioning material 1: Silicone rubber sheet (1mm thick) • Cushioning material 2: Silicone rubber sheet (1mm thick) • Cushioning material 3: Urethane rubber sheet (1mm thick) The hardness of each cushioning material is indicated by Type A durometer hardness.

[0323] Table 5 shows the evaluation results.

[0324] [Table 5]

[0325] The results in Table 5 confirm that when the laminate has a cushioning material during exposure (especially when the cushioning material is on the surface opposite to the photosensitive composition layer of the substrate), the adhesion between the photomask and the intermediate layer is improved, and the uniformity of the resist pattern line width is improved. It was confirmed that when the hardness of the cushioning material is 70 or higher, the variation in line width is better. [Explanation of Symbols]

[0326] 1 circuit board 2 patterns 3. Flared hem 10 Transfer film 11 Temporary support 13. Middle Class 15 Photosensitive composition layer 17 Composition layer 19 Protective film 20 Intersections< / tgy> < / tgx>

Claims

1. A bonding step is performed by bringing the surface of the photosensitive composition layer of a transfer film, which has a temporary support and a photosensitive composition layer, on the side opposite to the temporary support, into contact with a substrate, thereby bonding the transfer film and the substrate. An exposure step of pattern exposure of the photosensitive composition layer, The process includes a developing step in which the exposed photosensitive composition layer is developed using a developing solution to form a pattern, A method for manufacturing a laminate, wherein the glass transition temperature X of the photosensitive composition layer is 110°C or less, and the glass transition temperature Y determined by measurement Y is 125°C or more, The photosensitive composition layer comprises a resin and a polymerizable compound. The glass transition temperature of the resin is 60 to 118°C. The mass ratio of the polymerizable compound content to the resin content is 0.50 to 1.

50. A method for producing a laminate, wherein the polymerizable compound contains 1.0 mmol / g or more of polymerizable groups. Measurement Y: The surface of the photosensitive composition layer of the transfer film opposite to the temporary support side is brought into contact with the substrate, the transfer film and the substrate are bonded together, the temporary support is peeled off from the resulting laminate, the photosensitive composition layer in the laminate from which the temporary support was peeled off is fully exposed under the same exposure conditions as in the exposure step, and then the glass transition temperature of the resulting cured film is measured and defined as the glass transition temperature Y.

2. The method for manufacturing a laminate according to claim 1, wherein the difference between the glass transition temperature X and the glass transition temperature Y is 35 to 50°C.

3. The method for manufacturing a laminate according to claim 1 or 2, wherein the glass transition temperature of the resin is 70 to 115°C.

4. A method for producing a laminate according to any one of claims 1 to 3, wherein the resin has polymerizable groups.

5. A method for producing a laminate according to any one of claims 3 to 4, wherein the content of polymerizable groups in the polymerizable compound is 2.4 mmol / g or more.

6. A method for producing a laminate according to any one of claims 1 to 5, wherein the polymerizable compound has an ethyleneoxy group.

7. A method for producing a laminate according to any one of claims 1 to 6, wherein the photosensitive composition layer comprises three or more polymerizable compounds.

8. A method for producing a laminate according to any one of claims 1 to 7, wherein the mass ratio of the content of the polymerizable compound to the content of the resin is 0.70 to 1.

10.

9. The method for manufacturing a laminate according to any one of claims 1 to 8, wherein the transfer film further has an intermediate layer between the temporary support and the photosensitive composition layer.

10. The method for manufacturing a laminate according to claim 9, wherein the intermediate layer contains a water-soluble resin.

11. The method for producing a laminate according to claim 9 or 10, wherein the intermediate layer comprises at least one selected from the group consisting of water-soluble cellulose derivatives, polyhydric alcohols, oxide adducts of polyhydric alcohols, polyether resins, phenol derivatives, and amide compounds.

12. Between the lamination step and the exposure step, there is further a peeling step of peeling the temporary support from the laminate of the transfer film and the substrate, The method for manufacturing a laminate according to any one of claims 1 to 11, wherein the exposure step is an exposure step of pattern-exposing the photosensitive composition layer of the laminate from which the temporary support obtained in the peeling step has been peeled off, via a photomask.

13. Between the lamination step and the exposure step, there is further a peeling step of peeling the temporary support from the laminate of the transfer film and the substrate, The method for manufacturing a laminate according to any one of claims 1 to 11, wherein the exposure step is an exposure step in which the surface of the laminate from which the temporary support obtained in the peeling step has been peeled off is brought into contact with a photomask and the photosensitive composition layer is pattern-exposed.

14. Between the exposure step and the development step, there is further a peeling step of peeling the temporary support from the laminate of the transfer film and the substrate, The method for manufacturing a laminate according to any one of claims 1 to 11, wherein the exposure step is an exposure step of pattern-exposing the photosensitive composition layer of the laminate through a photomask.

15. The method for manufacturing a laminate according to any one of claims 12 to 14, wherein the photomask includes light-shielding portions arranged in a mesh-like manner.

16. The method for manufacturing a laminate according to any one of claims 12 to 14, wherein the photomask includes light-shielding portions arranged in a circular dot pattern.

17. The method for manufacturing a laminate according to any one of claims 12 to 14, wherein the photomask includes openings arranged in a circular dot pattern.

18. A seed layer formation step in which a seed layer is formed on a substrate to form a substrate with a seed layer, A lamination step in which the surface of the photosensitive composition layer opposite to the temporary support side is brought into contact with the seed layer of the substrate with the seed layer, and the transfer film and the substrate with the seed layer are laminated to obtain a substrate with a photosensitive composition layer having the substrate, the seed layer, the photosensitive composition layer and the temporary support in this order, A peeling step of peeling the temporary support from the substrate with the photosensitive composition layer, An exposure step in which the photosensitive composition layer is pattern-exposed by bringing the surface of the substrate with the photosensitive composition layer, from which the temporary support has been peeled off, on the side opposite to the substrate side, into contact with a photomask, A developing step in which the exposed photosensitive composition layer is developed using a developer to form a pattern, A metal plating layer formation step, in which a metal plating layer is formed on the seed layer in an area where the aforementioned pattern is not arranged by a plating process, A protective layer formation step of forming a protective layer on the metal plating layer, A removal step to remove the aforementioned pattern, The process includes a seed layer removal step of removing the exposed seed layer to obtain a conductive nanowire, A method for manufacturing circuit wiring, wherein the glass transition temperature X of the photosensitive composition layer is 110°C or less, and the glass transition temperature Y determined by measurement Y is 125°C or more, The photosensitive composition layer comprises a resin and a polymerizable compound. The glass transition temperature of the resin is 60 to 118°C. The mass ratio of the polymerizable compound content to the resin content is 0.50 to 1.

50. A method for manufacturing circuit wiring, wherein the polymerizable compound contains 1.0 mmol / g or more of polymerizable groups. Measurement Y: The surface of the photosensitive composition layer of the transfer film opposite to the temporary support side is brought into contact with the substrate, the transfer film and the substrate are bonded together, the temporary support is peeled off from the resulting laminate, the photosensitive composition layer in the laminate from which the temporary support was peeled off is fully exposed under the same exposure conditions as in the exposure step, and then the glass transition temperature of the resulting cured film is measured and defined as the glass transition temperature Y.

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