Method for manufacturing a laminate having a conductive pattern and transfer film

Abstract

To provide a method for manufacturing a laminate having a conductive pattern that, when plated, is more likely to form a finer conductive pattern with suppressed shape defects. [Solution] A method for manufacturing a laminate having a conductive pattern, comprising the steps of: laminating a transfer film having a temporary support and a photosensitive composition layer to a substrate; pattern exposing the photosensitive composition layer; performing a development process to form a resist pattern; performing a plating process; peeling off the resist pattern; removing the exposed metal layer to form a conductive pattern; and peeling off the temporary support, wherein the photosensitive composition layer contains a resin having crosslinkable groups, the weight-average molecular weight of the resin is 3000 or more, and the mass ratio of polymerizable compounds other than the resin contained in the photosensitive composition layer to the resin is 0.85 or less.

Description

[Technical Field]

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

[0002] Because it requires fewer steps to obtain a predetermined pattern, a method is widely used in which a photosensitive composition layer is placed on any substrate using a transfer film, and then the photosensitive composition layer is exposed to pattern exposure and developed. The resulting pattern can also be used as a resist pattern for pattern plating on areas not covered by the pattern.

[0003] For example, Patent Document 1 discloses a photosensitive resin composition containing an alkali-soluble polymer, a compound having an ethylenically unsaturated double bond, a photopolymerization initiator, a sensitizer, and an additive in a predetermined mass ratio, and also discloses a photosensitive resin laminate (transfer film) using the above photosensitive resin composition. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2016-139154 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] With the miniaturization and increased density of electronic devices, conductive patterns such as wiring patterns are becoming finer, and there is a great demand for finer resist patterns for plating.

[0006] The inventors examined the transfer film described in Patent Document 1 and formed a conductive pattern. They observed distortion and meandering in the fine line sections, as well as the formation of conductive areas in unwanted parts, in the resulting conductive pattern. They found that the pattern could not be obtained as designed and that improvements were necessary.

[0007] Therefore, the present invention aims to provide a method for manufacturing a laminate having a conductive pattern in which a finer conductive pattern with suppressed shape defects is more easily formed when a plating treatment is performed. Furthermore, the present invention also aims to provide a transfer film. [Means for solving the problem]

[0008] The inventors of this invention have diligently studied and developed the present invention to solve the above problems. Specifically, they have found that the above problems can be solved by the following configuration.

[0009] [1] A bonding step of bonding the transfer film and the substrate such that the surface of the transfer film having a temporary support and a photosensitive composition layer is in contact with the metal layer of the substrate having a metal layer on its surface, An exposure step of pattern exposure of the above photosensitive composition layer, A developing step is performed on the exposed photosensitive composition layer to form a resist pattern, A plating process is performed on the metal layer in the region where the above resist pattern is not placed, A peeling step to remove the above-mentioned resist pattern, The process includes removing the metal layer exposed by the above peeling process and forming a conductive pattern on the substrate, A method for manufacturing a laminate having a conductive pattern, comprising a temporary support peeling step for peeling off the temporary support between the bonding step and the exposure step, or between the exposure step and the development step, The above photosensitive composition layer contains a resin having a crosslinkable group, The weight-average molecular weight of the above resin is 3000 or more. A method for manufacturing a laminate having a conductor pattern, wherein the mass ratio of the polymerizable compound other than the resin contained in the photosensitive composition layer to the resin is 0.85 or less. 〔2〕 The method for manufacturing a laminate having a conductor pattern according to 〔1〕, wherein the total double bond content in the photosensitive composition layer is greater than 1.00 mmol / g with respect to the total mass of the photosensitive composition layer. 〔3〕 The method for manufacturing a laminate having a conductor pattern according to 〔1〕 or 〔2〕, wherein the double bond content derived from the resin is greater than 0.20 mmol / g with respect to the total mass of the photosensitive composition layer. 〔4〕 The method for manufacturing a laminate having a conductor pattern according to any one of 〔1〕 to 〔3〕, wherein the double bond content derived from the resin is greater than 1.00 mmol / g with respect to the total mass of the photosensitive composition layer. 〔5〕 The method for manufacturing a laminate having a conductor pattern according to any one of 〔1〕 to 〔4〕, wherein the glass transition temperature of the photosensitive composition layer after exposure with i-line at an exposure dose of 20 mJ / cm 2 is 30 °C or higher. 〔6〕 The method for manufacturing a laminate having a pattern according to any one of 〔1〕 to 〔5〕, wherein the glass transition temperature of the film composed only of the resin is 50 °C or higher. 〔7〕 The resin contains a structural unit having a group having a double bond, and the content of the structural unit is 10% by mass or more with respect to the total mass of the resin. The method for manufacturing a laminate having a conductor pattern according to any one of 〔1〕 to 〔6〕. 〔8〕 The method for manufacturing a laminate having a conductor pattern according to any one of 〔1〕 to 〔7〕, wherein the resin contains a structural unit derived from a monomer having an alicyclic structure or a polycyclic structure. 〔9〕 The method for manufacturing a laminate having a conductor pattern according to any one of 〔1〕 to 〔8〕, wherein the resin contains a structural unit derived from a (meth)acrylate monomer having a hydrocarbon group with 9 or more carbon atoms. 〔10〕 The method for manufacturing a laminate having a conductor pattern according to 〔9〕, wherein the hydrocarbon group has a branched chain. 〔11〕The method for manufacturing a laminate having a conductor pattern according to any one of 〔1〕 to 〔10〕, wherein the transfer film has an intermediate layer between the temporary support and the photosensitive composition layer. 〔12〕The method for manufacturing a laminate having a conductor pattern according to any one of 〔1〕 to 〔11〕, wherein the exposure step is a step of pattern exposure through a photomask. 〔13〕The method for manufacturing a laminate having a conductor pattern according to any one of 〔1〕 to 〔11〕, wherein the exposure step is a step of pattern exposure of the photosensitive composition layer through a lens using actinic rays having an image of the photomask projected thereon. 〔14〕The method has a temporary support peeling step between the bonding step and the exposure step, The method for manufacturing a laminate having a conductor pattern according to any one of 〔1〕 to 〔12〕, wherein the exposure step is a step of performing pattern exposure by bringing the surface exposed by peeling the temporary support into contact with the photomask. 〔15〕A transfer film having a temporary support and a photosensitive composition layer, wherein the photosensitive composition layer contains a resin having a crosslinkable group, the weight average molecular weight of the resin is 3000 or more, the mass ratio of the polymerizable compound other than the resin contained in the photosensitive composition layer to the resin is 0.85 or less, and the haze of the temporary support is 1.0% or less. 〔16〕The double bond content derived from the resin is greater than 0.55 mmol / g with respect to the total mass of the photosensitive composition layer, and the resin contains a structural unit derived from a monomer having an alicyclic structure or a polycyclic structure. 〔17〕The double bond content derived from the resin is greater than 0.55 mmol / g with respect to the total mass of the photosensitive composition layer, and the resin contains a structural unit derived from a (meth)acrylate monomer having a hydrocarbon group with 9 or more carbon atoms.

[18] The transfer film according to

[17] , wherein the hydrocarbon group has a branched chain.

[19] A transfer film according to any one of

[15] to

[18] , wherein the weight-average molecular weight of the resin is 3,000 to 18,000.

[20] A transfer film according to any one of

[15] to

[19] , wherein the thickness of the above-mentioned temporary support is 50 μm or less.

[21] The above photosensitive composition layer further contains a sensitizer, A transfer film according to any one of

[15] to

[20] , wherein the sensitizer is selected from the group consisting of distylylbenzene derivatives, styrylpyridine derivatives, and anthracene derivatives.

[22] The above photosensitive composition layer further comprises a polymerizable compound, The transfer film according to any one of

[15] to

[21] , wherein the polymerizable compound contains an alkylene oxide-modified bisphenol structure.

[23] A transfer film according to any one of

[15] to

[22] , having an intermediate layer between the temporary support and the photosensitive composition layer.

[24] The transfer film according to

[23] , wherein the intermediate layer is a water-soluble resin layer.

[25] A transfer film having the above-mentioned temporary support, the above-mentioned photosensitive composition layer, and a protective film in this order, A transfer film according to any one of

[15] to

[24] , wherein the arithmetic mean roughness Ra of the surface opposite to the surface of the protective film that is in contact with the photosensitive composition layer is 0.05 μm or more.

[26] A transfer film having the above-mentioned temporary support, the above-mentioned photosensitive composition layer, and a protective film in this order, The transfer film described in any one of

[15] to

[25] , wherein the protective film is a polypropylene film. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a method for manufacturing a laminate having a conductive pattern in which a conductive pattern of a desired shape can be easily formed. Furthermore, according to the present invention, a transfer film can be provided. [Brief explanation of the drawing]

[0011] [Figure 1] This is a schematic diagram showing an example of the configuration of a transfer film used in the manufacturing method of the present invention. [Modes for carrying out the invention]

[0012] The present invention will be described in detail below. The following description of the constituent elements may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

[0013] The following definitions are used in this specification. In this specification, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. In this specification, in numerical ranges described in stages, the upper or lower limit stated in one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in numerical ranges described in this specification, the upper or lower limit stated in one numerical range may be replaced with the values ​​shown in the examples.

[0014] In this specification, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes, as long as their intended purpose is achieved.

[0015] In this specification, "transparent" means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more, and preferably 90% or more. In this specification, the average transmittance of visible light is a value measured using a spectrophotometer, which can be measured using, for example, a Hitachi U-3310 spectrophotometer manufactured by Hitachi, Ltd.

[0016] In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are calculated using polystyrene as the standard substance, measured by a gel permeation chromatography (GPC) analyzer using TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all product names of Tosoh Corporation) as the column, THF (tetrahydrofuran) as the eluent, a differential refractometer as the detector, and polystyrene as the standard substance. In this specification, unless otherwise specified, the molecular weight of a compound with a molecular weight distribution is the weight-average molecular weight (Mw). In this specification, unless otherwise specified, the content of metallic elements is measured using an inductively coupled plasma (ICP) spectrometer. In this specification, unless otherwise specified, the refractive index is the value measured using an ellipsometer at a wavelength of 550 nm. In this specification, unless otherwise specified, hue values ​​are those measured using a colorimeter (CR-221, manufactured by Minolta, Inc.).

[0017] In this specification, "(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.

[0018] In this specification, "alkaline soluble" means that the solubility of sodium carbonate in 100 g of a 1% by mass aqueous solution at 22°C is 0.1 g or more.

[0019] In this specification, "water-soluble" means that the solubility in 100g of water at a pH of 7.0 at a liquid temperature of 22°C is 0.1g or more. Therefore, for example, a water-soluble resin refers to a resin that satisfies the above-mentioned solubility conditions.

[0020] In this specification, "solids" of a composition means the components that form the composition layer formed using the composition, and if the composition contains a solvent (organic solvent, water, etc.), it means all components excluding the solvent. Furthermore, any liquid components that form the composition layer are also considered to be solids.

[0021] <Method for manufacturing a laminate having a conductive pattern> The method for manufacturing a laminate having a conductive pattern of the present invention is: A lamination step in which a transfer film having a temporary support and a photosensitive composition layer is bonded to a substrate such that the surface of the transfer film opposite to the temporary support is in contact with the metal layer of the substrate having a metal layer on its surface, An exposure step in which a photosensitive composition layer is pattern-exposed, A developing step involves performing a developing process on an exposed photosensitive composition layer to form a resist pattern, A plating process in which a metal layer in an area where a resist pattern is not placed is plated, A peeling process to remove the resist pattern, The process includes a removal step to remove the metal layer exposed by the peeling step and to form a conductive pattern on the substrate, The conductive pattern has a temporary support peeling step, which peels off the temporary support between the bonding step and the exposure step, or between the exposure step and the development step. The distinguishing feature of the present invention is that the photosensitive composition layer of the transfer film contains a resin having crosslinkable groups, the weight-average molecular weight of the resin is 3000 or more, and the mass ratio of polymerizable compounds other than the resin contained in the photosensitive composition layer to the resin is 0.85 or less.

[0022] The mechanism by which a desired conductor pattern can be obtained when a plating treatment is performed using the manufacturing method for the laminate having the above conductor pattern is not entirely clear, but the inventors speculate as follows. Because the photosensitive composition layer of the transfer film has the above-mentioned characteristics, the plating solution used in the plating process is less likely to penetrate the formed resist pattern, and even if it does penetrate, the resist pattern is less likely to swell. As a result, distortion and meandering of fine lines are less likely to occur. Furthermore, due to the above-mentioned characteristics of the photosensitive composition layer, the formed resist pattern is less likely to peel off during the plating process, and as a result, the formation of conductive areas in unwanted areas is less likely to occur.

[0023] The method for manufacturing a laminate having a conductive pattern according to the present invention will be described below. The transfer film will be described in detail later. Furthermore, the ease with which a desired conductor pattern can be obtained after plating is also referred to as "excellent conductor pattern formation properties."

[0024] [Lamination process] The lamination process involves bonding a transfer film, which has a temporary support and a photosensitive composition layer, to a substrate such that the surface of the transfer film opposite to the temporary support is in contact with the metal layer of the substrate, which has a metal layer on its surface. By performing the lamination process, a substrate with a photosensitive composition layer is obtained, having the substrate, metal layer, photosensitive composition layer, and temporary support in this order. Furthermore, if the transfer film described later has a protective film, the protective film should be removed before performing the lamination process.

[0025] A substrate having a metal layer on its surface (a substrate with a metal layer) comprises a substrate and a metal layer disposed on the surface of the substrate. A substrate with a metal layer may have any other layer formed on it besides the metal layer, as needed. In other words, it is preferable that a substrate with a metal layer comprises at least a substrate and a metal layer disposed on the surface of the substrate. Examples of substrates include resin substrates, glass substrates, ceramic substrates, and semiconductor substrates, with the substrate described in paragraph

[0140] of International Publication No. 2018 / 155193 being preferred. As the material for the resin substrate, polyethylene terephthalate, cycloolefin polymer, or polyimide are preferred. The thickness of the resin substrate is preferably 5 to 200 μm, and more preferably 10 to 100 μm.

[0026] The metal layer is a layer containing metal, and there are no particular restrictions on the metal; known metals can be used. Preferably, the metal layer is a conductive layer. Examples of the main components (so-called primary metals) of the metal layer include copper, chromium, lead, nickel, gold, silver, tin, and zinc. Note that "primary component" refers to the metal present in the largest quantity among the metals contained in the metal layer.

[0027] The method for forming the metal layer is not particularly limited, and known methods include, for example, a method of applying a dispersion of metal nanoparticles and sintering the coating film, sputtering, and vapor deposition.

[0028] The thickness of the metal layer is not particularly limited, but is preferably 50 nm or more, and more preferably 100 nm or more. The upper limit is preferably 10 μm or less, and more preferably 2 μm or less.

[0029] One or more metal layers may be placed on the substrate. When arranging two or more metal layers, the metal layers arranged may be the same or different, but it is preferable that they be metal layers of different materials.

[0030] In the above bonding process, it is preferable to bring the photosensitive composition layer side of the transfer film (the surface opposite to the temporary support side) into contact with the metal layer on the substrate and press it down. There are no particular restrictions on the method of pressing as described above, and known transfer methods and lamination methods can be used. In particular, it is preferable to place the surface of the photosensitive composition layer on a substrate having a conductive part and apply pressure and heat using a roll or the like. For lamination, known laminators such as vacuum laminators and auto-cut laminators can be used. The lamination temperature is not particularly limited, but it is preferably, for example, 70 to 130°C.

[0031] [Synthesis process] The exposure process involves pattern exposure of the photosensitive composition layer. By performing an exposure process and a development process described later, a resist pattern is formed on the metal layer on the substrate, protecting at least a portion of the metal layer. "Pattern exposure" refers to a method of exposure that involves a pattern of exposure, resulting in a form of exposure where exposed and unexposed areas exist. The positional relationship between the exposed area (exposed region) and the unexposed area (unexposed region) in pattern exposure can be adjusted as appropriate. Exposure is preferably performed from the photosensitive composition layer side.

[0032] Examples of exposure methods in the exposure process include mask exposure, direct imaging exposure, and projection exposure, with mask exposure or projection exposure being preferred. In other words, the exposure process is preferably one in which exposure is performed through a photomask. Furthermore, the exposure process may also involve using an active light beam onto which the image of the photomask is projected, and exposing the photosensitive composition layer through a lens.

[0033] If a temporary support peeling step, described later, is performed between the lamination step and the exposure step, the exposure step is preferably one in which the surface of the laminate from which the temporary support obtained in the temporary support peeling step was peeled, opposite to the substrate side, is brought into contact with the photomask, and a pattern is exposed. In other words, the exposure step is preferably one in which the exposed surface of the laminate from which the temporary support was peeled, exposed by the peeling of the temporary support, is brought into contact with the photomask, and a pattern is exposed on the photosensitive composition layer. Note that, if the transfer film described later has a three-layer structure consisting of a temporary support, an intermediate layer, and a photosensitive composition layer, the exposed surface refers to the surface of the intermediate layer. By employing such an exposure process, a higher-resolution resist pattern can be obtained, and ultimately, a higher-resolution conductive pattern can be obtained. Such an exposure process is particularly preferable when a temporary support peeling process, described later, is performed between the lamination process and the exposure process. Furthermore, if a temporary support peeling step, described later, is performed between the exposure step and the development step, the exposure step is preferably one in which the photomask is brought into contact with the surface of the transfer film opposite to the side containing the substrate in the laminate of the substrate and transfer film obtained by the lamination step, and a pattern is exposed.

[0034] In the exposure process for pattern exposure, a curing reaction of 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, a development process is performed to remove the unexposed region of the photosensitive composition layer, forming a resist pattern.

[0035] The method of the present invention may also preferably include a photomask peeling step between the exposure step and the development step, in which the photomask used in the exposure step is peeled off. Examples of photomask peeling processes include known peeling processes.

[0036] As a light source for pattern exposure, any light source capable of irradiating with light in a wavelength range sufficient to cure the photosensitive composition layer (for example, 365 nm or 405 nm) can be appropriately selected and used. Among these, 365 nm is preferred as the dominant wavelength of the exposure light for pattern exposure. The dominant wavelength is 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.

[0038] Preferred embodiments of the light source, exposure amount, and exposure method used for exposure are described, for example, in paragraphs

[0146] to

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

[0039] [Temporary support removal process] The temporary support peeling step is a step of peeling the temporary support from the substrate with the photosensitive composition layer, which takes place between the bonding step and the exposure step, or between the exposure step and the development step described later. The peeling method is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs

[0161] to

[0162] of Japanese Patent Application Publication No. 2010-072589 can be used.

[0040] [Development process] The development process involves performing a development treatment on the exposed photosensitive composition layer to form a resist pattern. The above photosensitive composition layer can be developed using a developing solution. An alkaline aqueous solution is preferred as the developing solution. Examples of alkaline compounds that may be included in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0041] The temperature of the developing solution during the developing process is preferably 10 to 50°C, more preferably 15 to 40°C, and even more preferably 20 to 35°C. The pH of the developer solution used in the developing process is preferably 9 or higher, more preferably 10 or higher, and even more preferably 11 or higher. The upper limit is preferably 14 or lower, and more preferably less than 13. The pH can be measured using a known pH meter in accordance with the method specified in JIS Z8802-1984. The temperature for pH measurement is 25°C.

[0042] The water content in the developer is preferably 50% by mass or more and less than 100% by mass, and more preferably 90% by mass or more and less than 100% by mass, relative to the total mass of the developer. The content of alkaline compounds in the developer is preferably 0.01 to 20% by mass, and more preferably 0.1 to 10% by mass, relative to the total mass of the developer.

[0043] Examples of development methods include paddle development, shower development, spin development, and dip development.

[0044] Examples of developers preferred in this specification include the developer described in paragraph

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

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

[0045] After development, it is also preferable to perform a rinsing process to remove any remaining developer from the metal-layered substrate before proceeding to the next step. Water or the like can be used for the rinsing process. After developing and / or rinsing, a drying process may be performed to remove any excess liquid from the substrate with the metal layer.

[0046] The position and size of the resist pattern formed on the metal layer substrate are not particularly limited, but it is preferable that it includes a fine line shape. Specifically, the line width of the resist pattern is preferably 20 μm or less, more preferably 15 μm or less, even more preferably 10 μm or less, and particularly preferably 5 μm or less. The lower limit is often 1.0 μm or more.

[0047] [Plating process] The plating process is a process of applying a plating treatment to the metal layer in areas where a resist pattern is not present. More specifically, the above plating process is a process of forming a plating layer on a metal layer in an area where a resist pattern is not placed (a metal layer exposed on the surface by the developing process) by a plating treatment. Examples of plating methods include electrolytic plating and electroless plating, and electrolytic plating is preferred from the viewpoint of productivity. When the plating process is performed, a plating layer is obtained on the metal layer substrate that has a pattern shape similar to the areas where the resist pattern is not placed (openings in the resist pattern).

[0048] Examples of metals included in the plating layer include well-known metals. Specifically, these include metals such as copper, chromium, lead, nickel, gold, silver, tin, and zinc, as well as alloys of these metals. In particular, the plating layer preferably contains copper or an alloy thereof, as this provides superior conductivity of the conductive pattern. Furthermore, the plating layer preferably contains copper as its main component, as this provides superior conductivity of the conductive pattern.

[0049] The thickness of the 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.

[0050] [Peeling process] The stripping process is the process of removing any remaining resist pattern. There are no particular limitations on the method for removing the remaining resist pattern, but one method is to remove it by chemical treatment, and a method using a stripping solution is preferred. Alternatively, the material may be removed using a stripping solution by known methods such as the spray method, shower method, and paddle method.

[0051] Examples of stripping solutions include those obtained by dissolving an inorganic or organic alkaline component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixture thereof. Examples of inorganic alkaline components include sodium hydroxide and potassium hydroxide. Examples of organic alkaline components include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds. Tetramethylammonium hydroxide or alkanolamine compounds are preferred as alkaline organic compounds. It is also preferable that the stripping solution does not dissolve the metal layer.

[0052] A method for removing the resist pattern involves immersing a substrate having the remaining resist pattern in a stirring stripping solution, preferably at a liquid temperature of 30 to 80°C, more preferably 50 to 80°C, for 1 to 30 minutes.

[0053] The pH of the stripping solution used in the stripping process is preferably 11 or higher, more preferably 12 or higher, and even more preferably 13 or higher. The upper limit is preferably 14 or lower, and more preferably 13.8 or lower. The pH can be measured using a known pH meter in accordance with the method compliant with JIS Z8802-1984. The temperature for pH measurement is 25°C. The temperature of the stripping solution used during the stripping process is preferably higher than the temperature of the developing solution used during the developing process. Specifically, the value obtained by subtracting the temperature of the developing solution from the temperature of the stripping solution (temperature of the stripping solution - temperature of the developing solution) is preferably 10°C or higher, and more preferably 20°C or higher. The upper limit is preferably 100°C or lower, and more preferably 80°C or lower. The pH of the stripping solution used in the stripping process is preferably higher than the pH of the developing solution used in the developing process. Specifically, the value obtained by subtracting the pH of the developing solution from the pH of the stripping solution (pH of the stripping solution - pH of the developing solution) is preferably 1 or higher, and more preferably 1.5 or higher. The upper limit is preferably 5 or lower, and more preferably 4 or lower.

[0054] After removing the resist pattern with a stripping solution, it is also preferable to perform a rinsing process to remove any remaining stripping solution from the substrate. Water or the like can be used for the rinsing process. After stripping the resist pattern with a stripping solution and / or rinsing, a drying process may be performed to remove any excess solution from the substrate.

[0055] [Removal process] The removal process involves removing the metal layer exposed by the peeling process and forming a conductive pattern on the substrate. In the removal process, the plating layer formed by the plating process is used as an etching resist to etch the metal layer located in the non-pattern formation region (in other words, the region not protected by the plating layer).

[0056] There are no particular limitations on the method for removing a portion of the metal layer, but it is preferable to use a known etching solution. Examples of known etching solutions include ferric chloride solution, cupric chloride solution, ammonia alkali solution, sulfuric acid-hydrogen peroxide mixture, and phosphoric acid-hydrogen peroxide mixture.

[0057] When the removal process is performed, the metal layer exposed on the surface of the substrate is removed, while the plated layer (conductor pattern) with a pattern shape remains, resulting in a laminate having a conductor pattern.

[0058] The upper limit of the line width of the formed conductor pattern is preferably 8 μm or less, and more preferably 6 μm or less. There is no particular limit on the lower limit, but it is often 1 μm or more.

[0059] [Other processes] The method for manufacturing a laminate having a conductive pattern may include any steps other than those described above (other steps). Examples include, but are not limited to, the steps described in paragraph

[0172] of International Publication No. 2019 / 022089 for reducing the visible light reflectance, and the steps described in paragraph

[0172] of International Publication No. 2019 / 022089 for forming a new metal layer on an insulating film.

[0060] (A process to reduce the reflectance of visible light) A method for manufacturing a laminate having a conductive pattern may include a step of performing a treatment to reduce the visible light reflectance of some or all of the multiple metal layers having a substrate. One treatment that reduces visible light reflectivity is oxidation. If the substrate has a metal layer containing copper, the copper can be oxidized to copper oxide, which blackens the metal layer and reduces its visible light reflectivity. Treatments for reducing visible light reflectance are described in paragraphs

[0017] to

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

[0041] ,

[0042] ,

[0048] and

[0058] of Japanese Patent Publication No. 2013-206315, and the contents described in these publications are incorporated herein by reference.

[0061] (Steps to form an insulating film, steps to form a new conductive layer on the surface of the insulating film) A method for manufacturing a laminate having a conductor pattern may also preferably include the steps of forming an insulating film on the surface of the circuit wiring and forming a new conductive layer on the surface of the insulating film. Through the above process, a second electrode pattern insulated from the first electrode pattern can be formed. The process for forming the insulating film is not particularly limited and includes known methods for forming permanent films. Alternatively, an insulating film with a desired pattern may be formed by photolithography using an insulating photosensitive material. The process of forming a new conductive layer on an insulating film is not particularly limited, and for example, a new conductive layer with a desired pattern may be formed by photolithography using a conductive photosensitive material.

[0062] In the manufacturing method of a laminate having a conductive pattern, it is preferable to use a substrate having multiple metal layers on both surfaces of the substrate, and to form circuits sequentially or simultaneously on the metal layers formed on both surfaces of the substrate. With such a configuration, it is possible to form a touch panel circuit wiring in which a first conductive pattern is formed on one surface of the substrate and a second conductive pattern is formed on the other surface. It is also preferable to form such a touch panel circuit wiring from both sides of the substrate using a roll-to-roll method.

[0063] <Applications of laminates with conductive patterns> The method for manufacturing laminates having conductive patterns can be applied to the production of conductive films such as touch panels, transparent heaters, transparent antennas, electromagnetic shielding materials, and dimmable films; the production of printed circuit boards and semiconductor packages; the production of pillars and pins for interconnects between semiconductor chips and packages; the production of metal masks; the production of tape substrates such as COF (Chip on Film) and TAB (Tape Automated Bonding); and the like. Furthermore, the above-mentioned touch panel can be a capacitive touch panel. The method for manufacturing the laminate according to the present invention can be used to form conductive films and peripheral circuit wiring in the touch panel. The above-mentioned touch panel can be applied to display devices such as organic EL (electro-luminescence) display devices and liquid crystal display devices.

[0064] <Transfer film> The transfer film used in the method for manufacturing a laminate having a conductive pattern of the present invention comprises a temporary support and a photosensitive composition layer, wherein the photosensitive composition layer contains a resin having crosslinkable groups, the weight-average molecular weight of the resin is 5000 or more, and the mass ratio of polymerizable compounds other than the resin contained in the photosensitive composition layer to the resin is 0.85 or less. The transfer film may have other layers besides the temporary support and the photosensitive composition layer. Other layers include, for example, the intermediate layer described later. The transfer film may also have other components (for example, a protective film, etc.) described later.

[0065] Examples of the transfer film include the following configurations (1) or (2), with configuration (2) being preferred. (1) "Temporary support / photosensitive composition layer / protective film" (2) "Temporary support / intermediate layer / photosensitive composition layer / protective film" The transfer film preferably has an intermediate layer. 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.

[0066] 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 of the maximum width of the waviness is 0 μm or more, preferably 0.1 μm or more, and more preferably 1 μm or more. The maximum width of the waviness in the transfer film is the value measured by the following procedure. First, the transfer film is cut perpendicular to the main surface to a size of 20 cm x 20 cm to prepare a test sample. If the transfer film has a protective film, the protective film is removed. Next, the test sample is placed on a smooth and horizontal stage with the surface of the temporary support facing the stage. After placement, a 3D surface image is obtained by scanning the surface of the test sample within a 10 cm square area in the center of the test sample using a laser microscope (e.g., VK-9700SP manufactured by Keyence Corporation), and the minimum concave height is subtracted from the maximum convex height observed in the obtained 3D surface image. The above operation is performed for 10 test samples, and the arithmetic mean is defined as the "maximum waviness width of the transfer film".

[0067] In the photosensitive composition layer of the transfer film, if there is an additional composition layer (for example, a photosensitive composition layer and an intermediate layer) on the surface opposite to the temporary support 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 total thickness of the photosensitive composition layer.

[0068] 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.

[0069] 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 (e.g., the photosensitive composition layer and the intermediate layer, etc.) other than the protective film 19 that can be placed on the temporary support 11 is also referred to as a "composition layer".

[0070] The following provides a detailed description of each component and part of the transfer film.

[0071] [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.

[0072] The temporary support may have either a single-layer or multi-layer structure. A film is preferred as the temporary support, and a resin film is more preferred. Furthermore, a film that is flexible and does not undergo significant deformation, shrinkage, or stretching under pressure or under pressure and / or heating is also preferred as the temporary support, and a film that is free from deformation such as wrinkles and scratches is also preferred. Examples of films include polyethylene terephthalate film (e.g., biaxially oriented polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film, with polyethylene terephthalate film being preferred.

[0073] The temporary support is preferably highly transparent, as it allows for pattern exposure through the support. The transmittance at 365 nm is preferably 60% or higher, and more preferably 70% or higher. From the viewpoint of pattern formation during pattern exposure via the temporary support and the transparency of the temporary support, it is preferable that the haze of the temporary support be small. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 1.0% or less, and even more preferably 0.1% or less. There is no particular lower limit, but 0.01% is an example. From the standpoint of pattern formation during pattern exposure via a temporary support and the transparency of the temporary support, it is preferable to have a small number of fine particles, foreign matter, and defects in the temporary support. The number of fine particles, foreign matter, and defects with a diameter of 1 μm or more in the temporary support is 50 per 10 mm. 2 The following is preferable: 10 pieces / 10mm 2 The following is more preferable: 3 pieces / 10mm 2 The following is even more preferable: 0 pieces / 10mm 2 That is particularly preferable.

[0074] The thickness of the temporary support is preferably 5 μm or more, and more preferably 6 μm or more. The upper limit is preferably 200 μm or less, more preferably 150 μm or less, even more preferably 50 μm or less, particularly preferably 25 μm or less, and most preferably less than 16 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).

[0075] 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.

[0076] From the viewpoint of improving the adhesion between the temporary support and the photosensitive composition layer, the surface of the temporary support that contacts the photosensitive composition layer may be surface-modified. Examples of the surface modification treatment include treatments using UV irradiation, corona discharge, plasma, and the like. The exposure amount in UV irradiation is preferably 10 to 2000 mJ / cm 2 and more preferably 50 to 1000 mJ / cm 2 If the exposure amount is within the above range, the lamp output and illuminance are not particularly limited. Examples of the light source in UV irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes (LEDs) that emit light in the wavelength band of 150 to 450 nm.

[0077] Examples of the temporary support include biaxially stretched polyethylene terephthalate films with a film thickness of 16 μm, biaxially stretched polyethylene terephthalate films with a film thickness of 12 μm, and biaxially stretched polyethylene terephthalate films with a film thickness of 9 μm. Examples of the temporary support also include paragraphs

[0017] to

[0018] of JP-A No. 2014-085643, paragraphs

[0019] to

[0026] of JP-A No. 2016-027363, paragraphs

[0041] to

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

[0029] to

[0040] of International Publication No. 2018 / 179370, and the contents of these are incorporated herein. Examples of commercially available products of the temporary support include registered trademark Lumirror 16KS40 and registered trademark Lumirror 16FB40 (both manufactured by Toray Industries, Inc.); Cosmo Shine A4100, Cosmo Shine A4300, and Cosmo Shine A8300 (all manufactured by Toyobo Co., Ltd.).

[0078] [Photosensitive Composition Layer] The transfer film has a photosensitive composition layer. 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 resist pattern corresponds to a cured film.

[0079] The photosensitive composition layer contains resin A, which will be described later. The photosensitive composition layer may further contain a polymerizable compound and a polymerization initiator. Such a photosensitive composition layer preferably contains, based on the total mass of the photosensitive composition layer, resin A: 10-95% by mass; polymerizable compound: 0-70% by mass; and polymerization initiator: 0.01-20% by mass. The mass ratio of polymerizable compounds other than the resin contained in the photosensitive composition layer to resin A, as described later, is 0.85 or less. The following describes each component that the photosensitive composition layer may contain.

[0080] (resin) The photosensitive composition layer contains a resin having crosslinkable groups (hereinafter referred to as resin A). Furthermore, resin A has crosslinkable groups, and its weight-average molecular weight is 3000 or more. The form of the crosslinkable groups in resin A is not particularly limited, but it is preferable that resin A contains structural units having crosslinkable groups. Structural units having crosslinkable groups will be described in detail later.

[0081] Resin A is preferably an alkali-soluble polymer. The acid value of resin A is preferably 220 mg KOH / g or less, more preferably less than 200 mg KOH / g, and even more preferably less than 190 mg KOH / g, from the viewpoint of achieving better resolution by suppressing swelling of the negative-type photosensitive composition layer due to the developing solution. The lower limit of the acid value of resin A is not particularly limited, but from the viewpoint of superior developability, it is preferably 60 mg KOH / g or higher, more preferably 120 mg KOH / g or higher, even more preferably 150 mg KOH / g or higher, and particularly preferably 170 mg KOH / g or higher. The acid value (mgKOH / g) is the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample. The acid value can be calculated, for example, from the average content of acid groups in the compound. The acid value of resin A can be adjusted by the types of constituent units that make up resin A and the content of constituent units containing acid groups, as described later.

[0082] The constituent units that resin A may contain will be explained in detail below.

[0083] -Constituent units having crosslinking groups- Resin A preferably contains structural units having crosslinkable groups. Crosslinkable groups can link polymer chains constituting resin A together by covalent bonds. Examples of crosslinkable groups include polymerizable groups, with polymerizable groups being preferred. In other words, it is preferable that resin A contains constituent units having polymerizable groups. As polymerizable groups, radical polymerizable groups are preferred, and ethylenically unsaturated groups are more preferred. Furthermore, if resin A has ethylenically unsaturated groups, it is preferable that resin A has constituent units having ethylenically unsaturated groups in their side chains. In this specification, "main chain" refers to the relatively longest bonding chain in the polymer compound molecule constituting the resin, and "side chain" refers to an atomic group branching off from the main chain. As the ethylenically unsaturated group, an allyl group or a (meth)acryloxy group is more preferred.

[0084] As a constituent unit having polymerizable groups, the constituent unit represented by formula (P) is preferred.

[0085] [ka]

[0086] In formula (P), R P L represents a hydrogen atom or a methyl group. P represents a divalent linking group. P represents a crosslinking group.

[0087] RP represents a hydrogen atom or a methyl group. R P A hydrogen atom is preferred as the element.

[0088] 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 divalent hydrocarbon groups and divalent 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 arylene group may be monocyclic or polycyclic. The number of carbon atoms in the above arylene group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. A phenylene group is preferred as the above arylene group. The above-mentioned cycloalkylene group and arylene group may have a heteroatom as a ring member atom. The heteroatom is preferably an oxygen atom, a sulfur atom, or a nitrogen atom, and more preferably an oxygen atom. The above hydrocarbon group may further have substituents. Examples of the substituents mentioned above include halogen atoms (e.g., fluorine atoms), hydroxyl groups, nitro groups, cyano groups, alkyl groups, alkoxy groups, alkoxycarbonyl groups, and alkenyl groups, with hydroxyl groups being preferred. L PAs such, an alkylene group which may have a heteroatom is preferred.

[0089] P represents a crosslinking group. The crosslinkable group is as described above, and a polymerizable group is preferred.

[0090] Examples of constituent units having polymerizable groups are listed below, but are not limited to these.

[0091] [ka]

[0092] In the above constituent units, Rx represents a hydrogen atom or a methyl group. Also, in the above constituent units, Ry represents a hydrogen atom or a methyl group.

[0093] Resin A may contain one or more types of structural units having crosslinkable groups. The content of polymerizable structural units in resin A is preferably 2 to 70% by mass, more preferably 10 to 60% by mass, and even more preferably 20 to 55% by mass, relative to the total structural units of resin A, in terms of superior conductive pattern formation properties. Furthermore, the content of the reactive group-containing structural units in resin A is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and even more preferably 20 to 50 mol%, relative to the total structural units of resin A, in order to achieve superior effects of the present invention.

[0094] One method for introducing polymerizable groups into resin A is to react functional groups such as hydroxyl groups, carboxyl groups, primary amino groups, secondary amino groups, acetoacetyl groups, and sulfo groups with compounds such as epoxy compounds, blocked isocyanate compounds, isocyanate compounds, vinyl sulfone compounds, aldehyde compounds, methylol compounds, and carboxylic acid anhydrides. A preferred method for introducing polymerizable groups into resin A is to synthesize a polymer having carboxyl groups by polymerization, and then, by polymer reaction, react a portion of the carboxyl groups of the obtained polymer with an epoxy group-containing (meth)acrylate such as glycidyl (meth)acrylate to introduce (meth)acryloxy groups into the polymer. Another method is to synthesize a polymer having hydroxyl groups by polymerization, and then, by polymer reaction, react a portion of the hydroxyl groups of the obtained polymer with an isocyanate group-containing (meth)acrylate to introduce (meth)acryloxy groups into the polymer. This method makes it possible to obtain resin A having (meth)acryloxy groups in the side chains. The above polymerization reaction is preferably carried out at a temperature of 70 to 100°C, and more preferably at 80 to 90°C. As the polymerization initiator used in the above polymerization reaction, an azo-based initiator is preferred, and for example, V-601 (trade name) or V-65 (trade name) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. is more preferred. The above polymer reaction is preferably carried out at a temperature of 80 to 110°C. In the above polymer reaction, it is preferable to use a catalyst such as an ammonium salt.

[0095] -Constituent units containing acidic groups- Resin A is preferably composed of constituent units having acid groups, as this provides superior conductive pattern-forming properties. Examples of acidic groups include carboxyl groups, sulfol groups, phosphonic acid groups, and phosphate groups, with carboxyl groups being preferred. As for the constituent units having the above acid group, constituent units derived from (meth)acrylic acid are preferred, and constituent units derived from methacrylic acid are more preferred. Resin A may have one or more constituent units having acid groups. When resin A has constituent units having acidic groups, the content of constituent units having acidic groups is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 10 to 30% by mass, based on the total mass of constituent units of resin A. Furthermore, the content of constituent units having acid groups in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, and even more preferably 20 to 40 mol%, relative to the total constituent units of the binder polymer, in order to achieve superior effects of the present invention.

[0096] -Construction units having alicyclic or polycyclic structures- Resin A preferably has constituent units having an alicyclic or polycyclic structure. The rings constituting the polycyclic structure are preferably alicyclic rings. By using a monomer containing a group having an alicyclic structure, or a monomer containing a group having a polycyclic structure in its side chain, an alicyclic or polycyclic structure can be introduced into the side chain of resin A. Examples of monomers containing a group having an alicyclic structure include monomers having an alicyclic aliphatic hydrocarbon group, and (meth)acrylates having an alicyclic hydrocarbon group are preferred. Examples of monomers containing a polycyclic group include monomers having a polycyclic aliphatic hydrocarbon group, with (meth)acrylates having a polycyclic aliphatic hydrocarbon group being preferred.

[0097] Specific examples of (meth)acrylates having alicyclic hydrocarbon groups include (meth)acrylate-1-menthyl, (meth)acrylate-2,2,5-trimethylcyclohexyl, and (meth)acrylate-cyclohexyl. Among these, cyclohexyl (meth)acrylate and 1-menthyl (meth)acrylate are preferred as (meth)acrylates having an alicyclic hydrocarbon group.

[0098] Specific examples of (meth)acrylates having polycyclic aliphatic hydrocarbon groups include (meth)acrylic acid (bicyclo[2.2.1]heptyl-2), (meth)acrylic acid-1-adamantyl, (meth)acrylic acid-2-adamantyl, (meth)acrylic acid-3-methyl-1-adamantyl, (meth)acrylic acid-3,5-dimethyl-1-adamantyl, (meth)acrylic acid-3-ethyladamantyl, (meth)acrylic acid-3-methyl-5-ethyl-1-adamantyl, (meth)acrylic acid-3,5,8-triethyl-1-adamantyl, (meth)acrylic acid-3,5-dimethyl-8-ethyl-1-adamantyl, (meth)acrylic acid-2-methyl-2-adamantyl, and (meth)acrylic acid-2-ethyl Examples include -2-adamantyl, 3-hydroxy-1-adamantyl (meth)acrylate, octahydro-4,7-menthanoinden-5-yl (meth)acrylate, octahydro-4,7-menthanoinden-1-ylmethyl (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, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and fentyl (meth)acrylate. Among these, (meth)acrylates having polycyclic aliphatic hydrocarbon groups include (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, phentyl (meth)acrylate, or tricyclodecane (meth)acrylate.

[0099] When resin A has constituent units having an alicyclic or polycyclic structure, the content of constituent units having an alicyclic or polycyclic structure is preferably 5 to 50% by mass, more preferably 5 to 30% by mass, and even more preferably 10 to 20% by mass, based on the total mass of constituent units of resin A. Furthermore, the content of constituent units having an alicyclic or polycyclic structure in resin A is preferably 5 to 60 mol%, more preferably 10 to 40 mol%, and even more preferably 10 to 30 mol%, relative to the total constituent units of the binder polymer.

[0100] -Constituent units derived from (meth)acrylate monomers having hydrocarbon groups with 9 or more carbon atoms- Resin A preferably contains constituent units derived from (meth)acrylate monomers having hydrocarbon groups with 9 or more carbon atoms, as it exhibits excellent conductive pattern-forming properties. As the (meth)acrylate monomer having a hydrocarbon group with 9 or more carbon atoms, (meth)acrylate monomers having an alicyclic hydrocarbon group with 9 or more carbon atoms are preferred, and (meth)acrylate monomers having a polycyclic aliphatic hydrocarbon group with 9 or more carbon atoms are more preferred. Examples of (meth)acrylate monomers having a hydrocarbon group with 9 or more carbon atoms include isobornyl group, adamantyl group, dicyclopentanyl group, dicyclopentenyl group, phenethyl group, and menthyl group, as well as groups obtained by substituting the hydrogen atoms of these groups with alkyl or hydroxyl groups having 1 to 3 carbon atoms.

[0101] Furthermore, the hydrocarbon group in the (meth)acrylate monomer having 9 or more carbon atoms is preferably branched. Examples of such branched groups include isobornyl, dicyclopentenyl, phenethyl, and menthyl groups.

[0102] When resin A has constituent units derived from (meth)acrylate monomers having hydrocarbon groups with 9 or more carbon atoms, the content of constituent units derived from (meth)acrylate monomers having hydrocarbon groups with 9 or more carbon atoms is preferably 5 to 50% by mass, more preferably 5 to 30% by mass, and even more preferably 10 to 20% by mass, based on the total mass of constituent units of resin A. Furthermore, the content of constituent units derived from (meth)acrylate monomers having hydrocarbon groups with 9 or more carbon atoms in resin A is preferably 5 to 60 mol%, more preferably 10 to 40 mol%, and even more preferably 10 to 30 mol%, relative to the total constituent units of the binder polymer.

[0103] -Construction units having aromatic hydrocarbon groups- Furthermore, in order to suppress line width thickening and deterioration of resolution when the focal position shifts during exposure, it is preferable that resin A contains constituent units derived from monomers having aromatic hydrocarbon groups. Examples of such aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The content of constituent units derived from monomers having aromatic hydrocarbon groups in resin A is preferably 20% by mass or more, and more preferably 30% by mass or more, relative to the total constituent units of resin A. There is no particular upper limit, but it is preferably 95% by mass or less, and more preferably 85% by mass or less. When resin A contains multiple types, it is preferable that the average value of the content of constituent units derived from monomers having aromatic hydrocarbon groups falls within the above range.

[0104] Examples of monomers having aromatic hydrocarbon groups include monomers having aralkyl groups, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, styrene dimer, and styrene trimer). Among these, monomers having aralkyl groups or styrene are preferred. When the monomer having an aromatic hydrocarbon group is styrene, the content of constituent units derived from styrene is preferably 10 to 80% by mass, more preferably 15 to 65% by mass, and even more preferably 15 to 55% by mass, relative to the total constituent units of resin A. If the photosensitive composition layer contains multiple types of resin A, the content of constituent units having an aromatic hydrocarbon group is determined as a weight average.

[0105] Examples of aralkyl groups include phenylalkyl groups which may have substituents, and substituted benzyl groups which may have substituents.

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

[0107] Examples of monomers having a benzyl group, which may have substituents, 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 to 70% by mass, more preferably 15 to 65% by mass, even more preferably 20 to 60% by mass, and particularly preferably 25 to 55% by mass, relative to the total constituent units of resin A.

[0108] -Non-acidic constituent units- Resin A is non-acidic and may contain non-acidic constituent units derived from monomers having at least one polymerizable unsaturated group in the molecule. Examples of the above monomers (non-acidic monomers) include 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, isopropyl (meth)acrylate, and methacrylic acid. Examples include isobutyl, 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, tert-octyl (meth)acrylate, and (meth)acrylates such as 2-ethylhexyl (meth)acrylate; vinyl alcohol esters such as vinyl acetate; and (meth)acrylonitrile. Among these, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or n-butyl (meth)acrylate are preferred, and methyl (meth)acrylate is more preferred. The content of constituent units derived from non-acidic monomers in resin A is preferably 0.5 to 60% by mass, more preferably 1 to 50% by mass, and even more preferably 1 to 30% by mass, relative to the total constituent units of resin A.

[0109] Resin A may be used alone or in combination of two or more types. When using two or more types, it is preferable to use a mixture of two types of resin A containing constituent units derived from monomers having aromatic hydrocarbon groups, or to use a mixture of resin A containing constituent units derived from monomers having aromatic hydrocarbon groups and resin A not containing constituent units derived from monomers having aromatic hydrocarbon groups. In the latter case, the proportion of resin A containing constituent units derived from monomers having aromatic hydrocarbon groups is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of resin A.

[0110] Resin A can be synthesized by polymerizing one or more of the above-mentioned monomers using a peroxide-based polymerization initiator (e.g., benzoyl peroxide) and a radical polymerization initiator such as an azo-based polymerization initiator (e.g., azobisisobutyronitrile). The polymerization method is preferably carried out by adding a monomer solution and a radical polymerization initiator solution dropwise to a heated solvent (preferably acetone, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and isopropanol) under a nitrogen stream, and then heating and stirring. After the reaction is complete, additional solvent may be added to adjust to the desired concentration. In addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may also be used as synthesis methods.

[0111] -Properties of the resin- The glass transition temperature (Tg) of resin A is preferably 50°C or higher. That is, the Tg of a film made solely of resin A is preferably 50°C or higher. There is no particular upper limit to the Tg of a film made solely of resin A, but 135°C is an example. Using resin A having a Tg of 50°C or higher is preferable from the standpoint of improving edge fusing resistance. From this standpoint, the Tg of resin A is preferably 60°C or higher, and more preferably 70°C or higher. Furthermore, by using resin A having a Tg of 135°C or lower, line width thickening and deterioration of resolution when the focal position shifts during exposure can be suppressed. From this perspective, the Tg of resin A is more preferably 130°C or lower, even more preferably 120°C or lower, and particularly preferably 110°C or lower. The Tg of resin A refers to the value measured by a differential scanning calorimetry.

[0112] The weight-average molecular weight of resin A is 3000 or more, preferably between 5000 and 500000. A weight-average molecular weight of 500000 or less is preferred from the viewpoint of improving resolution and developability. A weight-average molecular weight of 100000 or less is more preferred, 60000 or less is even more preferred, 30000 or less is particularly preferred, and 18000 or less is most preferred. On the other hand, a weight-average molecular weight of 5000 or more is preferred from the viewpoint of controlling the properties of the developed aggregates, as well as the properties of the unexposed film, such as edge fusing and cut-tip properties, when used as a photosensitive resin laminate. A weight-average molecular weight of 8000 or more is more preferred, 10000 or more is even more preferred, and 15000 or more is particularly preferred. Edge fusing refers to the degree to which the photosensitive composition layer tends to protrude from the edge of a roll when the transfer film is wound into a roll as a photosensitive resin laminate. Cut-chip properties refer 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 photosensitive resin laminate, they can be transferred to the mask in subsequent exposure processes, causing defective products. The degree of dispersion of resin A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0. In this disclosure, the degree of dispersion is the ratio of the weight-average molecular weight to the number-average molecular weight (weight-average molecular weight / number-average molecular weight). In this disclosure, the weight-average molecular weight and the number-average molecular weight are values ​​measured using gel permeation chromatography.

[0113] The photosensitive composition layer may also contain resins other than resin A described above. Other resins include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyester resins, epoxy resins, polyacetal resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0114] The content of resin A is preferably 10 to 95% by mass, more preferably 20 to 80% by mass, even more preferably 30 to 70% by mass, and particularly preferably 40 to 60% by mass, based on the total mass of the photosensitive composition layer. A resin A content of 95% by mass or less is preferable from the standpoint of controlling the development time. On the other hand, a resin A content of 10% by mass or more is preferable from the standpoint of improving edge fusing resistance.

[0115] (polymerizable compound) The photosensitive composition layer may contain a polymerizable compound having polymerizable groups. Ethylene-unsaturated compounds are preferred as the polymerizable compound. In this specification, "polymerizable compound" refers to a compound that polymerizes under the action of a polymerization initiator, as described later, and is a compound different from resin A mentioned above.

[0116] The polymerizable group in the polymerizable compound can be any group that participates in the polymerization reaction. 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. Groups having ethylenically unsaturated groups are preferred, and acryloyl groups or methacryloyl groups are more preferred.

[0117] Examples of ethylenically unsaturated groups in ethylenically unsaturated compounds include vinyl groups, acryloyl groups, methacryloyl groups, styryl groups, and maleimide groups. Acryloyl or methacryloyl groups are preferred as the ethylenically unsaturated group. The polymerizable groups of polymerizable compounds other than ethylenically unsaturated compounds are not particularly limited as long as they are groups that participate in polymerization reactions, and examples include groups having cationic polymerizable groups such as epoxy groups and oxetane groups. The following describes ethylenically unsaturated compounds.

[0118] Ethylene-unsaturated compounds are preferred if they have two or more ethylenically unsaturated groups in a single molecule (polyfunctional ethylenically unsaturated compounds) because they exhibit superior photosensitivity. Furthermore, from the standpoint of superior resolution and exfoliation, the number of ethylenically unsaturated groups in one molecule of an ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and even more preferably 2 or less.

[0119] From the viewpoint of achieving a better balance between photosensitivity, resolution, and peelability of the photosensitive composition layer, it is preferable to include a difunctional or trifunctional ethylenically unsaturated compound having two or three ethylenically unsaturated groups in one molecule, and more preferable to include a difunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule. The content of the difunctional ethylenically unsaturated compound relative to the total mass of the polymerizable compound is preferably 20% by mass or more, more preferably over 40% by mass, and even more preferably 55% by mass or more, from the viewpoint of excellent peelability. There is no particular upper limit, and it may be 100% by mass. That is, all of the polymerizable compounds may be difunctional ethylenically unsaturated compounds. Furthermore, as the ethylenically unsaturated compound, (meth)acrylate compounds having a (meth)acryloyl group as a polymerizable group are preferred.

[0120] -Polymerizable compound B1- The photosensitive composition layer may also preferably contain polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups as a polymerizable compound.

[0121] In the photosensitive composition layer, the mass ratio of polymerizable compound B1 to the total mass of polymerizable compounds is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 55% by mass or more, and particularly preferably 60% by mass or more, from the viewpoint of superior resolution. There is no particular upper limit, but from the viewpoint of peelability, for example, it is 100% by mass or less, preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, and particularly preferably 85% by mass or less.

[0122] Examples of aromatic rings in polymerizable compound B1 include aromatic hydrocarbon rings such as benzene rings, naphthalene rings, and anthracene rings; aromatic heterocycles such as thiophene rings, furan rings, pyrrole rings, imidazole rings, triazole rings, and pyridine rings; and fused rings thereof. Aromatic hydrocarbon rings are preferred, and benzene rings are more preferred. The above aromatic rings may have substituents. Polymerizable compound B1 may have only one aromatic ring, or it may have two or more aromatic rings.

[0123] 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.

[0124] 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, and it is preferable that they are bonded via one or more alkylene oxy groups. In other words, it is preferable that polymerizable compound B1 has an alkylene oxide-modified bisphenol structure. The alkylene oxy groups added to both ends of the bisphenol structure are preferably ethylene oxy groups or propylene oxy groups, with ethylene oxy groups being more preferred. The number of alkylene oxy groups added to the bisphenol structure is not particularly limited, but 4 to 16 per molecule is preferred, and 6 to 14 is more preferred. Polymerizable compound B1 having a bisphenol structure is described in paragraphs

[0072] to

[0080] of Japanese Patent Application Publication No. 2016-224162, and the contents described in this publication are incorporated herein by reference.

[0125] As polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferred, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferred. Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and 2,2-bis(4-(methacryloxydodecaethoxytetrapropoxy)phenyl)propane. Examples include (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), ethoxylated (10)bisphenol A diacrylate (NK ester A-BPE-10, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and ethoxylated bisphenol A dimethacrylate (BPE-100, manufactured by Shin Nakamura Chemical Industry Co., Ltd.).

[0126] As polymerizable compound B1, compounds represented by the following general formula (B1) are also preferred.

[0127] [ka]

[0128] In general formula B1, R1 and R2 each independently represent a hydrogen atom or a methyl group. A represents C2H4. B represents C3H6. n1 and n3 are each independently integers from 1 to 39, and n1 + n3 is an integer from 2 to 40. n2 and n4 are each independently integers from 0 to 29, and n2 + n4 is an integer from 0 to 30. The arrangement of the constituent units of -(AO)- and -(BO)- may be random or in blocks. In the case of blocks, either -(AO)- or -(BO)- may be on the bisphenyl group side. In one embodiment, n1+n2+n3+n4 is preferably 2 to 20, more preferably 2 to 16, and even more preferably 4 to 12. Also, n2+n4 is preferably 0 to 10, more preferably 0 to 4, even more preferably 0 to 2, and particularly preferably 0.

[0129] Polymerizable compound B1 may be used alone or in combination of two or more types. The content of polymerizable compound B1 is preferably 10% by mass or more, and more preferably 20% by mass or more, relative to the total mass of the photosensitive composition layer, from the viewpoint of superior resolution. There is no particular upper limit, but from the viewpoint of transferability and edge fusion (the phenomenon in which the photosensitive resin seeps out from the edges of the transfer member), it is preferably 70% by mass or less, and more preferably 60% by mass or less.

[0130] The photosensitive composition layer may contain polymerizable compounds other than the polymerizable compound B1 described above. Polymerizable compounds other than polymerizable compound B1 are not particularly limited and can be appropriately selected from known compounds. Examples include compounds having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compounds), difunctional ethylenically unsaturated compounds without aromatic rings, and trifunctional or more ethylenically unsaturated compounds.

[0131] 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.

[0132] 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 tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), tricyclodecane dimethanol 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.), and polyethylene. Examples include glycol dimethacrylate (4G, 9G, 14G, and 23G, etc., manufactured by Shin Nakamura Chemical Industry Co., Ltd.), Aronics® M-220 (manufactured by Toagosei Co., Ltd.), Aronics® M-240 (manufactured by Toagosei Co., Ltd.), Aronics® M-270 (manufactured by Toagosei Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate. Examples of polyalkylene glycol di(meth)acrylates include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate. Examples of urethane di(meth)acrylates include propylene oxide-modified urethane di(meth)acrylates and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates. Examples of commercially available products include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., Ltd.).

[0133] Examples of ethylenically unsaturated compounds with three or more functions include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide modified products thereof. Here, "(tri / tetra / penta / hexa)(meth)acrylate" is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, while "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate. In one embodiment, the photosensitive composition layer may also contain the polymerizable compound B1 described above and a trifunctional or greater ethylenically unsaturated compound, and more preferably contains the polymerizable compound B1 described above and two or more trifunctional or greater ethylenically unsaturated compounds. In this case, the mass ratio of polymerizable compound B1 to trifunctional or greater ethylenically unsaturated compounds is preferably (total mass of polymerizable compound B1):(total mass of trifunctional or greater ethylenically unsaturated compounds) = 1:1 to 5:1, more preferably 1.2:1 to 4:1, and even more preferably 1.5:1 to 3:1. In one embodiment, the photosensitive composition layer preferably contains the polymerizable compound B1 described above and two or more trifunctional ethylenically unsaturated compounds.

[0134] Examples of alkylene oxide-modified ethylenically unsaturated compounds with three or more functions include caprolactone-modified (meth)acrylate compounds (such as KAYARAD® DPCA-20 from Nippon Kayaku Co., Ltd., and A-9300-1CL from Shin Nakamura Chemical Industry Co., Ltd.), ethoxylated trimethylolpropane triacrylate (such as SR454, SR499, and SR502 from Tomoe Industries Co., Ltd.), and alkylene oxide-modified (meth)acrylate compounds (such as KAYARAD RP-1040 from Nippon Kayaku Co., Ltd., ATM-35E and A-9300 from Shin Nakamura Chemical Industry Co., Ltd., and EBECRYL® from Daicel Ornex Co., Ltd.). Examples include 135, ethoxylated glycerin triacrylate (such as A-GLY-9E manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Arronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Arronix M-520 (manufactured by Toagosei Co., Ltd.), and Arronix M-510 (manufactured by Toagosei Co., Ltd.).

[0135] Furthermore, polymerizable compounds having an acidic group (such as a carboxyl group) may be used as the polymerizable compound. The above acidic group may form an acid anhydride group. Examples of polymerizable compounds having an acidic group include Arronix® TO-2349 (manufactured by Toagosei Co., Ltd.), Arronix® M-520 (manufactured by Toagosei Co., Ltd.), and Arronix® M-510 (manufactured by Toagosei Co., Ltd.). As a polymerizable compound having an acid group, for example, a polymerizable compound having an acid group described in paragraphs

[0025] to

[0030] of Japanese Patent Application Publication No. 2004-239942 may be used.

[0136] The molecular weight (or weight-average molecular weight if a molecular weight distribution exists) of the polymerizable compound (including polymerizable compound B1) is preferably 200 to 3000, more preferably 280 to 2200, and even more preferably 300 to 2200.

[0137] Polymerizable compounds may be used individually or in combination of two or more. The polymerizable compound content is preferably 0 to 70% by mass, more preferably 10 to 70% by mass, and even more preferably 20 to 60% by mass, based on the total mass of the photosensitive composition layer.

[0138] Furthermore, as mentioned above, the mass ratio of polymerizable compounds other than resin A contained in the photosensitive composition layer to resin A is 0.85 or less. The lower limit of the above mass ratio is 0.00. In terms of superior conductor pattern formation properties, the above mass ratio is preferably 0.00 to 0.80, more preferably 0.00 to 0.70, and even more preferably 0.30 to 0.65.

[0139] (Polymerization initiator) The photosensitive composition layer may contain a polymerization initiator. As polymerization initiators, for example, known polymerization initiators can be used depending on the type of polymerization reaction. Specifically, thermal polymerization initiators and photopolymerization initiators can be used. The polymerization initiator may be either a radical polymerization initiator or a cationic polymerization initiator.

[0140] 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. There are no particular limitations on the photopolymerization initiator; known photopolymerization initiators can be used. Examples of photopolymerization initiators include photoradical polymerization initiators and photocationic polymerization initiators, with photoradical polymerization initiators being preferred.

[0141] 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.

[0142] Furthermore, the photosensitive composition layer preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and their derivatives as a photoradical polymerization initiator, from the viewpoint of photosensitivity, visibility of exposed and unexposed areas, and resolution. The two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different. Examples of derivatives of the 2,4,5-triarylimidazole dimer include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0143] As photoradical polymerization initiators, for example, polymerization initiators described in paragraphs

[0031] to

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

[0064] to

[0081] of Japanese Patent Application Publication No. 2015-14783 may be used.

[0144] Examples of photoradical polymerization initiators include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (trade name: manufactured by Midori Chemical Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (trade name: manufactured by Midori Chemical Co., Ltd.), Irgacure OXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad 651 and 369 (trade name: manufactured by IGM Resins BV), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0145] Examples of commercially available photoradical polymerization initiators include 1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyl oxime) (trade name: IRGACURE® OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyl oxime) (trade name: IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), IRGACURE OXE-04 (manufactured by BASF), and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, IGM Resins). (Manufactured by BV), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (Trade name: Omnirad 907, manufactured by IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (Trade name: Omnirad 127 (manufactured by IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (product name: Omnirad 369, manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropan-1-one (product name: Omnirad 1173, manufactured by IGM Resins BV), 1-hydroxycyclohexylphenyl ketone (product name: Omnirad 184, manufactured by IGM Resins BV), 2,2-dimethoxy-1,2-diphenylethane-1-one (product name: Omnirad 651, manufactured by IGM Resins BV), 2,4,6-trimethylbenzolyl-diphenylphosphine oxide (product name: Omnirad TPO H, manufactured by IGM Resins BV), bis(2,4,6-trimethylbenzolyl)phenylphosphine oxide (product name: Omnirad 819, manufactured by IGM Resins (Manufactured by BV), oxime ester-based photopolymerization initiator (product name: Lunar 6, manufactured by DKSH Japan), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (product name: B-CIM, manufactured by Hampford), 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (product name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyl oxime) (product name: TR-PBG-305, manufactured by Changzhou Qiang) Examples include 1,2-propanedione,3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazole-3-yl]-,2-(O-acetyloxime) (trade name: TR-PBG-326, manufactured by Changzhou Strong Electronic Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazole-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, manufactured by Changzhou Strong Electronic Materials Co., Ltd.).

[0146] A photocationic polymerization initiator (photoacid generator) is a compound that generates acid upon receiving active light. While compounds that are sensitive to active light with a wavelength of 300 nm or higher, preferably 300-450 nm, and generate acid are preferred as photocationic polymerization initiators, their chemical structure is not limited. Furthermore, photocationic polymerization initiators that are not directly sensitive to active light with a wavelength of 300 nm or higher can also be preferably used in combination with a sensitizer, provided they become sensitive to active light with a wavelength of 300 nm or higher and generate acid. As the photocationic polymerization initiator, a photocationic polymerization initiator that generates an acid with a pKa of 4 or less is preferred, a photocationic polymerization initiator that generates an acid with a pKa of 3 or less is more preferred, and a photocationic polymerization initiator that generates an acid with a pKa of 2 or less is particularly preferred. There is no specific lower limit for the pKa, but for example, -10.0 or higher is preferred.

[0147] Examples of photocationic polymerization initiators include ionic photocationic polymerization initiators and nonionic photocationic polymerization initiators. Examples of ionic photocationic polymerization initiators include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, as well as quaternary ammonium salts. As the ionic photocationic polymerization initiator, the ionic photocationic polymerization initiator described in paragraphs

[0114] to

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

[0148] Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triazines, diazomethane compounds, imidosulfonate compounds, and oximesulfonate compounds. For trichloromethyl-s-triazines, diazomethane compounds, and imidosulfonate compounds, compounds described in paragraphs

[0083] to

[0088] of Japanese Patent Publication No. 2011-221494 may be used. For oximesulfonate compounds, compounds described in paragraphs

[0084] to

[0088] of International Publication No. 2018 / 179640 may be used.

[0149] The photosensitive composition layer preferably contains a photoradical polymerization initiator, and more preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and their derivatives.

[0150] Polymerization initiators may be used individually or in combination of two or more types. The content of the polymerization initiator (preferably a photopolymerization initiator) is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, based on the total mass of the photosensitive composition layer. The upper limit is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, based on the total mass of the photosensitive composition layer.

[0151] (Sensitizer) The photosensitive composition layer preferably contains a sensitizer. The sensitizer is not particularly limited, and known sensitizers, dyes, and pigments can be used. Examples of sensitizers include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, distylylbenzene compounds, styrylpyridine compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds. The compounds listed above also include derivatives of the above compounds. Among these, dialkylaminobenzophenone compounds, anthracene compounds, distylylbenzene compounds, or styrylpyridine compounds are preferred as sensitizers, anthracene compounds, distylylbenzene compounds, or styrylpyridine compounds are more preferred, and anthracene derivatives, distylylbenzene derivatives, or styrylpyridine derivatives are even more preferred.

[0152] The sensitizer may be used alone or in combination of two or more types. When the photosensitive composition layer contains a sensitizer, the amount of sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving sensitivity to light sources and improving curing speed by balancing polymerization rate and chain transfer, 0.01 to 5% by mass and more preferably 0.05 to 1% by mass is preferred based on the total mass of the photosensitive composition layer.

[0153] (dye) The photosensitive composition layer preferably contains a dye (also called "dye N") whose maximum absorption wavelength in the wavelength range of 400-780 nm during color development is 450 nm or higher, and whose maximum absorption wavelength changes with the presence of an acid, base, or radical, from the viewpoint of visibility of the exposed and unexposed areas, pattern visibility after development, and resolution. Although the detailed mechanism is unknown, the inclusion of dye N improves adhesion to adjacent layers (e.g., water-soluble resin layers) and results in superior resolution.

[0154] In this specification, the phrase "the maximum absorption wavelength of a dye changes due to an acid, base, or radical" may mean any of the following: a dye in a colored state is decolorized by an acid, base, or radical; a dye in a decolorized state is colored by an acid, base, or radical; or a dye in a colored state changes to a colored state of another hue. Specifically, the dye N may be a compound that changes from a decolorized state to a colored state upon exposure, or a compound that changes from a colored state to a decolorized state upon exposure. In this case, the dye may change its colored or decolorized state due to the generation and action of acids, bases, or radicals within the photosensitive composition layer upon exposure, or it may be a dye that changes its colored or decolorized state due to a change in the state (e.g., pH) within the photosensitive composition layer caused by acids, bases, or radicals. Furthermore, the dye may change its colored or decolorized state upon direct stimulation by acids, bases, or radicals without exposure.

[0155] In particular, from the viewpoint of visibility and resolution of the exposed and unexposed areas, the dye N is preferably a dye whose maximum absorption wavelength changes with acid or radicals, and more preferably a dye whose maximum absorption wavelength changes with radicals. If the photosensitive composition layer is a negative-type photosensitive composition layer, it is preferable that the negative-type photosensitive composition layer contains both a dye N whose maximum absorption wavelength changes due to radicals, and a photoradical polymerization initiator, from the viewpoint of visibility and resolution of the exposed and unexposed areas. Furthermore, from the viewpoint of visibility between the exposed and unexposed areas, it is preferable that the dye N is a dye that develops color in response to an acid, base, or radical.

[0156] An example of the color development mechanism of dye N is a configuration in which a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator), or a photobase generator is added to a photosensitive composition layer, and after exposure, radicals, acids, or bases generated from the photoradical polymerization initiator, photocationic polymerization initiator, or photobase generator cause a radical-reactive dye, an acid-reactive dye, or a base-reactive dye (e.g., a leuco dye) to develop color.

[0157] From the viewpoint of visibility of the exposed and unexposed areas, the maximum absorption wavelength of dye N in the wavelength range of 400 to 780 nm during color development is preferably 550 nm or higher, more preferably 550 to 700 nm, and even more preferably 550 to 650 nm. Furthermore, the dye N may have only one maximum absorption wavelength in the wavelength range of 400-780 nm during color development, or it may have two or more. If the dye N has two or more maximum absorption wavelengths in the wavelength range of 400-780 nm during color development, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths should be 450 nm or higher.

[0158] The maximum absorption wavelength of dye N is obtained by measuring the transmission spectrum of a solution containing dye N (at a temperature of 25°C) in the wavelength range of 400 to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) in an atmospheric environment, and detecting the wavelength at which the light intensity is minimum (maximum absorption wavelength).

[0159] Examples of dyes that develop or decolorize upon exposure include leuco compounds. Examples of pigments that decolorize upon exposure include leuco compounds, diarylmethane-based dyes, oxazine-based dyes, xanthene-based dyes, iminonaphthoquinone-based dyes, azomethine-based dyes, and anthraquinone-based dyes. As for the dye N, a leuco compound is preferred from the viewpoint of visibility between the exposed and unexposed areas.

[0160] 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.

[0161] As a leuco compound, it is preferable to have a lactone ring, sultine ring, or sultone ring from the viewpoint of visibility between the exposed and unexposed areas. 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 a leuco compound, it is preferable to have a lactone ring, sultine ring, or sultone ring, and the lactone ring, sultine ring, or sultone ring opens and develops color in response to radicals or acids, and it is more preferable to have a lactone ring, and the lactone ring opens and develops color in response to radicals or acids.

[0162] Examples of pigment N include the following dyes and leuco compounds. Specific examples of dyes among pigment N include Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuchsine, Methyl Violet 2B, Quinaldine Red, Rose Bengal, Methanyl Yellow, Thymol Sulfophthalein, Xylenol Blue, Methyl Orange, Paramethyl Red, Congofred, Benzopulpurine 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Parafuchsine, Victoria Pure Blue - Naphthalene Sulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Co., Ltd.), Oil Pink #312 (manufactured by Orient Chemical Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Co., Ltd.), Oil Scarlet #308 (manufactured by Orient Chemical Co., Ltd.) Examples include Orient Chemical Industries Co., Ltd.'s Oil Red OG, Orient Chemical Industries Co., Ltd.'s Oil Red RR, Orient Chemical Industries Co., Ltd.'s Oil Green #502, Orient Chemical Industries Co., Ltd.'s Spiron Red BEH Special, Hodogaya Chemical Co., Ltd.'s m-Cresol Purple, Cresol Red, Rhodamine B, Rhodamine 6G, Sulforhodamine B, Auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-pN,N-bis(hydroxyethyl)aminophenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0163] Specific examples of leuco compounds among the pigment N include p,p',p''-hexamethyltriaminotriphenylmethane (leucocrystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoylleucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(Np-tolyl-N-ethyl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluorane, 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, 3-(N-cyclohexyl-N-methylamino)- 6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-xylidinofluorane, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorane, 3-(N,N-diethylamino)-6-methoxy-7-aminofluorane, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluorane, 3-(N,N-diethylamino)-7-chlorofluorane, 3-(N,N-di Ethylamino)-7-benzylaminofluorane, 3-(N,N-diethylamino)-7,8-benzofluorane, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluorane, 3-(N,N-dibutylamino)-6-methyl-7-xylidinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3,3-bis(1-ethyl-2-methylindole-3-yl)phthalide, 3,3-bis(1-n-butyl-2- Examples include methylindole-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-zaphthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)phthalide, and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthene-3-one.

[0164] From the viewpoint of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, dye N is preferably a dye whose maximum absorption wavelength changes due to radicals, and more preferably a dye that develops color due to radicals. As the pigment N, leucocrystal violet, crystal violet lactone, brilliant green, or Victoria Pure Blue naphthalene sulfonate are preferred.

[0165] 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, from the viewpoint of visibility of exposed and unexposed areas, pattern visibility after development, and resolution.

[0166] 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 colored state. The following describes a method for quantifying the content of dye N, using a dye that develops color via radicals as an example. Solutions were prepared by dissolving 0.001 g and 0.01 g of dye in 100 mL of methyl ethyl ketone. To each of the resulting solutions, the photoradical polymerization initiator Irgacure OXE01 (trade name, BASF Japan Ltd.) was added, and radicals were generated by irradiating with light of a wavelength of 365 nm, causing all the dyes to develop color. Subsequently, under an atmospheric environment, the absorbance of each solution at a liquid temperature of 25°C was measured using a spectrophotometer (UV3100, Shimadzu Corporation), and a calibration curve was created. Next, the absorbance of the solution in which all of the dye has developed is measured, using the same method as above, except that 3 g of the photosensitive composition layer is dissolved in methyl ethyl ketone instead of the dye. The amount of dye contained in the photosensitive composition layer is calculated from the absorbance of the obtained solution containing the photosensitive composition layer based on the calibration curve. Note that 3g of the photosensitive composition layer is equivalent to 3g of the total solids in the photosensitive composition.

[0167] (Thermal crosslinkable compound) When the photosensitive composition layer is a negative-type photosensitive composition layer, it may contain a thermally crosslinkable compound, in terms of the strength of the resulting cured film and the tackiness of the resulting uncured film. In this specification, thermally crosslinkable compounds having ethylenically unsaturated groups, as described later, will not be treated as polymerizable compounds, but as thermally crosslinkable compounds. Examples of thermally crosslinkable compounds include methylol compounds and blocked isocyanate compounds. Among these, blocked isocyanate compounds are preferred in terms of the strength of the resulting cured film and the tackiness of the resulting uncured film. Since blocked isocyanate compounds react with hydroxyl and carboxyl groups, for example, if the resin and / or polymerizable compound has at least one of a hydroxyl and a carboxyl group, the hydrophilicity of the formed film tends to decrease, and the function of the film when the cured negative-type photosensitive composition layer is used as a protective film is enhanced. Blocked isocyanate compounds refer to "compounds having a structure in which the isocyanate group of an isocyanate is protected (so-called masked) with a blocking agent."

[0168] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160°C, and more preferably 130 to 150°C. The dissociation temperature of blocked isocyanates refers to "the temperature of the endothermic peak associated with the deprotection reaction of blocked isocyanates, as measured by differential scanning calorimetry (DSC) analysis using a differential scanning calorimeter." As a differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Corporation can be suitably used. However, the differential scanning calorimeter is not limited to this.

[0169] Examples of blocking agents with a dissociation temperature of 100-160°C include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)] and oxime compounds (compounds having a structure represented by -C(=N-OH)- in the molecule, such as formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime). Among these, as a blocking agent with a dissociation temperature of 100-160°C, at least one selected from oxime compounds is preferred, for example, from the viewpoint of storage stability.

[0170] Blocked isocyanate compounds are preferably configured to have an isocyanurate structure, for example, to improve the brittleness of the film and enhance adhesion to the substrate. Blocked isocyanate compounds having an isocyanurate structure can be obtained, for example, by isocyanurating and protecting hexamethylene diisocyanate. Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure using an oxime compound as a blocking agent are preferred because they make it easier to set the dissociation temperature within a favorable range and reduce development residue compared to compounds without an oxime structure.

[0171] The blocked isocyanate compound may have polymerizable groups. There are no particular restrictions on the polymerizable group; known polymerizable groups can be used, and radical polymerizable groups are preferred. Polymerizable groups include ethylenically unsaturated groups such as (meth)acryloxy groups, (meth)acrylamide groups, and styryl groups, as well as epoxy groups such as glycidyl groups. Among the polymerizable groups, ethylenically unsaturated groups are preferred, (meth)acryloxy groups are more preferred, and acryloxy groups are even more preferred.

[0172] Commercially available blocked isocyanate compounds can be used. Examples of commercially available blocked isocyanate compounds include Karenz® AOI-BM, Karenz® MOI-BM, Karenz® MOI-BP, etc. (all manufactured by Showa Denko Corporation), and the block-type Duranate series (for example, Duranate® TPA-B80E, Duranate® WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation). Furthermore, a compound with the following structure can also be used as a blocked isocyanate compound.

[0173] [ka]

[0174] The thermally crosslinkable compound may be used alone or in combination of two or more types. When the photosensitive composition layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass, relative to the total mass of the photosensitive composition layer.

[0175] (Pigment) The photosensitive composition layer may contain a pigment. When the photosensitive composition layer contains a pigment, the photosensitive composition layer 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.

[0176] 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.

[0177] 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.

[0178] 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 preferable to apply both alumina treatment and zirconia treatment.

[0179] When the photosensitive composition layer is a colored resin layer, from the viewpoint of transferability, it is also preferable that the photosensitive composition layer contains a colored pigment other than a black pigment and a white pigment. The particle diameter (number average particle diameter) of the colored pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, from the viewpoint of better dispersibility. The lower limit is preferably 10 nm or more. Examples of the colored pigment include Victoria Pure Blue BO (Color Index (hereinafter also referred to as "C.I.") 42595), Auramine (C.I. 41000), Fat Black HB (C.I. 26150), Monolite Yellow GT (C.I. Pigment Yellow 12), Permanent Yellow GR (C.I. Pigment Yellow 17), Permanent Yellow HR (C.I. Pigment Yellow 83), Permanent Carmine FBB (C.I. Pigment Red 146), Hostaperm Red ESB (C.I. Pigment Violet 19), Permanent Ruby FBH (C.I. Pigment Red 11), Fast Pink B Spr (C.I. Pigment Red 81), Monastral Fast Blue (C.I. Pigment Blue 15), Monolite Fast Black B (C.I. Pigment Black 1) and carbon, C.I. Pigment Red 97, C.I. Pigment Red 122, C.I. Pigment Red 149, C.I. Pigment Red 168, C.I. Pigment Red 177, C.I. Pigment Red 180, C.I. Pigment Red 192, C.I. Pigment Red 215, C.I. Pigment Green 7, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:4, C.I. Pigment Blue 22, C.I. Pigment Blue 60, C.I. Pigment Blue 64 and C.I. Pigment Violet 23, and C.I. Pigment Red 177 is preferred.

[0180] The pigments may be used alone or in combination of two or more. The content of the pigment 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, still 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.

[0181] When the photosensitive composition layer contains pigments other than black pigments (for example, white pigments and colored pigments, etc.), the content of the pigments other than black pigments is preferably 30% by mass or less, more preferably 1 to 20% by mass, and still more preferably 3 to 15% by mass, based on the total mass of the black pigments.

[0182] When the photosensitive composition layer contains a black pigment, the black pigment (preferably carbon black) is preferably introduced into the photosensitive composition in the form of a pigment dispersion. The dispersion may be prepared by adding a mixture obtained by premixing a black pigment and a pigment dispersant to an organic solvent (or vehicle) and dispersing it with a dispersing machine. The pigment dispersant may be selected according to the pigment and the solvent. For example, commercially available dispersants can be used. The "vehicle" means the part of the medium in which the pigment is dispersed when it is made into a pigment dispersion. The above vehicle is liquid and includes a binder component that holds the black pigment in a dispersed state and a solvent component (organic solvent) that dissolves and dilutes the binder component.

[0183] Examples of the dispersing machine include known dispersing machines such as kneaders, roll mills, attritors, super mills, dissolvers, homomixers, and sand mills. Also, it may be finely pulverized by utilizing the frictional force by mechanical grinding. Examples of the dispersing machine and the fine pulverization include the descriptions in "Dictionary of Pigments" (written by Kunizo Asakura, first edition, Asakura Shoten, 2000, page 438, page 310).

[0184] (Other additives) The photosensitive composition layer may contain known additives as necessary in addition to the above components. Examples of additives include radical polymerization inhibitors, antioxidants (e.g., phenidone), rust inhibitors (e.g., benzotriazoles and 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. Each additive may be used individually or in combination of two or more.

[0185] The photosensitive composition layer may contain a radical polymerization inhibitor. Examples of radical polymerization inhibitors include the thermal polymerization inhibitors described in paragraph

[0018] of Japanese Patent No. 4502784. Among these, phenothiazine, phenoxazine, or 4-methoxyphenol are preferred. Other radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. In order not to impair the sensitivity of the photosensitive composition layer, it is preferable to use nitrosophenylhydroxyamine aluminum salt as a radical polymerization inhibitor. 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, relative to the total mass of the polymerizable compound.

[0186] 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.

[0187] Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole. Commercially available carboxybenzotriazoles such as CBT-1 (Johoku Chemical Industry Co., Ltd., trade name) can be used.

[0188] The total content of benzotriazoles and carboxybenzotriazoles is preferably 0.01 to 3% by mass, and more preferably 0.05 to 1% by mass, relative to the total mass of the photosensitive composition layer. When the content is 0.01% by mass or more, the storage stability of the photosensitive composition layer is better. On the other hand, when the content is 3% by mass or less, the maintenance of sensitivity and suppression of dye decolorization are better.

[0189] 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.

[0190] As the surfactant, nonionic surfactants, fluorinated surfactants, or silicone surfactants are preferred. Examples of commercially available fluorine-based surfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP .MFS-330, EXP.MFS-578, EXP.MFS-579, EXP.MFS-586, EXP.MFS-587, EXP.MFS-628, EXP.MFS-631, EXP.MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (all manufactured by DIC Corporation), Florard FC430, FC431, FC171 (all manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC Inc.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA), Futegent Examples include 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (all manufactured by NEOS Corporation), and U-120E (Unichem Corporation). Furthermore, acrylic compounds having a molecular structure with a functional group containing a fluorine atom, in which the fluorine atom-containing functional group is cleaved and the fluorine atom volatilizes when heat is applied, can also be suitably used as fluorine-based surfactants. Examples of such fluorine-based surfactants include the Megafac DS series manufactured by DIC Corporation (Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), such as Megafac DS-21. Furthermore, as a fluorine-based surfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. In addition, block polymers can also be used as fluorine-based surfactants. Furthermore, as a fluorine-based surfactant, a fluorine-containing polymer compound can also be preferably used, which includes a structural unit derived from a (meth)acrylate compound having a fluorine atom and a structural unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkylene oxy groups (preferably ethylene oxy groups, propylene oxy groups). Furthermore, fluorine-containing polymers having ethylenically unsaturated bond-containing groups in their side chains can also be used as fluorine-based surfactants. Examples include Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0191] As for fluorine-based surfactants, from the viewpoint of improving environmental suitability, it is preferable that the surfactant is derived from a substitute material for compounds having a linear perfluoroalkyl group with 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, and the like. Specific examples include Pluronic® L10, L31, L61, L62, 10R5, 17R2, 25R2, HYDROPALAT WE 3323 (all manufactured by BASF), Tetronic® 304, 701, 704, 901, 904, 150R1 (all manufactured by BASF), Solspers 20000 (all manufactured by Lubrizol Nippon Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), Paionin D-1105, D-6112, D-6112-W, D-6315 (all manufactured by Takemoto Oil & Fat Co., Ltd.), Orfin E1010, Surfinol 104, 400, 440 (all manufactured by Nisshin Chemical Industry Co., Ltd.), and others.

[0192] Examples of silicone-based surfactants include linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

[0193] Specific examples of 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, Toray Silicone SH8400 (all manufactured by Toray Dow Corning Co., Ltd.), as well as X-22-4952, X-22-4272, X-22-626. 6, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF -6001, KF-6002, KP-101KP-103, KP-104, KP-105, KP-106, KP-109, KP-109, KP-112, KP-120, KP-121, KP-124 , KP-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, KP-652 (all manufactured by Shin-Etsu Silicone Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Pa Examples include BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, and BYK323 (all manufactured by Bic Chemie).

[0194] Surfactants can be used individually or in combination of two or more types. If the photosensitive composition layer contains a surfactant, the surfactant content is preferably 0.01 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, and even more preferably 0.05 to 0.80% by mass, based on the total mass of the photosensitive composition layer.

[0195] From the viewpoint of improving reliability and lamination properties, the water content in the photosensitive composition layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass, based on the total mass of the photosensitive composition layer.

[0196] Generally, the layer thickness (film thickness) of the photosensitive composition layer is 0.1 to 300 μm, preferably 0.2 to 100 μm, more preferably 0.5 to 50 μm, still more preferably 0.5 to 15 μm, particularly preferably 0.5 to 10 μm, and most preferably 0.5 to 8 μm. Thereby, the developability of the photosensitive composition layer is improved, and the resolution can be improved. Also, in one aspect, 0.5 to 5 μm is preferable, 0.5 to 4 μm is more preferable, and 0.5 to 3 μm is still more preferable.

[0197] (Impurities, etc.) The photosensitive composition layer may contain impurities. Examples of the impurities include metal impurities or their ions, halide ions, residual organic solvents, residual monomers, and water.

[0198] Examples of the metal impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, and their ions, as well as halide ions. Among them, sodium ions, potassium ions, and halide ions are preferably in the following contents because they are likely to be mixed in. The metal impurities are different compounds from the above-mentioned particles (e.g., metal oxide particles) that can be contained in the transfer film.

[0199] The content of the metal impurities is preferably 80 ppm by mass or less, more preferably 10 ppm by mass or less, still more preferably 2 ppm by mass or less, based on the total mass of the photosensitive composition layer. The lower limit is preferably 1 ppb by mass or more, more preferably 0.1 ppm by mass or more, based on the total mass of the photosensitive composition layer.

[0200] 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.

[0201] 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.

[0202] 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, relative to the total mass of the photosensitive composition layer, in order to improve reliability and lamination.

[0203] (Properties of the photosensitive composition layer) The properties of the photosensitive composition layer will be described below.

[0204] -Total double bond content- In terms of excellent conductive pattern formation properties, the total double bond content in the photosensitive composition layer is preferably greater than 1.00 mmol / g relative to the total mass of the photosensitive composition layer. The above total double bond content is more preferably greater than 1.20 mmol / g, and even more preferably greater than 2.00 mmol / g. There is no particular upper limit, but it is 4.00 mmol / g or less. The total double bond content can be calculated as the sum of the double bond content derived from the resin and the double bond content derived from the polymerizable compound. The double bond content derived from polymerizable compounds can be calculated using the following formula. (Formula) (Ratio of polymerizable compound to the total mass of the photosensitive composition layer) × (Number of double bonds in the polymerizable compound) / (Molecular weight of the polymerizable compound) Furthermore, if the photosensitive composition layer contains multiple polymerizable compounds, the double bond content derived from each polymerizable compound can be calculated using the above formula and then summed up. The method for calculating the double bond content derived from the resin is described below. The total double bond content mentioned above can be adjusted depending on the type of resin, the type of polymerizable compound, and their content and ratio.

[0205] - Resin-derived double bond content - In terms of excellent conductive pattern formation properties, the double bond content derived from resin A is preferably greater than 0.20 mmol / g relative to the total mass of the photosensitive composition layer. The double bond content is more preferably greater than 0.55 mmol / g, even more preferably greater than 0.70 mmol / g, particularly preferably greater than 1.00 mmol / g, and most preferably greater than 1.10 mmol / g. There is no particular upper limit, but it is generally 2.00 mmol / g or less. The double bond content mentioned above can be calculated, for example, using the following formula. In the formula below, "MD" represents a constituent unit containing a double bond. (Formula) (Ratio of resin content to total mass of photosensitive composition layer) × (Ratio of MD content to total mass of resin) × (Number of double bonds in MD) / (Molecular weight of MD) Furthermore, if the photosensitive composition layer contains multiple resins, the amount of double bonds derived from each resin can be calculated using the above formula and then summed up. The above double bond content can be adjusted by the resin content and / or the content of structural units having crosslinkable groups in the resin.

[0206] Furthermore, in terms of excellent conductive pattern formation properties, it is also preferable that the resin (resin A) contains constituent units having an alicyclic or polycyclic structure and satisfies the above-mentioned double bond content requirement (for example, greater than 0.55 mmol / g or greater than 1.00 mmol / g). Furthermore, it is preferable that the resin (resin A) contains constituent units derived from (meth)acrylate monomers having hydrocarbon groups with 9 or more carbon atoms, and that it satisfies the above-mentioned double bond content requirement (for example, greater than 0.55 mmol / g or greater than 1.00 mmol / g).

[0207] -Glass transition temperature- Exposure amount 20mJ / cm 2 Preferably, the glass transition temperature of the photosensitive composition layer after exposure with i-line light is 30°C or higher. The upper limit of the above glass transition temperature is not particularly limited, but 100°C is an example. The glass transition temperature being 30°C or higher makes swelling by the plating solution during the plating process less likely, resulting in superior conductive pattern formation. The above glass transition temperature is 20 mJ / cm² for a 3.0 μm photosensitive composition layer. 2 This refers to the glass transition temperature measured by a differential scanning calorimeter after exposure with i-line light.

[0208] -Thickness- The thickness of the photosensitive composition layer is not particularly limited and can be appropriately selected depending on the application, but 0.5 to 20 μm is preferred.

[0209] [Middle class] The transfer film preferably has an intermediate layer between the temporary support and the photosensitive composition 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 water-soluble resin layer (intermediate layer) may contain.

[0210] The water-soluble resin layer (intermediate layer) contains resin. The above resin preferably contains a water-soluble resin as part or all of it. Examples of resins that can be used as water-soluble resins include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and copolymers thereof. Furthermore, as the water-soluble resin, copolymers of (meth)acrylic acid / vinyl compounds can also be used. Among the copolymers of (meth)acrylic acid / vinyl compounds, copolymers of (meth)acrylic acid / (meth)acrylate are preferred, and copolymers of methacrylic acid / methacrylate are more preferred. When the water-soluble resin is a copolymer of (meth)acrylic acid / vinyl compound, the composition ratio (mol%) is preferably, for example, 90 / 10 to 20 / 80, and more preferably 80 / 20 to 30 / 70.

[0211] The lower limit of the weight-average molecular weight of the water-soluble resin is preferably 5000 or more, more preferably 7000 or more, and even more preferably 10000 or more. The upper limit is preferably 200000 or less, more preferably 100000 or less, and even more preferably 50000 or less. The dispersion degree (Mw / Mn) of the water-soluble resin is preferably 1 to 10, and more preferably 1 to 5.

[0212] Water-soluble resins may be used individually or in combination of two or more types. The content of the water-soluble resin is not particularly limited, but in terms of further improving oxygen barrier properties and interlayer mixing suppression ability, it is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of the water-soluble resin layer (intermediate layer). There is no particular upper limit, but for example, it is preferably 99.9% by mass or less, and even more preferably 99.8% by mass or less.

[0213] The intermediate layer may contain other components in addition to the water-soluble resin mentioned above. 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. Other ingredients include, for example, well-known surfactants.

[0214] 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.

[0215] 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.

[0216] The molecular weight of the other components is preferably less than 5000, more preferably 4000 or less, even more preferably 3000 or less, particularly preferably 2000 or less, and most preferably 1500 or less. The lower limit is preferably 60 or more.

[0217] 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.

[0218] The intermediate layer may contain impurities. Examples of impurities include those contained in the above-mentioned photosensitive composition layer.

[0219] The thickness of the water-soluble resin layer (interlayer) is not particularly limited, but is preferably 0.1 to 5 μm, and more preferably 0.5 to 3 μm. When the thickness of the water-soluble resin layer (interlayer) is within the above range, the oxygen barrier properties are not reduced, and the ability to suppress interlayer mixing is excellent. Furthermore, the increase in the time required to remove the water-soluble resin layer (interlayer) during development can also be suppressed.

[0220] [Protective film] The transfer film may have a protective film on the photosensitive composition layer. As protective films, resin films having heat resistance and solvent resistance can be used. Examples include polyolefin films such as polypropylene film and polyethylene film, polyester films such as polyethylene terephthalate film, polycarbonate film, and polystyrene film. Alternatively, a resin film made of the same material as the temporary support described above may be used as the protective film. Among these, polyolefin film is preferred as the protective film, polypropylene film or polyethylene film is more preferred, and polypropylene film is even more preferred.

[0221] The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, even more preferably 5 to 40 μm, and particularly preferably 15 to 30 μm. The thickness of the protective film is preferably 1 μm or more for superior mechanical strength, and 100 μm or less for relatively low cost.

[0222] Furthermore, in the case of protective films, the number of fisheyes with a diameter of 80 μm or more contained in the protective film is 5 per square meter. 2 The following is preferable: "Fish eyes" refer to foreign matter, undissolved material, and oxidatively degraded materials that are incorporated into the film during the manufacturing process, such as by heat melting, kneading, extrusion, biaxial stretching, and casting.

[0223] 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. This makes it possible to suppress defects caused by the transfer of irregularities resulting from particles contained in the protective film to the photosensitive composition layer or metal layer.

[0224] From the standpoint of providing windability, the arithmetic mean roughness Ra of the surface of the protective film opposite to the surface in contact with the photosensitive composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, even more preferably 0.03 μm or more, and particularly preferably greater than 0.05 μm. On the other hand, it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less. From the viewpoint of suppressing defects during transfer, the surface roughness Ra of the protective film in contact with the photosensitive composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0225] [Method for manufacturing transfer film] There are no particular limitations on the method for manufacturing the transfer film, and known methods can be used. Examples of methods for manufacturing the transfer film 10 include the steps of: applying an intermediate layer forming composition to the surface of a temporary support 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.

[0226] If the transfer film 10 has a protective film 19, the protective film 19 may be pressed onto the composition layer 17 of the transfer film 10 manufactured by the above manufacturing method. As a method for manufacturing the transfer film 10, it is preferable to include a step of providing a protective film 19 so as to contact the side of the composition layer 17 opposite to the side of the temporary support 11, thereby manufacturing a transfer film 10 comprising a temporary support 11, an intermediate layer 13, a photosensitive composition layer 15, and a protective film 19. After manufacturing the transfer film 10 using the above manufacturing method, the transfer film 10 may be wound up to produce and store a roll of transfer film. The roll of transfer film 10 can be provided in its original form for the lamination process with the substrate using the roll-to-roll method described later.

[0227] Furthermore, the method for manufacturing the transfer film 10 may also be a method of forming a composition layer 17 on the protective film 19.

[0228] (Water-soluble resin composition and method for forming an intermediate layer (water-soluble resin layer)) The water-soluble resin composition preferably contains the various components that form the intermediate layer (water-soluble resin layer) described above, as well as a solvent. In the water-soluble resin composition, the preferred range of content of each component relative to the total solid content of the composition is the same as the preferred range of content of each component relative to the total mass of the water-soluble resin layer described above. The solvent is not particularly limited as long as it can dissolve or disperse the water-soluble resin, but at least one selected from the group consisting of water and water-miscible organic solvents is preferred, and water or a mixed solvent of water and a water-miscible organic solvent is more preferred. Examples of water-miscible organic solvents include C1-C3 alcohols, acetone, ethylene glycol, and glycerin, with C1-C3 alcohols being preferred, and methanol or ethanol being more preferred. The solvent may be used individually or in combination of two or more types. The solvent content is preferably 50 to 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 composition.

[0229] The method for forming the water-soluble resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components, and examples include known coating methods (slit coating, spin coating, curtain coating, and inkjet coating, etc.).

[0230] (Photosensitive composition and method for forming a photosensitive composition layer) In terms of superior productivity, it is desirable to form the photosensitive composition layer by a coating method using a photosensitive composition containing the components that make up the photosensitive composition layer described above (for example, resin A, polymerizable compound, and polymerization initiator, etc.) and a solvent. A preferred method for manufacturing a transfer film is to apply a photosensitive composition onto an intermediate layer to form a coating, and then dry this coating at a predetermined temperature to form a photosensitive composition layer.

[0231] The photosensitive composition preferably contains the various components that form the photosensitive composition layer described above, as well as a solvent. In the photosensitive composition, the preferred range of content of each component relative to the total solid content of the composition is the same as the preferred range of content of each component relative to the total mass of the photosensitive composition layer described above. The solvent is not particularly limited as long as it can dissolve or disperse each component other than the solvent, and any known solvent can be used. Specifically, examples include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol and ethanol, etc.), ketone solvents (acetone and methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aprotic polar solvents (N,N-dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents (n-propyl acetate, etc.), amide solvents, lactone solvents, and mixed solvents containing two or more of these.

[0232] The solvent preferably contains at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. More preferably, a mixed solvent containing at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one selected from the group consisting of ketone solvents and cyclic ether solvents is preferred, and even more preferably, a mixed solvent containing at least three of the three: alkylene glycol ether, alkylene glycol ether acetate solvent, and ketone solvent.

[0233] Examples of alkylene glycol ether solvents include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether (such as propylene glycol monomethyl ether acetate), propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether. Examples of alkylene glycol ether acetate solvents include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate. Examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone. As solvents, the solvents described in paragraphs

[0092] to

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

[0014] of Japanese Patent Application Publication No. 2018-177889 may be used, and these contents are incorporated herein by reference. The solvent may be used individually or in combination of two or more types. The solvent content is preferably 50 to 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 composition.

[0234] Methods for applying the photosensitive composition include, for example, printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (i.e., slit coating).

[0235] For drying the photosensitive composition coating, heat drying and reduced-pressure drying are preferred methods. The drying temperature is preferably 90°C or higher, more preferably 100°C or higher, and even more preferably 110°C or higher. There is no particular upper limit to the temperature, but it is preferably 130°C or lower, and more preferably 120°C or lower. Furthermore, the drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. There is no particular upper limit to the drying time, but it is preferably 450 seconds or less, and more preferably 300 seconds or less. The drying temperature is preferably 80°C or higher, and more preferably 90°C or higher. Furthermore, the upper limit to the drying temperature is preferably 130°C or lower, and more preferably 120°C or lower. Drying can also be carried out by continuously changing the temperature. Furthermore, the drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. There is no particular upper limit to the drying time, but it is preferably 600 seconds or less, and more preferably 300 seconds or less.

[0236] Furthermore, a transfer film can be manufactured by laminating a protective film onto a photosensitive composition layer. The method for laminating the protective film onto the photosensitive composition layer is not particularly limited and includes known methods. Examples of devices for laminating a protective film onto a photosensitive composition layer include known laminators such as vacuum laminators and auto-cut laminators. The laminator is preferably equipped with a heat-sensitive roller, such as a rubber roller, and capable of applying pressure and heating. [Examples]

[0237] The present invention will be described in more detail below based on examples. The materials, quantities, proportions, processing details, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples. Unless otherwise specified, "parts" and "%" are based on mass. Furthermore, in the following examples, the weight-average molecular weight of the resin is the weight-average molecular weight obtained by gel permeation chromatography (GPC) on a polystyrene basis. In addition, the acid value of the resin is the theoretical acid value derived from the ratio of the resin's constituent units.

[0238] <Transfer film> A transfer film was prepared using the components shown in Tables 2 and 3 below. First, let's explain the individual components used in the manufacture of the transfer film.

[0239] [Photosensitive composition] The photosensitive composition layer of the transfer film was formed using a photosensitive composition. The materials shown in Tables 2 and 3 were mixed according to the formulations described in Tables 2 and 3 to obtain the photosensitive compositions used in the production of the transfer films in the examples and comparative examples. The following describes each component used in the manufacture of the photosensitive composition.

[0240] (resin) -Synthesis of resin A1- 67 g of propylene glycol monomethyl ether was placed in a flask and heated to 90°C under a nitrogen stream. To this solution, a solution prepared by dissolving 47.7 g of styrene, 1.3 g of methyl methacrylate, 19 g of methacrylic acid, and 4 g of polymerization initiator V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) in 33 g of propylene glycol monomethyl ether was added dropwise over 3 hours. After the dropwise addition was complete, 1 g of V-601 was added three times at 1-hour intervals. The reaction was then allowed to proceed for another 3 hours. After the reaction, the reaction solution was diluted with 33 g of propylene glycol monomethyl ether acetate and 100 g of propylene glycol monomethyl ether. Under an airflow, the diluted reaction solution was heated to 100°C, and 0.53 g of tetraethylammonium bromide and 0.26 g of p-methoxyphenol were added. To this solution, 32 g of glycidyl methacrylate (Bremmer G, manufactured by NOF Corporation) was added dropwise over 20 minutes. After reacting this solution at 100°C for 7 hours, it was diluted with propylene glycol monomethyl ether acetate to obtain a solution of resin A1 with a solid content of 30%. The amount of residual monomer measured using gas chromatography was less than 0.1% by mass relative to the polymer solids for all monomers.

[0241] Using a similar method, resins A2 to A9 shown in Table 1 were synthesized. The amount of residual monomer measured by gas chromatography for each resin was less than 0.1% by mass relative to the polymer solids for all monomers.

[0242] Table 1 shows the amount of constituent units, weight-average molecular weight, double bond content, and glass transition temperature (Tg) of each synthesized resin. In Table 1, the abbreviations are as follows: ·st:Styrene • MMA: Methyl methacrylate • MAA: Methacrylic acid • GMA-MAA: A structural unit formed by adding glycidyl methacrylate to a structural unit derived from methacrylic acid. • DCPMA: Dicyclopentanyl methacrylate • IBMA: Isobornyl methacrylate BzMA: Benzyl methacrylate GMA-MAA represents the constituent units shown in the following chemical formula.

[0243] [ka]

[0244] [Table 1]

[0245] (polymerizable compound) • BPE-100: Ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. (Double bond content: 4.30 mmol / g) • M-270: Arronix M-270, polypropylene glycol diacrylate (n≒12), manufactured by Toagosei Co., Ltd. (double bond content: 2.50 mmol / g) • SR494: Ethoxylated (4) pentaerythritol tetraacrylate, manufactured by Tomoe Industrial Co., Ltd. (double bond content: 7.58 mmol / g) • BPE-500: Ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. (Double bond content: 2.49 mmol / g)

[0246] (Photopolymerization initiator) B-IMD: 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer

[0247] (Sensitizer) • EAB-F: 4,4'-bis(diethylamino)benzophenone • DBA: 9,10-dibutoxyanthracene • DSP: 2,5-distyrylpyridine DSB: Trans,trans-1,4-distyrylbenzene

[0248] (Polymerization inhibitor) Phenothiazine Phenidone: Phenidone 1% MEK solution

[0249] (Chain transfer agent) Compound A: N-phenylcarbamoylmethyl-N-carboxymethylaniline (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0250] (Coloring agent) • LCV: Leucocrystal violet: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0251] (Rust inhibitor) • CBT-1: Carboxybenzotriazole, manufactured by Johoku Chemical Co., Ltd.

[0252] (Surfactants) • F-552: Megafuck F-552, manufactured by DIC Corporation.

[0253] (solvent) • MMPGAc: 1-Methoxy-2-propylacetate • MEK: Methyl ethyl ketone • MFG: Propylene glycol monomethyl ether

[0254] [Composition for forming intermediate layer] The intermediate layer of the transfer film was formed using an intermediate layer-forming composition. The materials shown in Tables 2 and 3 were mixed according to the formulations described in Tables 2 and 3 to obtain the intermediate layer-forming compositions used in the production of the transfer films in the examples and comparative examples.

[0255] (resin) • PVA: Polyvinyl alcohol, product name "Kuraray Poval PVA-205", manufactured by Kuraray Co., Ltd. • PVP: Polyvinylpyrrolidone, product name "Polyvinylpyrrolidone K-30", manufactured by Nippon Shokubai Co., Ltd.

[0256] (Surfactants) • F444: Megafuck F444, fluorine-based surfactant, manufactured by DIC Corporation.

[0257] (solvent) ·Pure water • MeOH: methanol

[0258] [Preparation of transfer film] Each transfer film used in each example was prepared, consisting of a temporary support, an intermediate layer, and a photosensitive composition layer. The transfer film used in the comparative example was prepared in the same manner as the transfer films in each example, except that it did not have an intermediate layer. Specifically, it was as follows: First, an intermediate layer-forming composition was applied to the surface of a temporary support (a 16 μm thick polyethylene terephthalate film (Lumirror® 16KS40, manufactured by Toray Industries, Inc.)) using a bar coater, so that the thickness after drying was 1.1 μm. The coated film was dried in an oven at 90°C to form an intermediate layer. Next, a photosensitive composition was applied to the surface of the formed intermediate layer using a bar coater to a thickness of 3.0 μm after drying. The coated film was dried in an oven at 80°C to form a photosensitive composition layer (negative type photosensitive composition layer). A 16 μm thick polyethylene terephthalate (16KS40, manufactured by Toray Industries, Inc.) protective film was pressed onto the obtained photosensitive composition layer to prepare a transfer film for use in each example or comparative example.

[0259] <Rating> [Formation of resist pattern] As a substrate with a metal layer, a copper-layered PET substrate was used, in which a 500 nm thick copper layer was formed on a 188 μm thick PET film (polyethylene terephthalate film) by sputtering. The transfer film prepared using the above procedure was cut into 50 cm squares, the protective film was peeled off, and the photosensitive composition layer was laminated onto a PET substrate with a copper layer under lamination conditions of roll temperature 90°C, linear pressure 0.8 MPa, and linear speed 3.0 m / min, so that the photosensitive composition layer was in contact with the copper layer on the surface of the PET substrate, to obtain a laminate. At this point, the laminate has the following configuration: "PET film - copper layer - photosensitive composition layer - intermediate layer - temporary support".

[0260] Next, the temporary support was peeled off the resulting laminate, exposing the intermediate layer (a photosensitive composition layer in Comparative Example 1) on the surface of the laminate. A photomask having a line (μm) / space (μm) ratio of 1 / 1 and line widths of 0.5-1.0 μm (increasing by 0.1 μm), 1.2-1.8 μm (increasing by 0.3 μm), and 2.0-10.0 μm (increasing by 1.0 μm) was brought into close contact with the exposed intermediate layer of the laminate. The photosensitive composition layer was exposed to the laminate by irradiating it with light using a high-pressure mercury lamp exposure machine (MAP-1200L, manufactured by Dainippon Kaken Co., Ltd., main wavelength: 365 nm). The exposure amount was set so that the resist pattern in the area corresponding to the 5 μm line-and-space shape of the photomask reproduced the 5 μm line-and-space shape after development. Subsequently, development was performed using a 1.0% sodium carbonate aqueous solution (pH=11.4) at 30°C as the developer. Specifically, the film was showered with the developer for 30 seconds, then the developer was removed using an AirKnife treatment, followed by a 30-second shower treatment with pure water, and then another AirKnife treatment. This resulted in a laminate having a line-and-space shaped resist pattern with a line width:space width ratio of 1:1. At this point, the laminate has the configuration of "PET film - copper layer - resist pattern".

[0261] [Formation of conductor patterns] The laminate obtained through the above process was immersed in an acidic degreasing agent (ATS Pure Clean N3, manufactured by Okuno Pharmaceutical Co., Ltd.) at a liquid temperature of 45°C for 5 minutes to perform acid degreasing treatment. Furthermore, it was immersed in 10% sulfuric acid at room temperature for 3 minutes to perform acid activation treatment. Place in copper sulfate plating solution (Toplutina SF, manufactured by Okuno Pharmaceutical Co., Ltd.) and apply at 1 A / dm 2 Copper plating was performed under the following conditions. After copper plating, the laminate was washed with water and dried, and then the resist pattern was removed by immersion in a 1% by mass potassium hydroxide aqueous solution (pH=13.5) at 50°C. The copper layer (seed layer) of the laminate after the resist pattern peeling step was removed with an aqueous solution containing 0.1% by mass sulfuric acid and 0.1% by mass hydrogen peroxide to obtain a conductor pattern (copper wiring pattern).

[0262] [Evaluation of conductor pattern formation ability] The conductor patterns were observed using a field emission scanning electron microscope (FE-SEM, JEOL JSM-7200F) to determine the minimum pattern line width corresponding to the above-mentioned photomask in which the conductor pattern could be formed without defects such as breaks, short circuits, or tilting. The minimum pattern line widths are shown in Tables 2 and 3. Based on the minimum pattern line width mentioned above, the conductor pattern formation ability was evaluated according to the following evaluation criteria. The evaluation results for conductor pattern formation ability are shown in Tables 2 and 3. Conductor pattern formation performance is better when the minimum pattern line width is small, and in practical terms, an evaluation of C or higher is preferable.

[0263] (Evaluation criteria for conductor pattern formation) A: Minimum pattern line width is 1.0 μm or less B: Minimum pattern line width greater than 1.0 μm and less than or equal to 1.5 μm C: Minimum pattern line width greater than 1.5 μm and less than or equal to 2.0 μm D: Minimum pattern line width exceeds 2.0 μm

[0264] <Result> Tables 2 and 3 show the composition of the intermediate layer and transfer film components for each example and comparative example, as well as the evaluation results of the conductor pattern formation properties. The components of the photosensitive composition and the intermediate layer forming composition in Tables 2 and 3 are as described above. In Tables 2 and 3, the content of each component is expressed in parts by mass. In Tables 2 and 3, the notation "polymerizable compound / resin" represents the ratio of the polymerizable compound content to the solid content of the resin.

[0265] [Table 2]

[0266] [Table 3]

[0267] The results in Tables 2 and 3 confirm that the method for manufacturing a laminate having a conductive pattern according to the present invention achieves the desired effect. From a comparison of Example 4 with other examples, it was confirmed that when the double bond content derived from the resin is greater than 0.20 mmol / g relative to the total mass of the photosensitive composition layer, the conductive pattern formation properties are superior. From a comparison of Examples 2, 7, and 10-12 with other examples, it was confirmed that when the double bond content derived from the resin is greater than 1.00 mmol / g relative to the total mass of the photosensitive composition layer, the conductive pattern formation properties are superior. From a comparison between Example 3 and the other examples, the exposure dose was 20 mJ / cm². 2 It was confirmed that when the glass transition temperature of the photosensitive composition layer after exposure with the i-line is 30°C or higher, the conductive pattern formation properties are superior. From a comparison of Example 4 with other examples, it was confirmed that when the resin contains structural units having groups with double bonds, and the content of such structural units is 10% by mass or more of the total mass of the resin, the conductive pattern-forming properties are superior. From a comparison of Example 9 with other examples, it was confirmed that when the weight-average molecular weight of the resin is between 3,000 and 18,000, the conductive pattern formation properties are superior.

[0268] [Examples 13-18] Transfer films used in Examples 13 to 18 were prepared in the same manner as in Examples 1 to 6, except that the photosensitive composition was applied so that the thickness of the photosensitive composition layer after drying was 19.0 μm. Using the transfer films used in Examples 13-18, resist patterns were formed in the same manner as in Examples 1-6, and conductive patterns were formed. However, for the formation of the resist patterns, a photomask was used with a line (μm) / space (μm) ratio of 1 / 1, and line widths of 0.5-1.0 μm (increasing by 0.1 μm), 1.2-1.8 μm (increasing by 0.3 μm), and 2.0-20.0 μm (increasing by 1.0 μm). The exposure amount was set so that the resist pattern in the portion of the photomask corresponding to the 10.0 μm line-and-space shape reproduced the 10.0 μm line-and-space shape after development. The formed conductor patterns were observed using a field emission scanning electron microscope in the same manner as described above, and the minimum pattern line width was confirmed. In Examples 13 to 18, the conductor pattern formation ability was evaluated based on the minimum pattern line width using the following evaluation criteria. The evaluation results for the minimum pattern line width and conductor pattern formation ability are shown in Table 4. Conductor pattern formation performance is better when the minimum pattern line width is small, and in practical terms, an evaluation of C or higher is preferable.

[0269] (Evaluation criteria for conductor pattern formation) A: Minimum pattern line width is 5.0 μm or less B: Minimum pattern line width greater than 5.0 μm and 6.0 μm or less C: Minimum pattern line width greater than 6.0 μm and 8.0 μm or less D: Minimum pattern line width exceeds 8.0 μm

[0270] [Table 4]

[0271] The results in Table 4 confirm that the method for manufacturing a laminate having a conductive pattern according to the present invention achieves the desired effect. A comparison of Example 16 with other examples confirmed that when the double bond content derived from the resin is greater than 0.20 mmol / g relative to the total mass of the photosensitive composition layer, the conductive pattern formation properties are superior. From a comparison of Example 14 with other examples, it was confirmed that when the double bond content derived from the resin is greater than 1.00 mmol / g relative to the total mass of the photosensitive composition layer, the conductive pattern formation properties are superior. From a comparison between Example 15 and other examples, the exposure dose was 20 mJ / cm². 2 It was confirmed that when the glass transition temperature of the photosensitive composition layer after exposure with the i-line is 30°C or higher, the conductive pattern formation properties are superior. From a comparison of Example 16 with other examples, it was confirmed that when the resin contains structural units having groups with double bonds, and the content of such structural units is 10% by mass or more of the total mass of the resin, the conductive pattern-forming properties are superior.

[0272] [Examples 19-25] In Example 2, the transfer films used in Examples 19 to 25 were prepared in the same manner as in Example 2, except that the types of surfactants used in the intermediate layer and the photosensitive composition layer were changed, as shown in Table 5 below. Using the transfer films used in Examples 19-25, resist patterns were formed in the same manner as in Example 2, and then conductive patterns were formed. The formed conductor patterns were observed using a field emission scanning electron microscope in the same manner as described above, and the minimum pattern line width was confirmed. In Examples 19 to 25, the conductor pattern formation ability was evaluated based on the minimum pattern line width using the same evaluation criteria as in Example 2. The evaluation results for the minimum pattern line width and conductor pattern formation ability are shown in Table 5.

[0273] In Table 5, the abbreviations for the surfactants used in the intermediate layer and the surfactants used in the photosensitive composition layer are as follows: (Surfactants) • F-552: Megafuck F-552, manufactured by DIC Corporation. • EXP.S-315: Silicone-based surfactant, manufactured by DIC. • EXP.S-503-2: Silicone-based surfactant, manufactured by DIC Corporation. • KP-124: Silicone-based surfactant, manufactured by Shin-Etsu Chemical Co., Ltd. • F444: Megafuck F444, fluorine-based surfactant, manufactured by DIC Corporation. • BYK-345: Silicone-based surfactant, manufactured by Big Chemie Japan Co., Ltd. • BYK-348: Silicone-based surfactant, manufactured by Big Chemie Japan Co., Ltd. • EXP.S-506: Silicone-based surfactant, manufactured by DIC Corporation.

[0274] [Table 5]

[0275] The results in Table 5 confirm that the manufacturing method for laminates having a conductive pattern according to the present invention achieves the desired effect, and Examples 19 to 25 yielded evaluation results similar to those of Example 2.

[0276] [Examples 101-107] Furthermore, the transfer films used in Examples 101 to 107 were prepared in the same manner as in Example 2, except that the protective film was changed to the one shown in Table 6 below. In Table 6, "P2" in the column for the type of photosensitive composition layer indicates that the same photosensitive composition layer as the one used in Example 2 was used. The transfer films used in Examples 101 to 107 were evaluated for their conductor pattern formation properties in the same manner as in Example 2, and the evaluation results were the same as in Example 2. Furthermore, when the transfer films used in Examples 101-107 were unwound and transported at a rate of 4 m / min, the transportability was good and no blocking occurred. Specifically, when the transfer films were transported using a roll-to-roll method, it was visually confirmed that no wrinkles or kinks occurred in the transfer films. In particular, when the transfer films used in Examples 101-106 were unwound and transported at a rate of 4 m / min, the transportability was even better.

[0277] [Examples 108-114] Furthermore, the transfer films used in Examples 108 to 114 were prepared in the same manner as in Example 14, except that the protective film was changed to the one shown in Table 6 below. In Table 6, "P14" in the column for the type of photosensitive composition layer indicates that the same photosensitive composition layer as the one used in Example 14 was used. The transfer films used in Examples 108 to 114 were evaluated for their conductor pattern formation properties in the same manner as in Example 14, and the evaluation results were the same as in Example 14. Furthermore, when the transfer films used in Examples 108-114 were unwound and transported at a rate of 4 m / min, the transportability was good and no blocking occurred. Specifically, when the transfer films were transported using a roll-to-roll method, it was visually confirmed that no wrinkles or kinks occurred in the transfer films. In particular, when the transfer films used in Examples 108-113 were unwound and transported at a rate of 4 m / min, the transportability was even better.

[0278] [Examples 115-121] Furthermore, in Examples 19 to 25, the transfer films used in Examples 115 to 121 were prepared in the same manner as in Examples 19 to 25, except that the protective film was changed to the one shown in Table 7 below. In Table 7, "P19" in the column for the type of photosensitive composition layer indicates that the same photosensitive composition layer as the one used in Example 19 was used, and the same applies to P20 to P25. The transfer films used in Examples 115 to 121 were evaluated for their conductor pattern formation properties in the same manner as in Examples 19 to 25, and the evaluation results were the same as in Examples 19 to 25. Furthermore, when the transfer films used in Examples 115 to 121 were unwound and transported at a rate of 4 m / min, the transportability was good and no blocking occurred. Specifically, it was visually confirmed that no wrinkles or kinks occurred in the transfer film when it was transported using a roll-to-roll method.

[0279] [Table 6]

[0280] [Table 7] [Explanation of Symbols]

[0281] 10 Transfer film 11 Temporary support 13. Middle Class 15 Photosensitive composition layer 17 Composition layer 19 Protective film

Claims

1. A transfer film having a temporary support and a photosensitive composition layer, The photosensitive composition layer comprises a resin having crosslinkable groups, The weight-average molecular weight of the aforementioned resin is 3000 or more. The mass ratio of polymerizable compounds other than the resin contained in the photosensitive composition layer to the resin is 0.85 or less. A transfer film in which the haze of the temporary support is 1.0% or less.

2. The double bond content derived from the resin is greater than 0.55 mmol / g relative to the total mass of the photosensitive composition layer. The transfer film according to claim 1, wherein the resin comprises constituent units derived from monomers having an alicyclic or polycyclic structure.

3. The double bond content derived from the resin is greater than 0.55 mmol / g relative to the total mass of the photosensitive composition layer. The transfer film according to claim 1 or 2, wherein the resin comprises structural units derived from a (meth)acrylate monomer having a hydrocarbon group having 9 or more carbon atoms.

4. The transfer film according to claim 3, wherein the hydrocarbon group has a branched chain.

5. The transfer film according to claim 1 or 2, wherein the weight-average molecular weight of the resin is 3,000 to 18,000.

6. The transfer film according to claim 1 or 2, wherein the thickness of the temporary support is 50 μm or less.

7. The photosensitive composition layer further comprises a sensitizer, The transfer film according to claim 1 or 2, wherein the sensitizer is selected from the group consisting of distylylbenzene derivatives, styrylpyridine derivatives, and anthracene derivatives.

8. The photosensitive composition layer further comprises a polymerizable compound, The transfer film according to claim 1 or 2, wherein the polymerizable compound comprises an alkylene oxide-modified bisphenol structure.

9. The transfer film according to claim 1 or 2, further comprising an intermediate layer between the temporary support and the photosensitive composition layer.

10. The transfer film according to claim 9, wherein the intermediate layer is a water-soluble resin layer.

11. A transfer film comprising the temporary support, the photosensitive composition layer, and a protective film in this order, The transfer film according to claim 1 or 2, wherein the arithmetic mean roughness Ra of the surface of the protective film opposite to the surface in contact with the photosensitive composition layer is greater than 0.05 μm.

12. A transfer film comprising the temporary support, the photosensitive composition layer, and a protective film in this order, The transfer film according to claim 1 or 2, wherein the protective film is a polypropylene film.

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