Method for producing laminate having conductor pattern, transfer film

Abstract

A method for manufacturing a laminate with a conductor pattern comprises, in sequence: a bonding step, wherein a transfer film is bonded to a substrate such that the surface of the transfer film opposite to the dummy support side contacts the metal layer of a substrate having a metal layer on its surface; an exposure step, wherein a photosensitive composition layer is exposed to a pattern; a development step, wherein a development process is performed to form a photoresist pattern; a heating step, wherein the photoresist pattern is heated; a cleaning step, wherein the heated photoresist pattern is cleaned with an acidic solution; an electroplating step, wherein an electroplating process is performed; a peeling step, wherein the photoresist pattern is peeled off; and a removal step, wherein the metal layer exposed by the peeling step is removed and a conductor pattern is formed on the substrate, wherein the photosensitive composition layer comprises a thermal crosslinking agent.

Description

Technical Field

[0001] This invention relates to a method for manufacturing a laminate with a conductor pattern and a transfer film. Prior Technology

[0002] The method of using a transfer film to deposit a photosensitive composition layer on any substrate, exposing the photosensitive composition layer through a mask, and then developing it is widely used because it requires few steps to obtain a predetermined pattern.

[0003] Patent document 1 discloses a method in which a photosensitive resin layer containing predetermined components is deposited on a support and the photosensitive resin layer is transferred to a substrate. A photoresist pattern is formed by exposure and development processes, and then an electroplating process is performed to manufacture a circuit board.

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2016-139154

[0005] Recently, there has been a demand for further miniaturization of the shape of conductor patterns, and the requirements for shape control have become even more stringent. The inventors referred to the method described in Patent Document 1 and performed an electroplating process by performing a cleaning process based on an acidic solution to remove dirt from the photoresist pattern before electroplating. As a result, they found that the shape of the obtained conductor pattern was deformed from the desired shape and needed to be improved. Summary of the Invention

[0006] The objective of this invention is to provide a method for manufacturing a laminate with a conductor pattern that can produce a conductor pattern of a desired shape even when the photoresist pattern has been cleaned with an acidic solution before electroplating. Furthermore, another objective of this invention is to provide a transfer film.

[0007] As a result of in-depth research into the above-mentioned problems, the inventors discovered that the above-mentioned problems can be solved by the following configuration.

[0008] (1) A method for manufacturing a laminate with a conductor pattern, comprising, in sequence: In the bonding step, the transfer film, which has a dummy support and a negative-type photosensitive component layer, is bonded to the substrate by contacting the surface of the transfer film opposite to the dummy support side with the metal layer of the substrate. The exposure step involves patterning the photosensitive constituent layer. The developing step involves developing the exposed photosensitive component layer to form a photoresist pattern; The heating step involves heating the photoresist pattern. The cleaning step involves cleaning the heated photoresist pattern with an acidic solution. The electroplating step involves electroplating the metal layer in areas where no photoresist pattern is configured. The stripping step involves stripping the photoresist pattern; and The removal step removes the metal layer exposed during the stripping step and forms a conductor pattern on the substrate. Between the bonding step and the exposure step, or between the exposure step and the development step, there is a further step of removing the dummy support. The photosensitive component layer contains a thermal crosslinking agent. (2) The method for manufacturing a laminate with a conductor pattern as described in (1), wherein The elastic modulus of the surface of the photoresist pattern heated by the heating step, on the side opposite to the substrate, is 5.0 GPa or higher. (3) A method for manufacturing a laminate with a conductor pattern as described in (1) or (2), wherein The elastic modulus of the surface of the photoresist pattern heated by the heating step, on the side opposite to the substrate, is defined as the elastic modulus X. When the elastic modulus near the substrate side of the photoresist pattern heated by the heating step is set as the elastic modulus Y, The condition X / Y ≤ 1.2 is satisfied. (4) A method for manufacturing a laminate with a conductor pattern as described in any one of (1) to (3), wherein The photosensitive composition layer contains polymerizable compounds and polymerization initiators. (5) The method for manufacturing a laminate with a conductor pattern as described in (4), wherein The polymerizable compound has an epoxide-modified bisphenol structure. (6) A method for manufacturing a laminate with a conductor pattern as described in any one of (1) to (5), wherein The thermal crosslinking agent contains a capped isocyanate compound. (7) A method for manufacturing a laminate with a conductor pattern as described in any one of (1) to (6), wherein The haze of the pseudo-support is below 1.0%. (8) A method for manufacturing a laminate with a conductor pattern as described in any one of (1) to (7), wherein The thickness of the pseudo-support is less than 50 μm. (9) A method for manufacturing a laminate with a conductor pattern as described in any one of (1) to (8), wherein The transfer film has an intermediate layer between the pseudo-support and the photosensitive component layer. (10) A method for manufacturing a laminate with a conductor pattern as described in (9), wherein The middle layer is a water-soluble resin layer. (11) A method for manufacturing a laminate with a conductor pattern as described in any one of (1) to (10), wherein The exposure step involves exposing the pattern to a photomask. (12) A method for manufacturing a laminate with a conductor pattern as described in any one of (1) to (10), wherein The exposure step involves using active light projected onto an image of a photomask and exposing the photosensitive constituent layer to a pattern via a lens. (13) A method for manufacturing a laminate with a conductor pattern as described in any one of (1) to (10), wherein There is a pseudo-support peeling step between the bonding step and the exposure step. The exposure step is a step of patterning the photosensitive composition layer by bringing the surface exposed after the dummy support is peeled off into contact with the photomask. (14) A transfer film having a pseudo-support and a negative photosensitive component layer, wherein The photosensitive component layer contains a thermal crosslinking agent. The haze of the pseudo-support is below 1.0%. (15) The transfer film as described in (14), wherein The thickness of the pseudo-support is less than 50 μm. (16) The transfer film as described in (14) or (15), wherein The photosensitive composition layer contains polymerizable compounds and polymerization initiators. (17) The transfer film as described in (16), wherein The polymerizable compound has an epoxide-modified bisphenol structure. (18) The transfer film as described in any one of (14) to (17) has an intermediate layer between the pseudo-support and the photosensitive component layer. (19) The transfer film as described in (18), wherein The middle layer is a water-soluble resin layer. [Invention Effects]

[0009] According to the present invention, a method for manufacturing a laminate with a conductor pattern is provided, which can produce a conductor pattern of a desired shape even when the photoresist pattern has been cleaned with an acidic solution before electroplating. Furthermore, according to the present invention, a transfer film can be provided. Simple Explanation of the Diagram

[0010] Figure 1 is a schematic diagram showing an example of the layer composition of the transfer film in an embodiment. Implementation

[0011] The present invention will now be described in detail. The description of the constituent elements described below is sometimes based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0012] The following explains the meaning of each statement in this specification. In this specification, the numerical range represented by "~" refers to the range including the values ​​recorded before and after "~" as the lower and upper limits. In this specification, within the numerical ranges described in stages, the upper or lower limit value recorded in a certain numerical range can be replaced with the upper or lower limit value of a numerical range described in other stages. Furthermore, within the numerical ranges described in this specification, the upper or lower limit value recorded in a certain numerical range can also be replaced with the values ​​shown in the embodiments.

[0013] In this specification, the term "step" includes not only independent steps, but also steps that achieve their intended purpose, even if they cannot be clearly distinguished from other steps.

[0014] In this specification, "transparent" means that the average transmittance of visible light with a wavelength of 400~700nm is above 80%, and above 90% is preferred. In this specification, the average transmittance of visible light is a value measured using a spectrophotometer, such as the Hitachi U-3310 spectrophotometer manufactured by Hitachi, Ltd.

[0015] Unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) in this specification are values ​​converted from polystyrene measured using a gel permeation chromatography (GPC) analyzer with TSKgel GMHxL, TSKgel G4000HxL or TSKgel G2000HxL (all trade names manufactured by TOSOH CORPORATION) as the column, THF (tetrahydrofuran) as the eluent, a differential refractometer as the detector, and polystyrene as the standard. Unless otherwise specified, the molecular weight of compounds with molecular weight distribution in this specification is the weight average molecular weight (Mw). Unless otherwise specified, the content of metal elements in this specification is measured using an inductively coupled plasma (ICP) spectrophotometer. Unless otherwise specified, the refractive index in this specification is the value measured using an ellipsometer at a wavelength of 550 nm. Unless otherwise specified, the hue values ​​in this manual are measured using a colorimeter (CR-221, manufactured by Minolta Co., Ltd.).

[0016] In this specification, "(meth)acrylic" includes both acrylic and methacrylic groups, and "(meth)acryloxy" includes both acryloxy and methacryloxy groups.

[0017] In addition, in this specification, "alkali solubility" means that the solubility of 100g of a 1% by mass aqueous solution of sodium carbonate at 22°C is 0.1g or more.

[0018] In this specification, "water-soluble" means having a solubility of 0.1g or more in 100g of water at pH 7.0 and a liquid temperature of 22°C. Therefore, for example, a water-soluble resin refers to a resin that meets the above solubility requirement.

[0019] In this specification, "solid component" refers to the component that forms the composition layer formed using the composition. When the composition contains a solvent (organic solvent, water, etc.), it refers to all components other than the solvent. Furthermore, if it is a component that forms the composition layer, liquid components are also considered solid components.

[0020] As a feature of the manufacturing method of the laminate with conductor pattern of the present invention, the following point can be cited: the photosensitive composition layer contains a thermal crosslinking agent. Based on prior art research into the causes of the aforementioned problems, the inventors discovered that cleaning photoresist patterns with acidic solutions can cause the photoresist patterns to peel off or decompose, resulting in the inability to obtain conductor patterns of the desired shape. Therefore, they discovered that by including a thermal crosslinking agent in the photosensitive composition layer and performing a heat treatment after development to crosslink the photoresist pattern, the resistance to acidic solutions is improved, resulting in conductor patterns of the desired shape.

[0021] <Method for manufacturing laminates with conductor patterns> The method for manufacturing a laminate with a conductor pattern according to the present invention includes, in sequence: In the bonding step, the transfer film, which has a dummy support and a negative-type photosensitive component layer, is bonded to the substrate by contacting the surface of the transfer film opposite to the dummy support side with the metal layer of the substrate. The exposure step involves patterning the photosensitive constituent layer. The developing step involves developing the exposed photosensitive component layer to form a photoresist pattern; The heating step involves heating the photoresist pattern. The cleaning step involves cleaning the heated photoresist pattern with an acidic solution. The electroplating step involves electroplating the metal layer in areas where no photoresist pattern is configured. The stripping step involves stripping the photoresist pattern; and The removal step removes the metal layer exposed during the stripping step and forms a conductor pattern on the substrate. Between the bonding step and the exposure step, or between the exposure step and the development step, there is a pseudo-support peeling step to peel off the pseudo-support. The following is a detailed description of each step.

[0022] [Adhesion Steps] The bonding step involves bonding the transfer film to the substrate by contacting the surface of the transfer film, which has a dummy support and a negative photosensitive composition layer, opposite to the dummy support side, with the metal layer of the substrate having a metal layer on its surface. By performing this step, a substrate with a photosensitive composition layer that sequentially comprises a substrate, a metal layer, a photosensitive composition layer, and a dummy support can be obtained.

[0023] The composition of the transfer film will be described in detail later.

[0024] A substrate with a metal layer on its surface (a substrate with a metal layer) has 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. Polyethylene terephthalate, cyclic olefin polymers, or polyimide are preferred materials for resin substrates. A thickness of 5~200μm for the resin substrate is preferred, and 10~100μm is even better.

[0025] A metal layer system comprises a layer of metal. The metal itself is not particularly restricted and can be any known metal. It is preferable that the metal layer is a conductive layer. Examples of main components (so-called main metals) in a metal layer include copper, chromium, lead, nickel, gold, silver, tin, and zinc. Furthermore, "main component" refers to the metal with the highest abundance among the metals contained in the metal layer.

[0026] The method for forming a metal layer is not particularly limited. For example, known methods such as coating a dispersion of metal particles and sintering the coating, sputtering, and deposition can be cited.

[0027] The thickness of the metal layer is not particularly limited, but 50 nm or more is preferred, and 100 nm or more is even better. The upper limit is preferably below 2 μm.

[0028] One or more metal layers can be disposed on the substrate. When configuring two or more metal layers, the metal layers can be the same or different from each other, with metal layers of different materials being preferred.

[0029] In the above bonding process, it is preferable to press the photosensitive component layer side of the transfer film (the surface opposite to the dummy support side) into contact with the metal layer on the substrate. There are no particular limitations on the above-mentioned lamination method, and known transfer and lamination methods can be used. Among them, it is preferable to overlap the surface of the photosensitive component layer onto a substrate with a metal layer and apply pressure and heat based on rollers or the like. The bonding process can utilize known laminators such as vacuum laminators and automatic cutting laminators. The lamination temperature is not particularly limited, but 70~130℃ is preferred.

[0030] [Exposure Steps] The exposure step is a step of patterning the photosensitive constituent layer. "Pattern exposure" refers to an exposure that presents a pattern, meaning that there are exposed and unexposed areas. The positional relationship between the exposed and unexposed areas in pattern exposure can be adjusted appropriately. Exposure is preferably performed from the photosensitive component layer side.

[0031] Exposure methods in the exposure process include masking exposure, direct imaging exposure, and projection exposure, with masking exposure or projection exposure being preferred. In other words, as an exposure step, it is better to expose the pattern through a photomask. Furthermore, as an exposure step, it is also preferable to use active light that projects an image onto a photomask and exposes the photosensitive composition layer in a pattern via a lens.

[0032] When the dummy support peeling step (described later) is performed between the bonding step and the exposure step, it is preferable to perform an exposure step in which the exposed surface of the peeled dummy support contacts the photomask for pattern exposure. In other words, it is preferable to perform an exposure step in which the exposed surface of the laminate, where the dummy support has been peeled off, contacts the photomask for pattern exposure of the photosensitive composition layer. Furthermore, when the transfer film is composed of three layers—a dummy support, an intermediate layer, and a photosensitive composition layer—the surface of the intermediate layer corresponds to this exposed surface. If this exposure step is used, a finer photoresist pattern can be obtained, which in turn can result in a finer conductor pattern. When performing the pseudo-support peeling step described later, it is preferable to use this exposure step, especially between the bonding step and the exposure step. Furthermore, when the pseudo-support peeling step (described later) is performed between the exposure step and the development step, it is preferable to perform an exposure step in which the surface of the transfer film in the laminate of the substrate and the transfer film obtained by the bonding step, opposite to the side with the substrate, comes into contact with the photomask to expose the pattern.

[0033] During the exposure step of pattern exposure, a hardening reaction occurs in the exposed area of ​​the photosensitive composition layer (corresponding to the opening of the photomask), causing the components contained in the photosensitive composition layer to harden. By performing a development step after exposure, the unexposed areas of the photosensitive composition layer are removed, thus forming a pattern.

[0034] The method of the present invention is preferably further characterized by a photomask stripping step between the exposure step and the development step, whereby the photomask used in the exposure step is stripped. As a photomask stripping step, well-known stripping steps can be cited as examples.

[0035] As a light source for pattern exposure, any light capable of illuminating a wavelength range sufficient to harden the photosensitive composition layer (e.g., 365nm or 405nm) can be appropriately selected. Among these, a dominant wavelength of 365nm is preferred for pattern exposure. Furthermore, the dominant wavelength is the wavelength with the highest intensity.

[0036] As light sources, examples include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps. An exposure of 5~200mJ / cm² is preferred, and 10~200mJ / cm² is even better.

[0037] Preferred examples of light sources, exposure amounts, and exposure methods used in exposure are described, for example, in paragraphs

[0146] to

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

[0038] [Steps for removing the pseudo-support] A pseudo-support peeling step is performed between the bonding step and the exposure step, or between the exposure step and the development step. It is preferable to have a pseudo-support peeling step between the above-mentioned bonding step and the above-mentioned exposure step. The pseudo-support peeling step is the step of peeling the pseudo-support from the laminate between the transfer film and the substrate with the metal layer. As a method for peeling off the pseudo-support, well-known peeling methods can be cited, for example. Specifically, the covering film peeling mechanism described in paragraphs

[0161] to

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

[0039] [Developing Steps] The developing step is a process of developing the exposed photosensitive component layer to form a photoresist pattern. The development of the aforementioned photosensitive component layer can be performed using a developing solution. An alkaline aqueous solution is preferred as a developer. Examples of alkaline compounds that may be contained in an 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).

[0040] The optimal temperature of the developing solution during the developing process is 10~50℃, 15~40℃ is even better, and 20~35℃ is even better. The pH of the developer solution used for developing is preferably 9 or higher, more preferably 10 or higher, and even more preferably 11 or higher. A pH of 14 or lower is preferred, and a pH below 13 is even better. The pH can be measured using a known pH meter in accordance with JIS Z8802-1984. The pH measurement temperature is set to 25°C.

[0041] In the developer, a water content of 50% to 100% by mass relative to the total mass of the developer is preferred, and 90% to 100% by mass is even better. In the developer, the content of alkaline compounds is preferably 0.01~20% by mass relative to the total mass of the developer, and even more preferably 0.1~10% by mass.

[0042] Examples of development methods include rotary immersion development, spray development, rotational development, and immersion development.

[0043] As a preferred developer used in this specification, for example, the developer described in paragraph

[0194] of International Publication No. 2015 / 093271 can be cited as an example. As a preferred developing method, for example, the developing method described in paragraph

[0195] of International Publication No. 2015 / 093271 can be cited as an example.

[0044] It is preferable to perform a rinsing process to remove residual developer from the substrate with the metal layer after development and before moving to the next step. Water or similar substances can be used in the rinsing process. After development and / or rinsing, a drying process can be performed to remove excess liquid from the substrate with the metal layer.

[0045] The position and size of the photoresist pattern formed on the substrate with the metal layer are not particularly limited, but fine lines are preferred. Specifically, a linewidth of less than 20 μm for the photoresist pattern is preferred, less than 15 μm is even better, less than 10 μm is further preferred, and less than 5 μm is exceptionally good. Linewidths above 1.0 μm are more common.

[0046] [Heating Steps] The heating step involves heating the photoresist pattern. By performing this step, a cross-linked structure is formed in the photoresist pattern by the thermal cross-linking agent described later, which imparts resistance to cleaning with an acidic solution in the cleaning step described later. The heating temperature is not particularly limited, but 100~200℃ is preferred, and 120~150℃ is even better. There is no particular limitation on the heating time, but 10 to 60 minutes is preferred, and 20 to 40 minutes is even better.

[0047] The elastic modulus of the surface of the photoresist pattern heated by the heating step, on the side opposite to the substrate, is not particularly limited. However, from the viewpoint of achieving better results in this invention, 5.0 GPa or higher is preferred, and 5.5 GPa or higher is even better. The upper limit is not particularly limited, but it is often below 7.0 GPa. The method for measuring the above-mentioned elastic modulus is as follows. The elastic modulus was measured using atomic force microscopy (AFM). The specific procedure is as follows: Measurements were performed in QNM mode using an atomic force microscope (e.g., the Bruker Dimension Icon AFM). An RTESA-150 probe (150 kHz, 5 N / m) was used as a probe. Force curves were measured at 5 fields (1 μm square) for a total of 50 points (10 points per field). Using Hertz contact theory, the elastic modulus was calculated from the slope of the return force curve (the region of 20% to 90% of the maximum load). Furthermore, the specific example of AFM probe calibration is as follows: The force curve of the quartz substrate was measured beforehand, and the warpage sensitivity was calculated from the slope of the force curve. The spring constant was calculated by measuring the thermal fluctuations of the probe. For example, the spring constant was calculated using the thermal tuning method included in the AFM software manufactured by Bruker. The shape of the front curvature correction sample (RM-12M: Ti Roughness Sample) is measured, for example, by using the image analysis mode (Tip Qualification) included with the AFM software manufactured by Bruker to calculate the front curvature.

[0048] When the elastic modulus of the surface opposite to the substrate side of the photoresist pattern heated by the heating step is defined as elastic modulus X, and the elastic modulus near the substrate side of the photoresist pattern heated by the heating step is defined as elastic modulus Y, X / Y is not particularly limited. However, from the viewpoint of achieving better results in this invention, X / Y is preferred to be 1.20 or less, and X / Y is even more preferred to be 1.10 or less. The lower limit is not particularly limited, but X / Y is preferred to be 1.05 or more. The above-mentioned method for measuring the elastic modulus X can be exemplified by the method based on the atomic force microscope (AFM) described above. The method for measuring the elastic modulus Y is as follows. Along the thickness direction, the photoresist pattern is cut using a slicing machine to expose its vertical cross-section. The elastic modulus at any position within this vertical cross-section, representing 0-20% of the overall thickness of the photoresist pattern from the substrate, is measured using the same method as for the elastic modulus X. This value is then taken as the elastic modulus Y. In other words, the area near the substrate side of the photoresist pattern refers to the range within the vertical cross-section of the photoresist pattern, representing 0-20% of the overall thickness of the photoresist pattern from the substrate.

[0049] [Cleaning Steps] The cleaning step involves cleaning the photoresist pattern heated during the heating step with an acidic solution. As an acidic solution, it is not particularly restricted as long as it contains acid. Examples of acids in acidic solutions include sulfuric acid, nitric acid, hydrogen chloride, phosphoric acid, hydrofluoric acid, sulfonic acid, and oxalic acid. The concentration of acid in an acidic solution is not particularly limited, but a concentration of acid component relative to the total mass of the acidic solution of 5-30% by mass is preferred, and 10-20% by mass is even better.

[0050] It is preferable for acidic solutions to contain solvents. Examples of solvents include water and organic solvents. Examples of organic solvents include alcohol solvents, ester solvents, ketone solvents, amide solvents, and hydrocarbon solvents.

[0051] There are no particular limitations on the method of cleaning photoresist patterns with acidic solutions, as long as the photoresist pattern can come into contact with the acidic solution. For example, methods such as supplying acidic solution to the photoresist pattern and immersing the photoresist pattern in acidic solution can be cited. The contact time between the photoresist pattern and the acidic solution is not particularly limited, but 1 to 20 minutes is preferred, and 3 to 10 minutes is even better. The ideal temperature for the acidic solution when the photoresist pattern comes into contact with the acidic solution is 25~50℃, and even better is 30~40℃.

[0052] [Electroplating Steps] The electroplating step is a process of electroplating the metal layer located in the area where no photoresist pattern is configured. By performing this step, an electroplated layer can be formed on a metal layer located in an area where no photoresist pattern is configured.

[0053] As for electroplating methods, examples include electrolytic electroplating and electroless electroplating. From a production point of view, electrolytic electroplating is better. If an electroplating step is performed, an electroplated layer with the same pattern shape as the area (opening of the photoresist pattern) without a photoresist pattern can be obtained on the substrate with the metal layer.

[0054] As for the metal contained in the electroplated layer, well-known metals can be cited as examples. Specifically, examples include metals such as copper, chromium, lead, nickel, gold, silver, tin, and zinc, as well as alloys of these metals. From the viewpoint of superior conductivity of the conductor pattern, it is preferable that the electroplated layer contains copper or its alloy. Furthermore, from the viewpoint of superior conductivity of the conductor pattern, it is preferable that the electroplated layer contains copper as a main component.

[0055] For the thickness of the electroplated layer, 0.1 μm or more is preferred, and 1 μm or more is even better. The upper limit is 20 μm or less, which is preferred.

[0056] [Peeling Steps] The stripping step is the step of stripping the photoresist pattern. There are no particular limitations on the method for removing residual photoresist patterns. Methods such as removal by chemical treatment can be cited, but removal by stripping solution is preferred. Alternatively, stripping fluid can be used and known methods such as spraying, spraying, and immersion can be employed to remove it.

[0057] Examples of stripping solutions include those made by dissolving an inorganic or organic base in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixture thereof. Examples of inorganic bases include sodium hydroxide and potassium hydroxide. Examples of organic bases include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds. Tetramethylammonium hydroxide or alkanolamine compounds are preferred as basic organic compounds. It is also preferable that the stripping solution does not dissolve the metal layer.

[0058] As a method for removing photoresist patterns, one example is to immerse a substrate with residual photoresist patterns in a stirring stripping solution at a preferred temperature of 30-80°C, more preferably 50-80°C, for 1-30 minutes.

[0059] The pH of the stripping solution used for 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 even better if it is below 13.8. The pH can be measured using a known pH meter in accordance with the method of JIS Z8802-1984. The pH measurement temperature is set to 25°C. It is preferable that the temperature of the stripping solution during the stripping process is higher than the temperature of the developing solution during the developing process. Specifically, it is preferable that the difference between the temperature of the stripping solution and the temperature of the developing solution (the temperature of the stripping solution - the temperature of the developing solution) is 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. It is preferable that the pH of the stripping solution during the stripping process is higher than the pH of the developing solution during the developing process. Specifically, it is preferable that the value of 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 1 or higher, and more preferably 1.5 or higher. It is preferable that the upper limit is 5 or lower, and more preferably 4 or lower.

[0060] After stripping the photoresist pattern using a stripping solution, it is preferable to perform a rinsing process to remove any remaining stripping solution from the substrate. Water or similar substances can be used during the rinsing process. After the photoresist pattern is stripped and / or rinsed using the stripping fluid, a drying process can be performed to remove excess fluid from the substrate.

[0061] [Removal Steps] The removal step is the step of removing the metal layer exposed by the stripping step and forming a conductor pattern on the substrate. In the removal step, the electroplated layer formed by the electroplating step is used as an etching resist to perform etching of the metal layer located in the non-patterning area (in other words, the area not protected by the electroplated layer).

[0062] As part of the process of removing the metal layer, there are no particular restrictions, and it is preferable to use a known etching solution. Examples of known etching solutions include ferric chloride solution, copper chloride solution, ammonia-alkali solution, sulfuric acid-hydrogen peroxide mixture, and phosphoric acid-hydrogen peroxide mixture.

[0063] If a removal step is performed, the exposed metal layer on the surface is removed from the substrate, and an electroplated layer (conductor pattern) with a patterned shape remains, thereby obtaining a laminate with a conductor pattern.

[0064] The upper limit for the linewidth of the formed conductor pattern is preferably below 8 μm, and even better below 6 μm. The lower limit is not particularly limited, but is often above 1 μm.

[0065] [Other steps] The method for manufacturing a laminate with a conductor pattern may include any steps other than those described above (other steps). For example, the steps of reducing visible light reflectivity described in paragraph

[0172] of International Publication No. 2019 / 022089, and the steps of forming a new metal layer on an insulating film described in paragraph

[0172] of International Publication No. 2019 / 022089, can be cited, but are not limited to these steps.

[0066] -Steps to reduce visible light reflectivity- A method for manufacturing a laminate with a conductor pattern may include a step of performing a process to reduce the visible light reflectivity of some or all of the plurality of metal layers on the substrate. As a method to reduce visible light reflectivity, oxidation treatment can be cited. When the substrate has a metal layer containing copper, the copper is oxidized to become copper oxide, and the metal layer is blackened, thereby reducing the visible light reflectivity of the metal layer. Regarding the treatment of reducing visible light reflectivity, paragraphs

[0017] to

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

[0041] ,

[0042] ,

[0048] and

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

[0067] -The steps of forming an insulating film and forming a new metal layer on the surface of the insulating film- A method for manufacturing a multilayer with a conductor pattern that includes the steps of forming an insulating film on the surface of the circuit wiring and forming a new metal layer on the surface of the insulating film is also preferred. Through the above steps, a second electrode pattern that is insulated from the first electrode pattern can be formed. The steps for forming the insulating film are not particularly limited, and well-known methods for forming permanent films can be cited. Alternatively, an insulating film with the desired pattern can be formed by using photolithography with a photosensitive material that has insulating properties.

[0068] In the manufacturing method of the laminate with conductor patterns, it is preferable to use a substrate having a plurality of metal layers on each of the two surfaces of the substrate, and to form circuits sequentially or simultaneously on the metal layers formed on the two surfaces of the substrate. With this configuration, it is possible to form touch panel circuit wiring with a first conductor pattern formed on one surface of the substrate and a second conductor pattern formed on the other surface. Furthermore, it is also preferable to form this type of touch panel circuit wiring from both sides of the substrate in a roll-to-roll manner.

[0069] Applications of laminates with conductor patterns The manufacturing method of the laminate with conductor pattern can be applied to the manufacture of conductive films such as touch panels, transparent heaters, transparent antennas, electromagnetic wave shielding materials and dimming films; the manufacture of printed wiring boards and semiconductor packages; the manufacture of pillars and pins for interconnection between semiconductor wafers or packages; the manufacture of metal masks; and the manufacture of strip substrates such as COF (Chip on Film) and TAB (Tape Automated Bonding). Furthermore, an electrostatic capacitive touch panel can be cited as an example of the aforementioned touch panel. The manufacturing method of the laminate of the present invention can be used for the formation of conductive films or peripheral circuit wiring in a touch panel. The aforementioned touch panel can be applied, for example, to display devices such as organic EL (electroluminescence) display devices and liquid crystal display devices.

[0070] <Transfer film> The transfer film used in the manufacturing method of the laminate with conductor pattern of the present invention has a pseudo-support and a negative photosensitive composition layer, the photosensitive composition layer containing a thermal crosslinking agent. In addition to the pseudo-support and photosensitive component layer, the transfer film may have other layers. Other layers include, for example, the intermediate layer described later. Furthermore, the transfer film may have other components described later (e.g., a protective film, etc.).

[0071] As an embodiment of the transfer film, examples of configurations (1) or (2) can be given, with configuration (2) being preferred. (1) "Pseudo-support / Photosensitive component layer / protective film" (2) "Pseudo-support / intermediate layer / photosensitive component layer / protective film" A transfer film with an intermediate layer is preferable.

[0072] From the viewpoint of suppressing the generation of air bubbles in the above-mentioned bonding step, it is preferable that the maximum width of the ripples in the transfer film is 300 μm or less, more preferably 200 μm or less, and even more preferably 60 μm or less. In addition, as a lower limit for the maximum width of the ripples, it is preferable that it is 0 μm or more, 0.1 μm or more, and even more preferably 1 μm or more. The maximum width of the corrugations on the transfer film is measured using the following procedure. First, test samples were prepared by cutting the transfer film to 20cm x 20cm dimensions perpendicular to the main surface. If the transfer film had a protective film, the protective film was peeled off. Next, the test samples were placed on a smooth, level worktable with the surface of the dummy support facing the worktable. After standing, a three-dimensional surface image was obtained by scanning the surface of the test sample within a 10cm square area at its center using a laser microscope (e.g., a VK-9700SP manufactured by KEYENCE CORPORATION). The maximum convex height observed in the obtained three-dimensional surface image was subtracted from the minimum concave height. This process was performed on 10 test samples, and the arithmetic mean was taken as the "maximum ripple width of the transfer film".

[0073] In the photosensitive component layer of the transfer film, when other component layers are further present on the surface of the photosensitive component layer opposite to the dummy support, the total thickness of the other component layers relative to the total thickness of the photosensitive component layer is preferably 0.1~30%, and more preferably 0.1~20%.

[0074] From the perspective of superior adhesion, a transmittance of 365nm light in the photosensitive component layer of 10% or higher is preferred, 30% or higher is even better, and 50% or higher is further preferred. An upper limit of 99.9% or lower is preferred, and 99.0% or lower is even better.

[0075] Examples of implementation forms of transfer films are explained. The transfer film 10 shown in Figure 1 has a pseudo-support 11, a composition layer 17 including an intermediate layer 13 and a photosensitive composition layer 15, and a protective film 19 in sequence. The transfer film 10 shown in Figure 1 has an intermediate layer 13 and a protective film 19, but it may also be without the intermediate layer 13 and the protective film 19. In Figure 1, the layers other than the protective film 19 that can be disposed on the pseudo-support 11 (e.g., photosensitive composition layers and intermediate layers) are also referred to as "composition layers".

[0076] The following is a detailed description of each component and element of the transfer film.

[0077] [Pseudo-support] The transfer film has a pseudo-support. The pseudo-support system, which supports the photosensitive component layer, is ultimately removed through a peeling process.

[0078] The pseudo-support can be either a single-layer structure or a multi-layer structure. As a pseudo-support, a thin film is preferred, and a resin film is even better. Furthermore, as a pseudo-support, a thin film that is flexible and does not exhibit significant deformation, shrinkage, or elongation under pressure or under pressure and heat is also preferred, as is a thin film without wrinkles or other deformations and scratches. Examples of films include polyethylene terephthalate films (e.g., biaxially stretched polyethylene terephthalate films), polymethyl methacrylate films, cellulose triacetate films, polystyrene films, polyimide films, and polycarbonate films, with polyethylene terephthalate films being preferred.

[0079] From the perspective of being able to expose patterns through a dummy support, higher transparency of the dummy support is better, a transmittance of 60% or more at 365nm is better, and 70% or more is even better. From the viewpoint of pattern formation during exposure of a pattern via a dummy support and the transparency of the dummy support, a low haze of the dummy support is preferable. Specifically, a haze value of 2.0% or less is preferable, 1.0% or less is even better, and 0.5% or less is further preferable. The lower limit is not particularly limited, and values ​​of 0.1% or more can be cited as examples. From the viewpoint of pattern formation and transparency of the dummy support during pattern exposure, it is preferable to have a low number of particles, foreign objects, and defects contained in the dummy support. It is preferable that the number of particles, foreign objects, and defects with a diameter of 1 μm or larger in the dummy support is 50 or less per 10 mm², more preferably 10 or less per 10 mm², further preferably 3 or less per 10 mm², and especially preferably 0 per 10 mm².

[0080] A thickness of 5 μm or more for the dummy support is preferred. An upper limit of 200 μm or less is preferred. From the viewpoint of ease of operation and versatility, 150 μm or less is preferred, 50 μm or less is even better, 20 μm or less is excellent, and 16 μm or less is optimal. The thickness of the pseudo-support was calculated as the average of any five points measured by cross-sectional observation using SEM (Scanning Electron Microscope).

[0081] From a processing point of view, a pseudo-support can have a layer containing microparticles (lubricant layer) on one or both sides of the pseudo-support. The diameter of the particles contained in the lubricant layer is preferably 0.05~0.8μm. A lubricant layer thickness of 0.05~1.0μm is preferred.

[0082] From the perspective of improving the adhesion between the pseudo-support and the photosensitive composition layer, the surface of the pseudo-support in contact with the photosensitive composition layer can be modified. As a surface modification treatment, examples include treatments such as UV irradiation, corona discharge, and plasma. The optimal exposure level for UV irradiation is 10~2000mJ / cm², and even better is 50~1000mJ / cm². If the exposure is within the above range, the lamp output and illuminance are not subject to any special restrictions. Examples of light sources used 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 150-450nm wavelength range.

[0083] Examples of pseudo-supports include biaxially stretched polyethylene terephthalate (PET) films with a thickness of 16 μm, 12 μm, and 9 μm. Furthermore, as pseudo-supporting elements, examples include paragraphs

[0017] to

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

[0019] to

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

[0041] to

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

[0029] to

[0040] of International Publication No. 2018 / 179370, all of which are incorporated into this specification. Commercially available products that serve as pseudo-supports include, for example, the registered trademarks LUMIRROR 16KS40 and LUMIRROR 16FB40 (manufactured by TORAY INDUSTRIES, INC.); Cosmoshine A4100, Cosmoshine A4300, and Cosmoshine A8300 (manufactured by Toyobo Co., Ltd.).

[0084] [Photosensitive constituent layer] The transfer film has a negative photosensitive component layer. The components contained in the photosensitive composition layer will be described in order below. Furthermore, the description will begin with the thermal crosslinking agent, which is one of the characteristic features of this invention.

[0085] (Thermal crosslinking agent) The photosensitive component layer contains a thermal crosslinking agent. Examples of thermal crosslinking agents include hydroxymethyl compounds and end-capped isocyanate compounds. Among these, end-capped isocyanate compounds are preferred from the viewpoint of the strength of the resulting cured film and the adhesiveness of the resulting uncured film. The capped isocyanate compound reacts with hydroxyl and carboxyl groups, so when, for example, the resin and / or polymeric compound has at least one of hydroxyl and carboxyl groups, the hydrophilicity of the formed film decreases, and it tends to enhance the function of the film formed by curing the negative photosensitive component layer as a protective film. In addition, capped isocyanate compounds refer to "compounds having a structure in which the isocyanate group of the isocyanate is protected (so-called masking) by a capping agent".

[0086] The dissociation temperature of capped isocyanate compounds is not particularly limited, but 100~160℃ is preferred, and 130~150℃ is even better. The dissociation temperature of capped isocyanates refers to "the temperature of the endothermic peak accompanying the deprotection reaction of capped isocyanates when measured using a differential scanning calorimeter and analyzed by DSC (Differential scanning calorimetry)". As a differential scanning calorimeter, the differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. is preferred, for example. However, the differential scanning calorimeter is not limited to this.

[0087] Examples of end-capping agents with dissociation temperatures of 100-160°C include active methylene compounds (malonate (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)) and oxime compounds (formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime, etc., which have the structure represented by -C (=N-OH)- in the molecule). Among these, at least one of the oxime compounds is preferred as a capping agent with a dissociation temperature of 100 to 160°C, for example, from the viewpoint of preservation stability.

[0088] For example, from the perspective of improving the brittleness of the film and enhancing the adhesion to the substrate, it is preferable for the end-capped isocyanate compound to have an isocyanurate structure. End-capped isocyanate compounds having an isocyanurate structure can be obtained, for example, by isocyanuration of hexamethylene diisocyanate to protect it. Among isocyanate compounds with an isocyanurate structure, compounds with an oxime structure that allow the use of an oxime compound as a capping agent are preferred, from the viewpoint that it is easier to set the dissociation temperature in a better range and reduce development residue compared to compounds without an oxime structure.

[0089] End-capped isocyanate compounds can have polymerizable groups. There are no particular restrictions on the polymerizable group; any known polymerizable group can be used, with free radical polymerizable groups being preferred. Examples of polymerizable groups include vinyl unsaturated groups such as (meth)acryloxy, (meth)acrylamine, and styrene, as well as groups with epoxy groups such as glycidyl. Among them, as a polymerizable group, an ethylene unsaturated group is preferred, (meth)acryloxy is more preferred, and acryloxy is even more preferred.

[0090] As a capped isocyanate compound, it can be used in commercially available products. Examples of commercially available isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (all manufactured by SHOWA DENKO KK), and the Duranate series of end-capped compounds (e.g., Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, Duranate (registered trademark) SBB-70P, etc., manufactured by ASAHI KASEI CORPORATION). Furthermore, compounds with the following structure can also be used as end-capped isocyanate compounds.

[0091] [Chemical Formula 1]

[0092] A single thermal crosslinking agent can be used, or two or more can be used. The content of thermal crosslinking agent in the photosensitive composition layer is preferably 0.01~10% by mass relative to the total mass of the photosensitive composition layer, and even more preferably 0.1~5% by mass.

[0093] (resin) The photosensitive composition layer may contain resin. The resin contained in the photosensitive composition layer can be exemplified by resin A, which is an alkali-soluble resin. From the perspective of achieving better resolution by suppressing the swelling of the negative photosensitive component layer caused by the developer, the acid value of resin A is preferably below 220 mg KOH / g, even better if it does not reach 200 mg KOH / g, and further better if it does not reach 190 mg KOH / g. The lower limit of the acid value of resin A is not particularly limited, but from the viewpoint of superior developability, 120 mg KOH / g or above is better, 150 mg KOH / g or above is even better, and 170 mg KOH / g or above is especially good. Furthermore, the acid value (mgKOH / g) is the mass [mg] of potassium hydroxide required to neutralize 1g 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 below.

[0094] The weight-average molecular weight of resin A is not particularly limited, but 5,000 to 500,000 is preferred. When the weight-average molecular weight is 500,000 or less, it is preferable from the viewpoint of improving resolution and developability. A weight-average molecular weight of 100,000 or less is even more preferable, and 60,000 or less is even more preferable. On the other hand, when the weight-average molecular weight is 5,000 or more, it is preferable from the viewpoint of controlling the properties of the developed aggregates and the properties of the unexposed film, such as edge melting and chipping, when it is a negative photosensitive resin laminate. A weight-average molecular weight of 10,000 or more is more preferable, 20,000 or more is even more preferable, and 30,000 or more is particularly preferable. Edge melting refers to the ease with which the negative photosensitive component layer overflows from the end face of the roll when the transfer film is wound into a roll as a negative photosensitive resin laminate. Chipping refers to the ease with which chips scatter when the unexposed film is cut with a cutter. If these chips adhere to the upper surface of the negative photosensitive resin laminate, they can transfer to the mask in subsequent exposure steps, resulting in a defective product. The dispersion of resin A is preferably 1.0~6.0, more preferably 1.0~5.0, further preferably 1.0~4.0, and especially preferably 1.0~3.0. In this disclosure, the dispersion is the ratio of weight average molecular weight to number average molecular weight (weight average molecular weight / number average molecular weight). In this disclosure, the weight-average molecular weight and number-average molecular weight are values ​​measured using gel permeation chromatography.

[0095] The glass transition temperature (Tg) of resin A is preferably between 30 and 135°C. By using resin A with a Tg below 135°C, the deterioration of linewidth or resolution due to focus position shift during exposure can be suppressed. From this perspective, a Tg of alkali-soluble polymer below 130°C is more preferable, below 120°C is further preferable, and below 110°C is particularly preferable. Furthermore, from the viewpoint of improving edge melt resistance, using resin A with a Tg above 30°C is preferable. From this viewpoint, a Tg of resin A above 40°C is more preferable, above 50°C is further preferable, above 60°C is particularly preferable, and above 70°C is optimal.

[0096] -Derived from the constituent units of monomers containing aromatic hydrocarbon groups- Furthermore, from the viewpoint of suppressing the deterioration of linewidth or resolution due to focus position shift 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 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 all the constituent units of resin A. As an upper limit, it is not particularly limited, but 95% by mass or less is preferred, and 85% by mass or less is even more preferred. Furthermore, when multiple types of resin A are included, the average content of monomers having aromatic hydrocarbon groups is preferably within the above-mentioned range.

[0097] Examples of monomers containing aromatic hydrocarbon groups include monomers containing aralkyl groups, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tributoxystyrene, acetylstyrene, styrene dimers, and styrene trimers). Among these, monomers containing aralkyl groups or styrene are preferred. When the monomer having an aromatic hydrocarbon group is styrene, the content of the constituent units from styrene relative to all constituent units of resin A is preferably 10-70% by mass, more preferably 15-65% by mass, further preferably 20-60% by mass, and especially preferably 25-55% by mass. Furthermore, when the photosensitive composition layer contains multiple base-soluble polymers, the content of the constituent units from the monomer having an aromatic hydrocarbon group is calculated as a weight average.

[0098] As an aralkyl group, phenylalkyl groups that can have substituents are preferred, as are benzyl groups that can have substituents.

[0099] Examples of monomers containing phenylalkyl groups that can have substituents include phenylethyl (meth)acrylate.

[0100] Examples of monomers containing a benzyl group that may have a substituent include (meth)acrylates such as benzyl methacrylate and benzyl chloride (meth)acrylate; vinyl monomers such as vinyl benzyl chloride and vinyl benzyl alcohol; (meth)acrylates containing a benzyl group are preferred, and (meth)acrylate is even more preferred. When the monomer having an aromatic hydrocarbon group is benzyl methacrylate, the content of the constituent units derived from benzyl methacrylate relative to all constituent units of resin A is preferably 10-90% by mass, and more preferably 15-85% by mass.

[0101] -Derived from the constituent units of monomers containing carboxyl groups- Resin A may have constituent units derived from monomers containing carboxyl groups. Examples of monomers containing a carboxyl group include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic half-ester. Among these, (meth)acrylic acid is preferred. The content of constituent units derived from monomers with carboxyl groups in resin A is preferably 5-50% by mass relative to all constituent units of resin A, more preferably 10-40% by mass, and even more preferably 15-30% by mass. From the viewpoints of good developability and control of edge melting, it is preferable to set the above content to 5% by mass or more. From the viewpoints of high resolution and curled edge shape of the photoresist pattern, and further from the viewpoints of chemical resistance of the photoresist pattern, it is preferable to set the above content to 50% by mass or less.

[0102] -Non-acidic building blocks- Resin A may contain non-acidic constituent units derived from a non-acidic monomer having at least one polymerizable unsaturated group in the molecule. Examples of the aforementioned monomers (non-acidic monomers) include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tributyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, cyclohexyl methacrylate, and 2-ethylhexyl methacrylate, etc., which are methacrylates; vinyl acetate and other vinyl alcohol esters; and methacrylonitrile, etc. Among these, methyl methacrylate, 2-ethylhexyl methacrylate, or n-butyl methacrylate are preferred, with methyl methacrylate being even more preferred. The content of non-acidic monomer constituent units in resin A is preferably 1-60% by mass relative to all constituent units of resin A, more preferably 2-50% by mass, and further preferably 2-40% by mass.

[0103] Resin A can have any of the following structures in its side chain: straight chain, branched chain, and alicyclic chain. In this specification, "main chain" refers to the longest bonded chain in the molecule of the polymer compound that constitutes the resin, and "side chain" refers to a group of atoms that branch off from the main chain. By using monomers containing a branched structure in the side chain or a group containing an alicyclic structure in the side chain, branched or alicyclic structures can be introduced into the side chains of alkali-soluble polymers. The alicyclic group can be monocyclic or polycyclic. Specific examples of monomers containing a branched group in the side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, dibutyl (meth)acrylate, tributyl (meth)acrylate, isoamyl (meth)acrylate, triamyl (meth)acrylate, diamyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and trioctyl (meth)acrylate. Among these, isopropyl (meth)acrylate, isobutyl (meth)acrylate, or tributyl (meth)acrylate are preferred, and isopropyl (meth)acrylate or tributyl (meth)acrylate is even more preferred. Specific examples of monomers containing alicyclic groups in their side chains include monomers having monocyclic aliphatic hydrocarbon groups and monomers having polycyclic aliphatic hydrocarbon groups. Also, (meth)acrylates having alicyclic hydrocarbon groups with 5 to 20 carbon atoms can be cited. More specific examples include (meth)acrylate (bicyclo[2.2.1]heptyl-2) ester, (meth)acrylate-1-adamantyl ester, (meth)acrylate-2-adamantyl ester, (meth)acrylate-3-methyl-1-adamantyl ester, (meth)acrylate-3,5-dimethyl-1-adamantyl ester, (meth)acrylate-3-ethyladamantyl ester, (meth)acrylate-3-methyl-5-ethyl-1-adamantyl ester, (meth)acrylate-3,5,8-triethyl-1-adamantyl ester, (meth)acrylate-3,5-dimethyl-8-ethyl-1-adamantyl ester, (meth)acrylate-2-methyl-2-adamantyl ester, and (meth)acrylate-2-ethyl-2-adamantyl ester. 3-hydroxy-1-adamantyl ester of (meth)acrylate, octahydro-4,7-methyl-indene-5-yl ester of (meth)acrylate, octahydro-4,7-methyl-indene-1-yl methyl ester of (meth)acrylate, 1-menthol ester of (meth)acrylate, tricyclodecane of (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl ester of (meth)acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl ester of (meth)acrylate, (nor)camphenyl ester of (meth)acrylate, isocamphenyl ester of (meth)acrylate, fumarate of (meth)acrylate, 2,2,5-trimethylcyclohexyl ester of (meth)acrylate, and cyclohexyl ester of (meth)acrylate, etc. Among these (meth)acrylates, cyclohexyl (meth)acrylate, norborneol (meth)acrylate, isoborneol (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fumarate, 1-menthol (meth)acrylate, or tricyclodecane (meth)acrylate are preferred, and cyclohexyl (meth)acrylate, norborneol (meth)acrylate, isoborneol (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate are even more preferred.

[0104] -Constructing units with polymerizable groups- Resin A may have polymerizable groups or may contain constituent units with polymerizable groups. As a polymerizable group, a free radical polymerizable group is preferred, and an ethylene unsaturated group is even more preferred. Furthermore, when resin A has an ethylene unsaturated group, it is preferable that resin A contains a constituent unit having an ethylene unsaturated group in its side chain. As an ethylene unsaturated group, allyl or (meth)acryloxy is preferred.

[0105] As a constituent unit with a polymerizable group, the constituent unit represented by formula (P) is preferred.

[0106] [Chemical Formula 2]

[0107] In formula (P), RP represents a hydrogen atom or a methyl group. LP represents a divalent linker. P represents a polymerizable group.

[0108] RP stands for hydrogen atom or methyl group. Hydrogen atoms are preferred as RP.

[0109] LP represents a divalent linker. Examples of divalent linking groups include -CO-, -O-, -S-, -SO-, -SO2-, -NRN-, divalent hydrocarbon groups, and divalent groups formed by combining these. RN represents a substituent. Examples of the aforementioned hydrocarbon groups include alkyl, cycloalkyl, and aryl groups. The aforementioned alkyl group can be either straight-chain or branched. It is preferred that the alkyl group has 1 to 10 carbon atoms, more preferably 2 to 8, and further preferably 3 to 5. The aforementioned alkyl group can have heteroatoms, and the methylene group in the alkyl group can be replaced by heteroatoms. As the aforementioned heteroatoms, oxygen, sulfur, or nitrogen atoms are preferred, with oxygen atoms being more preferred. The aforementioned cycloalkyl group can be any of a monocyclic or polycyclic compound. It is preferred that the cycloalkyl group has 3 to 20 carbon atoms, more preferably 5 to 10, and even more preferably 6 to 8. The aforementioned aryl group can be either monocyclic or polycyclic. It is preferred that the aryl group has 6 to 20 carbon atoms, more preferably 6 to 15, and further preferably 6 to 10. As the aforementioned aryl group, the phenyl group is preferred. The aforementioned cycloalkyl and aryl groups may have heteroatoms as ring members. Oxygen, sulfur, or nitrogen atoms are preferred as heteroatoms, with oxygen atoms being more preferred. The aforementioned hydrocarbon group may further have substituents. Examples of substituents 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. As an LP, it is preferable to have a heteroatom-containing alkyl group.

[0110] P represents a polymerizable group. The polymeric groups described above are as described in the text.

[0111] Examples of constituent units having polymerizable groups include those shown below, but are not limited to these.

[0112] [Chemical Formula 3]

[0113] In the above-mentioned constituent units, Rx represents a hydrogen atom or a methyl group. Also, in the above-mentioned constituent units, Ry represents a hydrogen atom or a methyl group.

[0114] Resin A may contain only one type of polymerizable unit, or it may contain two or more types. When resin A contains constituent units with polymerizable groups, from the viewpoint of better performance of the present invention, it is preferable that the content of constituent units with polymerizable groups is 5 to 70% by mass relative to all constituent units of resin A, more preferably 10 to 50% by mass, and even more preferably 20 to 40% by mass. Furthermore, from the viewpoint of achieving even better results from the present invention, it is preferable that the content of polymerizable units in resin A is 5 to 70 mol% relative to all the constituent units of resin A, more preferably 10 to 60 mol%, and even more preferably 20 to 50 mol%.

[0115] As a method for introducing polymerizable groups into resin A, the following methods can be used: reacting compounds such as epoxy compounds, end-capped isocyanate compounds, isocyanate compounds, vinyl compounds, aldehyde compounds, hydroxymethyl compounds, and carboxylic anhydrides with functional groups such as hydroxyl groups, carboxyl groups, primary amino groups, secondary amino groups, acetoacetyl groups, and sulfonyl groups. A preferred example of a method for introducing polymerizable groups into resin A is as follows: after synthesizing a polymer having carboxyl groups by polymerization, a (meth)acrylate having epoxy groups, such as glycidyl methacrylate, is reacted with a portion of the carboxyl groups of the obtained polymer by polymerization to introduce (meth)acryloxy groups into the polymer. Another method is as follows: after synthesizing a polymer having hydroxyl groups by polymerization, a (meth)acrylate having isocyanate groups is reacted with a portion of the hydroxyl groups of the obtained polymer by polymerization to introduce (meth)acryloxy groups into the polymer. By means of this method, resin A having (meth)acryloxy groups in its side chain can be obtained. The above polymerization reaction is preferably carried out at a temperature of 70-100°C, and more preferably at a temperature of 80-90°C. As the polymerization initiator used in the above polymerization reaction, an azo-based initiator is preferred, such as V-601 (trade name) or V-65 (trade name) manufactured by FUJIFILM Wako Pure Chemical Corporation. The above polymer reaction is preferably carried out at a temperature of 80-110°C. In the above polymer reaction, the use of a catalyst such as an ammonium salt is preferred.

[0116] Resin A can be used alone or in combination with two or more resins. When using two or more resins, it is preferable to use a mixture of two resins A containing monomers having aromatic hydrocarbon groups, or to use a mixture of resin A containing monomers having aromatic hydrocarbon groups and resin A not containing monomers having aromatic hydrocarbon groups. In the latter case, it is preferable that the proportion of resin A containing monomers having aromatic hydrocarbon groups is 50% by mass or more relative to the total mass of resin A, more preferably 70% by mass or more, further preferably 80% by mass or more, and especially preferably 90% by mass or more.

[0117] The synthesis of resin A can be carried out by polymerizing the above-mentioned single or multiple monomers using free radical polymerization initiators such as peroxide-based polymerization initiators (e.g., benzoyl peroxide) and azo-based polymerization initiators (e.g., azobisisobutyronitrile).

[0118] The content of resin A relative to the total mass of the photosensitive composition layer is preferably 10-90% by mass, more preferably 20-80% by mass, further preferably 30-70% by mass, and especially preferably 40-60% by mass. From the viewpoint of controlling development time, it is preferable to set the content of resin A to 90% by mass or less. On the other hand, from the viewpoint of improving resistance to edge melting, it is preferable to set the content of resin A to 10% by mass or more.

[0119] The photosensitive composition layer may contain resins other than resin A mentioned above. Other resins that can be cited include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyethylene formaldehyde, polyester resins, epoxy resins, polyacetal resins, polybenzo[a]azole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0120] (polymeric compounds) The photosensitive composition layer may contain a polymeric compound having a polymeric group. Ethylene-unsaturated compounds are preferred as polymeric compounds. In addition, in this specification, "polymerizable compound" refers to a compound that is different from resin A and polymerizes under the action of the polymerization initiator described below.

[0121] As for the polymerizable group in a polymerizable compound, it is only necessary to have a group that participates in the polymerization reaction. Examples include vinyl, acrylonitrile, methacrylonitrile, styrene, and maleic anhydride groups, which have vinyl unsaturated groups; epoxy and oxybutane groups, which have cationic polymerizable groups. Groups with vinyl unsaturated groups are preferred, and acrylonitrile or methacrylonitrile are even more preferred.

[0122] Examples of vinyl unsaturated groups in vinyl unsaturated compounds include vinyl, acrylonitrile, methacrylonitrile, styrene, and maleicadiimino. Acrylonitrile or methacrylonitrile are preferred as vinyl unsaturated groups. As polymerizable compounds other than ethylene-based unsaturated compounds, the polymerizable groups are not particularly limited as long as they participate in the polymerization reaction. Examples include groups with cationic polymerizable groups such as epoxy groups and cyclobutane groups. The following describes ethylene-unsaturated compounds.

[0123] From the perspective of superior photosensitivity, vinyl unsaturated compounds with two or more vinyl unsaturated groups in one molecule (polyfunctional vinyl unsaturated compounds) are preferred. Furthermore, from the viewpoint of superior resolution and exfoliation, it is preferable for an vinyl unsaturated compound to have 6 or fewer vinyl unsaturated groups in a molecule, more preferably 3 or fewer, and even more preferably 2 or fewer.

[0124] From the perspective of achieving a better balance between photosensitivity, resolution, and peelability of the photosensitivity composition layer, it is preferable to contain a difunctional or trifunctional vinyl unsaturated compound having two or three vinyl unsaturated groups in one molecule, and even better to contain a difunctional vinyl unsaturated compound having two vinyl unsaturated groups in one molecule. From the perspective of excellent exfoliation properties, it is preferable that the content of difunctional vinyl unsaturated compounds relative to the total mass of polymerizable compounds is 20% by mass or more, more than 40% by mass is even better, and 55% by mass or more is further preferred. The upper limit is not particularly limited and can be 100% by mass. That is, the polymerizable compounds can be entirely difunctional vinyl unsaturated compounds. Furthermore, as an ethylene-unsaturated compound, (meth)acrylate compounds having (meth)acrylic acid groups as polymerizable groups are preferred.

[0125] -Polymerizing compound B1- The photosensitive composition layer contains a polymeric compound B1 having an aromatic ring and two vinyl unsaturated groups, which is also preferred as a polymeric compound.

[0126] In the photosensitive composition layer, from the viewpoint of superior resolution, it is preferable that the content of polymeric compound B1 relative to the total mass of the polymeric compound is 40% by mass or more, more preferably 50% by mass or more, further preferably 55% by mass or more, and especially preferably 60% by mass or more. The upper limit is not particularly limited, but from the viewpoint of peelability, for example, 100% by mass or less, 99% by mass or less is preferable, 95% by mass or less is more preferably, 90% by mass or less is further preferably, and 85% by mass or less is especially preferred.

[0127] Examples of aromatic rings in the 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 condensed rings of these compounds. Aromatic hydrocarbon rings are preferred, and benzene rings are even more preferred. Furthermore, the aforementioned aromatic rings may have substituents. Polymerizable compound B1 may have only one aromatic ring or more than two aromatic rings.

[0128] From the perspective of improving resolution by inhibiting the swelling of the photosensitive component layer caused by the developer, the polymeric compound B1 with a bisphenol structure is preferable. 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.

[0129] As a polymerizable compound B1 having a bisphenol structure, examples include compounds having a bisphenol structure and two polymerizable groups (preferably (meth)acrylyl) bonded to both ends of the bisphenol structure. The two ends of the bisphenol structure can be directly bonded to the two polymerizable groups, or they can be bonded through one or more alkoxy groups, with the latter being preferred. As the alkoxy groups at both ends of the bisphenol structure, alkoxy groups, ethoxy groups, or propoxy groups are preferred, with ethoxy groups being more preferred. The number of alkoxy groups added to the bisphenol structure is not particularly limited, but 4 to 16 per molecule is preferred, and 6 to 14 per molecule is even more preferred. Regarding the polymerizable compound B1 having a bisphenol structure, it is described in paragraphs

[0072] to

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

[0130] As a polymerizable compound B1, a difunctional vinyl unsaturated compound having a bisphenol A structure is preferred, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is even more preferred. Examples of 2,2-bis(4-((meth)propenyloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methpropenyloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methpropenyloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methpropenyloxypentethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methpropenyloxydodecethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), and 2,2-bis(4-(methpropenyloxydodecadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.). 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.), and ethoxylated bisphenol A dimethacrylate (BPE-100, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0131] Polymer compound B1 can be used alone or in combination with two or more compounds. From the viewpoint of superior resolution, it is preferable that the content of polymeric compound B1 is 10% by mass or more relative to the total mass of the photosensitive composition layer, and even more preferably 20% by mass or more. There is no particular upper limit, but from the viewpoint of transferability and edge melting (the phenomenon of photosensitive resin seeping out from the ends of the transfer member), 70% by mass or less is preferable, and 60% by mass or less is even more preferable.

[0132] As a polymerizable compound, a polymerizable compound having an epoxide-modified bisphenol structure is preferred, and the compound represented by the following general formula (B1) (which also corresponds to the above-mentioned polymerizable compound B1) is even more preferred.

[0133] [Chemical Formula 4]

[0134] In general formula (B1), R1 and R2 independently represent a hydrogen atom or a methyl group, respectively. A represents C2H4. B represents C3H6. n1 and n3 are each independent integers from 1 to 39, and n1+n3 is an integer from 2 to 40. n2 and n4 are each independent 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)- can be random or block. Moreover, in the case of block, either -(AO)- or -(BO)- can be on the biphenyl side. In a single-state sample, n1+n2+n3+n4 of 2~20 is better, 2~16 is even better, and 4~12 is further better. Also, n2+n4 of 0~10 is better, 0~4 is even better, 0~2 is further better, and 0 is particularly better.

[0135] The photosensitive composition layer may contain other polymeric compounds besides the polymeric compounds mentioned above. Other polymerizable compounds are not particularly limited and can be appropriately selected from known compounds. For example, compounds having one vinyl unsaturated group in one molecule (monofunctional vinyl unsaturated compounds), difunctional vinyl unsaturated compounds without an aromatic ring, and trifunctional or more vinyl unsaturated compounds can be cited.

[0136] Examples of monofunctional vinyl unsaturated compounds include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate.

[0137] Examples of difunctional vinyl unsaturated compounds that do not have an aromatic ring include alkyl diol di(meth)acrylate, polyalkyl diol di(meth)acrylate, amine di(meth)acrylate, and trimethylolpropane diacrylate. Examples of alkyl glycol di(meth)acrylates include tricyclodecanediethanol diacrylate (manufactured by A-DCP, Shin-Nakamura Chemical Co., Ltd.), tricyclodecanediethanol dimethacrylate (DCP, Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (manufactured by A-NOD-N, Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (manufactured by A-HD-N, Shin-Nakamura Chemical Co., Ltd.), polyethylene glycol dimethacrylate (4G, 9G, 14G and 23G, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.), ARONIX (registered trademark) M-220 (manufactured by TOAGOSEI CO.,LTD.), and ARONIX (registered trademark) M-240 (manufactured by TOAGOSEI CO.,LTD.). (Manufactured by CO.,LTD.), ARONIX (registered trademark) 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 amine di(meth)acrylates include propylene oxide-modified amine di(meth)acrylates and ethylene oxide and propylene oxide-modified amine di(meth)acrylates. Commercially available examples include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0138] Examples of trifunctional or higher ethylene unsaturated compounds include, for example, dinepentetreol (tri / tetra / penta / hexa)methacrylate, neopentetreol (tri / tetra)methacrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanurate tri(meth)acrylate, glycerol tri(meth)acrylate, and epoxide-modified versions of the like. Among them, "(tri / tetra / penta / hexa)meth)acrylate" includes the concepts of tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate and hexa(meth)acrylate, and "(tri / tetra)meth)acrylate" includes the concepts of tri(meth)acrylate and tetra(meth)acrylate. In one sample, it is preferable that the photosensitive composition layer includes the aforementioned polymeric compound B1 and a trifunctional or higher vinyl unsaturated compound, and it is even more preferable that it includes the aforementioned polymeric compound B1 and two or more trifunctional or higher vinyl unsaturated compounds. In this case, it is preferable that the mass ratio of polymeric compound B1 to trifunctional or higher vinyl unsaturated compounds is 1:1 to 5:1 (total mass of polymeric compound B1 : (total mass of trifunctional or higher vinyl unsaturated compounds) = 1:1 to 5:1, more preferable that it is 1.2:1 to 4:1, and further preferable that it is 1.5:1 to 3:1. Furthermore, in one state sample, it is preferable that the photosensitive composition layer contains the aforementioned polymeric compound B1 and two or more trifunctional vinyl unsaturated compounds.

[0139] Examples of epoxide-modified compounds that are trifunctional or higher-functionalized ethylene unsaturated compounds include caprolactone-modified (meth)acrylate compounds (such as KAYARAD DPCA-20 manufactured by Nippon Kayaku Co., Ltd., and A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd.), ethoxylated trimethylolpropane trimethacrylate (such as SR454, SR499, and SR502 manufactured by TOMOE Engineering Co., Ltd.), epoxide-modified (meth)acrylate compounds (such as KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL 135 manufactured by DAICEL-ALLNEX LTD.), and ethoxylated glycerol trimethacrylate (such as Shin-Nakamura Chemical Co., Ltd.). A-GLY-9E, etc. manufactured by Co., Ltd.), ARONIX (registered trademark) TO-2349 (manufactured by TOAGOSEI CO.,LTD.), ARONIX M-520 (manufactured by TOAGOSEI CO.,LTD.) and ARONIX M-510 (manufactured by TOAGOSEI CO.,LTD.).

[0140] Furthermore, polymerizable compounds containing acid groups (such as carboxyl groups) can be used. These acid groups can form anhydride groups. Examples of polymerizable compounds containing acid groups include ARONIX (registered trademark) TO-2349 (manufactured by TOAGOSEI CO.,LTD.), ARONIX (registered trademark) M-520 (manufactured by TOAGOSEI CO.,LTD.), and ARONIX (registered trademark) M-510 (manufactured by TOAGOSEI CO.,LTD.). As 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 can be used.

[0141] The molecular weight (weight average molecular weight when there is a molecular weight distribution) 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.

[0142] Polymers can be used alone or in combination with two or more compounds. The content of polymeric compounds relative to the total mass of the photosensitive composition layer is preferably 0-70% by mass, more preferably 10-70% by mass, and further preferably 20-60% by mass.

[0143] (Polymerization initiator) The photosensitive composition layer may contain a polymerization initiator. As polymerization initiators, known polymerization initiators can be used, for example, depending on the form of the polymerization reaction. Specifically, examples include thermal polymerization initiators and photopolymerization initiators. The polymerization initiator can be either a free radical polymerization initiator or a cationic polymerization initiator.

[0144] It is preferable that the photosensitive composition layer contains a photopolymerization initiator. Photopolymerization initiators are compounds that initiate the polymerization of polymerizable compounds upon exposure to active light sources such as ultraviolet light, visible light, and X-rays. There are no particular limitations on the use of photopolymerization initiators; any known photopolymerization initiator can be used. Examples of photopolymerization initiators include photoradical polymerization initiators and photocationic polymerization initiators, with photoradical polymerization initiators being preferred.

[0145] Examples of photoradical polymerization initiators include photopolymerization initiators with oxime ester structures, photopolymerization initiators with α-aminoalkylphenyl ketone structures, photopolymerization initiators with α-hydroxyalkylphenyl ketone structures, photopolymerization initiators with acetylsphosphine oxide structures, and photopolymerization initiators with N-phenylglycine structures.

[0146] Furthermore, from the viewpoints of photosensitivity, visibility of the exposed and unexposed portions, and resolution, it is preferable that the photosensitive component layer contains at least one selected from the group consisting of 2,4,5-triarylimidazolium dimers and their derivatives as a photoradical polymerization initiator. Additionally, the two 2,4,5-triarylimidazolium structures in the 2,4,5-triarylimidazolium dimers and their derivatives may be identical or different. Examples of derivatives of 2,4,5-triarylimidazolium dimers include 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazolium dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazolium dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazolium dimer.

[0147] As a photoradical polymerization initiator, for example, the polymerization initiators described in paragraphs

[0031] to

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

[0064] to

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

[0148] Examples of photoradical polymerization initiators include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, (p,p'-dimethoxybenzyl)anisyl ester, TAZ-110 (trade name: manufactured by Midori Kagaku Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (trade name: manufactured by Midori Kagaku 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.).

[0149] Commercially available photoradical polymerization initiators include, for example, 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoxime) (trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]acetone-1-(O-acetime) (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 IGM Resins BV), 2-methyl-1-(4-methylthiophenyl)-2-morpholinylprop-1-one (trade name: Omnirad 907, manufactured by IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionic)benzyl]phenyl}-2-methylprop-1-one (trade name: Omnirad 127, manufactured by IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone-1 (trade name: Omnirad 369, manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenylprop-1-one (trade name: Omnirad 1173, manufactured by IGM Resins BV), 1-hydroxycyclohexylphenyl ketone (trade name: Omnirad 184, manufactured by IGM Resins BV) Omnirad 651 (manufactured by IGM Resins BV), 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: Omnirad 651, manufactured by IGM Resins BV), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, manufactured by IGM Resins BV), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, manufactured by IGM Resins BV), and oxime ester-based photopolymerization initiators (trade name: Lunar 6, DKSH Japan). KK manufactures), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (trade name: B-CIM, manufactured by Hampford), 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, Tokyo Chemical Industry Co., Ltd.).(Manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoxyxime) (trade name: TR-PBG-305), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazole-3-yl]-,2-(O-acetyloxime) (trade name: TR-PBG-326), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazole-3-yl]-,2-(O-acetyloxime) (trade name: TR-PBG-326), Changzhou Tronly New Electronic Materials Co., Ltd. Manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.) and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)octyl)-9-ethyl-9H-carbazole-3-yl)-propane-1,2-dione-2-(O-benzoxyxime) (trade name: TR-PBG-391, manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.).

[0150] Photocationic polymerization initiators (photoacid generators) are compounds that generate acids upon receiving active light. As photocationic polymerization initiators, compounds that generate acids upon receiving active light with wavelengths above 300 nm, preferably between 300 nm and 450 nm, are preferred, but their chemical structure is not limited. Furthermore, regarding photocationic polymerization initiators that do not directly sense active light with wavelengths above 300 nm, as long as they are compounds that generate acids upon receiving active light with wavelengths above 300 nm by being used in conjunction with a sensitizer, they can also be used in combination with the sensitizer for optimal results. As a photocationic polymerization initiator, it is preferable to produce an acid photocationic polymerization initiator with a pKa of 4 or less, more preferably an acid photocationic polymerization initiator with a pKa of 3 or less, and even more preferably an acid photocationic polymerization initiator with a pKa of 2 or less. There is no particular specification for the lower limit of pKa, but for example, it is preferable to have a value of -10.0 or higher.

[0151] Examples of photocationic polymerization initiators include ionic and nonionic photocationic polymerization initiators. Examples of onion salts that can be used as initiators for ionic photocationic polymerization include diaryl strontium salts, triaryl strontium salts, and quaternary ammonium salts. As an 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.

[0152] Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triwell derivatives, diazomethane compounds, oxime sulfonate compounds, and oxime sulfonate compounds. As trichloromethyl-s-triwell derivatives, diazomethane compounds, and oxime sulfonate compounds, compounds described in paragraphs

[0083] to

[0088] of Japanese Patent Application Publication No. 2011-221494 can be used. Furthermore, as oxime sulfonate compounds, compounds described in paragraphs

[0084] to

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

[0153] 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-triarylimidazolium dimers and their derivatives.

[0154] A polymerization initiator can be used alone or in combination with two or more. The content of the polymerization initiator (preferably a photopolymerization initiator) is not particularly limited, but it is preferable to be 0.1% by mass or more relative to the total mass of the photosensitive composition layer, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more. The upper limit is not particularly limited, but it is preferable to be 20% by mass or less relative to the total mass of the photosensitive composition layer, more preferably 15% by mass or less, and further preferably 10% by mass or less.

[0155] (Sensitizer) It is preferable that the photosensitive composition layer 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, acridinium compounds, tebuconazole compounds, benzotebuconazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), piracene compounds, distyrylbenzene, styrylbenzene, tri-well compounds, thiophene compounds, naphthyldimethylimine compounds, triarylamine compounds, and aminoacridine compounds. Furthermore, derivatives of the compounds listed above are also included. Among them, as sensitizers, dialkylaminobenzophenone compounds, anthracene compounds, stilbene compounds or styrylpyridine compounds are preferred, anthracene compounds, stilbene compounds or styrylpyridine compounds are more preferred, and anthracene derivatives, stilbene derivatives or styrylpyridine derivatives are even more preferred.

[0156] A single sensitizer can be used, or two or more sensitizers can be used. When the photosensitive composition layer contains a sensitizer, the content of the sensitizer can be appropriately selected according to the purpose. However, from the viewpoint of improving the sensitivity to the light source and improving the curing speed by balancing the polymerization rate and chain transfer, it is better to have 0.01 to 5% by mass relative to the total mass of the photosensitive composition layer, and even better to have 0.05 to 1% by mass.

[0157] (pigment) From the perspective of visibility of both exposed and unexposed areas, visibility of the developed pattern, and resolution, it is preferable for the photosensitive composition layer to contain a pigment (also known as "pigment N") with a maximum absorption wavelength of 450 nm or higher within the wavelength range of 400–780 nm during color development, and whose maximum absorption wavelength changes with acids, bases, or free radicals. While the detailed mechanism is not fully understood, the inclusion of pigment N improves adhesion to adjacent layers (e.g., water-soluble resin layers) and results in superior resolution.

[0158] In this specification, the phrase "the maximum absorption wavelength of a pigment changes due to acid, alkali, or free radicals" can refer to any of the following states: a pigment in a chromogenic state that is decolorized by acid, alkali, or free radicals; a pigment in a decolorized state that is chromogenic by acid, alkali, or free radicals; or a pigment in a chromogenic state that is chromogenic and changes to another hue. Specifically, pigment N can be a compound that changes color from a decolorized state upon exposure, or a compound that changes color from a color-developed state upon exposure. In this case, it can be a pigment that changes color or decolorization upon exposure by generating acids, bases, or free radicals within the photosensitive component layer, or a pigment whose state (e.g., pH) within the photosensitive component layer changes due to acids, bases, or free radicals, thus changing its color or decolorization state. Alternatively, it can be a pigment that changes color or decolorization upon direct exposure to acids, bases, or free radicals without exposure.

[0159] From the perspective of visibility and resolution of both the exposed and unexposed areas, pigment N is preferred if its maximum absorption wavelength changes due to acid or free radicals, and even better if its maximum absorption wavelength changes due to free radicals. When the photosensitive composition layer is a negative photosensitive composition layer, from the viewpoint of visibility and resolution of the exposed and unexposed areas, it is better for the negative photosensitive composition layer to contain a pigment with a maximum absorption wavelength that changes by free radicals as pigment N and a photoradical polymerization initiator. Furthermore, from the perspective of visibility of the exposed and unexposed areas, pigment N, which is a pigment that develops color through acids, bases, or free radicals, is better.

[0160] Examples of color-developing mechanisms for pigment N include free radical reactive pigments, acid reactive pigments, or base reactive pigments (e.g., colorless pigments) that develop color by adding a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator), or a photobase generator to a photosensitive composition layer and then exposing it to light, resulting in color development from free radicals, acids, or bases generated by the photoradical polymerization initiator, photocationic polymerization initiator, or photobase generator.

[0161] From the viewpoint of visibility of both the exposed and unexposed areas, it is preferable that the maximum absorption wavelength of pigment N in the wavelength range of 400-780nm is 550nm or higher, 550-700nm is even better, and 550-650nm is even more preferable. Furthermore, pigment N may have only one maximum absorption wavelength in the wavelength range of 400-780 nm for color development, or it may have two or more. When pigment N has two or more maximum absorption wavelengths in the wavelength range of 400-780 nm for color development, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths should be 450 nm or higher.

[0162] The maximum absorption wavelength of pigment N was obtained by measuring the transmission spectrum of a solution containing pigment N (liquid temperature 25°C) in an atmospheric environment using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) in the wavelength range of 400nm to 780nm, and detecting the wavelength at which the light intensity became minimal (maximum absorption wavelength).

[0163] As pigments that develop or fade color through exposure, colorless compounds can be cited as an example. Examples of pigments that are decolorized by exposure include colorless compounds, diarylmethane pigments, tetrodotoxin pigments, tetrodotoxin pigments, iminonaphthoquinone pigments, azomethine pigments, and anthraquinone pigments. From the viewpoint of visibility of both the exposed and unexposed areas, colorless compounds are preferred as pigment N.

[0164] Examples of colorless compounds include colorless compounds with a triarylmethane skeleton (triarylmethane pigments), colorless compounds with a spiropyran skeleton (spiropyran pigments), colorless compounds with a fluorescent yellow parent skeleton (fluorescent yellow parent system pigments), colorless compounds with a diarylmethane skeleton (diarylmethane pigments), colorless compounds with a rhodamine lactone skeleton (rhodamine lactone pigments), colorless compounds with an indolephthalide skeleton (indolephthalide pigments), and colorless compounds with a colorless golden yellow amine skeleton (colorless golden yellow amine pigments). Among them, triarylmethane-based pigments or fluorescent yellow parent system pigments are preferred, and colorless compounds with a triphenylmethane skeleton (triphenylmethane-based pigments) or fluorescent yellow parent system pigments are even better.

[0165] From the viewpoint of visibility of both exposed and unexposed areas, it is preferable for a colorless compound to possess a lactone ring, a sultine ring, or a sulfonyl ring. This allows the lactone ring, sultine ring, or sulfonyl ring of the colorless compound to react with a free radical generated by a photoradical polymerization initiator or an acid generated by a photocationic polymerization initiator, thereby changing the colorless compound to a closed-ring state and thus decolorizing it, or changing the colorless compound to an open-ring state and thus making it colored. As a colorless compound, it is preferable for a compound to possess a lactone ring, sultine ring, or sulfonyl ring, and for which the lactone ring, sultine ring, or sulfonyl ring becomes colored by ring-opening with a free radical or acid; a compound to possess a lactone ring, and for which the lactone ring becomes colored by ring-opening with a free radical or acid, is even more preferable.

[0166] As pigment N, examples include the following dyes and colorless compounds. Among pigments N, specific examples of dyes include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsine, methyl violet 2B, quinaldine red, rose bengal, metanil yellow, thymol sulfonphthalein, xylenol blue, methyl orange, p-methyl red, Congo red, benzopurpurine 4B, α-naphthyl red, Nile blue 2B, Nile blue A, methyl violet, malachite green, parafuchsin, Victoria pure blue naphthalene sulfonate, Victoria pure blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Industries Co., Ltd.), and Oil Pink #312 (manufactured by Orient Chemical Industries). Oil Red 5B (manufactured by Orient Chemical Industries Co., Ltd.), Oil Scarlet #308 (manufactured by Orient Chemical Industries Co., Ltd.), Oil Red OG (manufactured by Orient Chemical Industries Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Industries Co., Ltd.), Oil Green #502 (manufactured by Orient Chemical Industries Co., Ltd.), Spilon Red BEH Special (manufactured by Hodogaya Chemical Co., Ltd.) (Manufactured by Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0167] Among pigments N, specific examples of colorless compounds include p,p',p”-hexamethyltriaminetriphenylmethane (colorless crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl colorless methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)amino fluorescent yellow precursor, 2-anilino-3-methyl-6-(N-ethyl-p-tolyl) fluorescent yellow precursor, 3,6-dimethoxy fluorescent yellow precursor, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino) fluorescent yellow precursor, 3-(N-cyclohexyl-N-methylamino)-6-methyl- 7-Aniline fluorescent yellow parent material, 3-(N,N-diethylamino)-6-methyl-7-aniline fluorescent yellow parent material, 3-(N,N-diethylamino)-6-methyl-7-amino fluorescent yellow parent material, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorescent yellow parent material, 3-(N,N-diethylamino)-6-methoxy-7-aminofluorescent yellow parent material, 3-(N,N-diethylamino)-7-(4-chloroaniline)fluorescent yellow parent material, 3-(N 3-(N,N-diethylamino)-7-benzylamino fluorescent yellow parent material, 3-(N,N-diethylamino)-7,8-benzofluoro yellow parent material, 3-(N,N-dibutylamino)-6-methyl-7-aniline fluorescent yellow parent material, 3-(N,N-dibutylamino)-6-methyl-7-aniline fluorescent yellow parent material, 3-piperidinyl-6-methyl-7-aniline fluorescent yellow parent material, 3-pyrrolidinyl-6-methyl-7-aniline fluorescent yellow parent material, 3,3-bis(1-ethyl-2-methylindole-3-yl)phthalolide (phthali de), 3,3-bis(1-n-butyl-2-methylindole-3-yl)phthalolide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalolide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-azaphthalolide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)phthalolide and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]-yamagata-3-one.

[0168] From the perspective of visibility of the exposed and unexposed areas, the visibility and resolution of the developed pattern, pigment N, which has a maximum absorption wavelength that changes due to free radicals, is better, and pigment that develops color through free radicals is even better. As pigment N, colorless crystal violet, crystal violet lactone, brilliant green, or Victoria blue naphthalene sulfonate are preferred.

[0169] Pigment N can be used alone or in combination with two or more pigments. From the viewpoint of visibility of the exposed and unexposed areas, the visibility and resolution of the developed pattern, the content of pigment N relative to the total mass of the photosensitive composition layer is preferably 0.1% by mass or more, more preferably 0.1 to 10% by mass, further preferably 0.1 to 5% by mass, and especially preferably 0.1 to 1% by mass.

[0170] The content of pigment N refers to the amount of pigment required to make all of the pigment N contained in the total mass of the photosensitive composition layer in a colored state. The following explanation uses pigments that develop color via free radicals as an example to illustrate the quantitative method for determining the content of pigment N. Solutions were prepared by dissolving 0.001 g and 0.01 g of pigment in 100 mL of methyl ethyl ketone. A photoradical polymerization initiator (trade name: Irgacure OXE01, manufactured by BASF Japan Ltd.) was added to each solution, and the solutions were irradiated with light at a wavelength of 365 nm to generate free radicals, thereby causing all pigments to become colored. Then, under atmospheric conditions, the absorbance of each solution at a liquid temperature of 25°C was measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), and calibration curves were constructed. Next, 3g of the photosensitive composition layer was dissolved in methyl ethyl ketone instead of the pigment. The absorbance of the solution in which the pigment was fully developed was then measured using the same method as described above. Based on the calibration curve, the pigment content in the photosensitive composition layer was calculated from the absorbance of the resulting solution containing the photosensitive composition layer. In addition, the 3g of photosensitive composition layer is the same as the 3g of total solids in the photosensitive composition.

[0171] (pigment) The photosensitive composition layer may contain pigments. When the photosensitive composition layer contains pigment, the photosensitive composition layer corresponds to the coloring resin layer. In recent years, cover glass, which has a black frame-like light-shielding layer formed on the back periphery of a transparent glass substrate or the like, has been installed on the liquid crystal display window of electronic devices to protect the liquid crystal display window. Colored resin layers can be used to form this light-shielding layer. As for pigments, you can choose the appropriate one based on the desired hue. For example, you can choose black pigment, white pigment, and colored pigments other than black and white. When forming a black pattern, black pigment is the best choice.

[0172] Examples of black pigments include well-known black pigments (e.g., organic and inorganic pigments). From the viewpoint of optical concentration, carbon black, titanium oxide, titanium carbide, iron oxide, or graphite are preferred as black pigments, with carbon black being even more preferred. From the viewpoint of surface resistivity, surface-modified carbon black in which at least a portion of the surface is coated with resin is preferred as carbon black.

[0173] From the perspective of dispersion stability, a particle size (number average particle size) of 0.001~0.1μm is preferred for black pigments, and 0.01~0.08μm is even better. "Particle size" refers to the diameter of a circle whose area is determined from a photograph of pigment particles taken with an electron microscope, and which is then considered to be the area of ​​a circle with the same area as the pigment particle. "Number-average particle size" refers to the average value obtained by averaging the above particle sizes for any 100 particles.

[0174] Examples of white pigments include inorganic pigments and the white pigments described in paragraphs

[0015] and

[0114] of Japanese Patent Application Publication No. 2005-007765. As inorganic pigments, titanium dioxide, zinc oxide, zinc barium white, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate are preferred, with titanium dioxide or zinc oxide being even better, titanium dioxide being further preferred, rutile or anatase titanium dioxide being particularly good, and rutile titanium dioxide being the best. Furthermore, the surface of titanium oxide can be treated with silicon dioxide, aluminum oxide, titanium dioxide, zirconium dioxide, or organic substances, or two or more of these treatments can be applied. This suppresses the catalytic activity of titanium oxide, thereby improving its heat resistance and fading properties. From the viewpoint of reducing the thickness of the photosensitive component layer after heating, it is preferable to perform at least one of alumina treatment and zirconium dioxide treatment as a surface treatment for titanium oxide, and it is even better to perform both alumina treatment and zirconium dioxide treatment.

[0175] When the photosensitive composition layer is a colored resin layer, from the viewpoint of transferability, it is preferable that the photosensitive composition layer includes colored pigments other than black and white pigments. From the viewpoint of superior dispersibility, a particle size (number average particle size) of less than 0.1 μm is preferred for colored pigments, and less than 0.08 μm is even better. A lower limit of 10 nm or more is preferred. Examples of colored pigments include Victoria Blue BO (Color Index 42595), Golden Ammonium (CI 41000), Fat Black HB (CI 26150), Monolight Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hostaperm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11), Pastel Pink B Supura (CI Pigment Red 81), and Monastella Fast Blue. The following pigments are preferred: Monolight Black B (CI Pigment Black 1), Carbon, CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red 215, CI Pigment Green 7, CI Pigment Blue 15:1, CI Pigment Blue 15:4, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64, CI Pigment Violet 23, and CI Pigment Red 177.

[0176] Pigments can be used alone or in combination with more than one type. The pigment content relative to the total mass of the photosensitive composition layer is preferably more than 3% by mass and less than 40% by mass, more than 3% by mass and less than 35% by mass is even better, more than 5% by mass and less than 35% by mass is further better, and 10 to 35% by mass is particularly good.

[0177] When the photosensitive composition layer contains pigments other than black pigment (e.g., white pigments and colored pigments), it is preferable that the content of pigments other than black pigment is 30% by mass or less relative to the total mass of black pigment, 1 to 20% by mass is more preferable, and 3 to 15% by mass is even more preferable.

[0178] When the photosensitive composition layer contains a black pigment, it is preferable that the black pigment (preferably carbon black) is introduced into the photosensitive composition in the form of a pigment dispersion. A dispersion can be prepared by adding a mixture of pre-mixed black pigment and pigment dispersant to an organic solvent (or vehicle) and dispersing it using a disperser. The pigment dispersant can be selected based on the pigment and solvent; for example, commercially available dispersants can be used. "Mediator" refers to the medium that disperses the pigment during the preparation of a pigment dispersion. The aforementioned mediator is liquid and contains binder components that hold the black pigment in a dispersed state, and solvent components (organic solvents) that dissolve and dilute the binder components.

[0179] Examples of dispersing machines include kneaders, roller mills, attritors, super mills, dissolvers, homogenizers, and sand mills. Alternatively, mechanical grinding can be used to micronize the material using friction. Examples of dispersers and micronizers include those described in the "Dictionary of Pigments" (by Kunio Asakura, first edition, Asakura Shoten, 2000, pp. 438, 310).

[0180] (Other additives) In addition to the above-mentioned components, the photosensitive composition layer may contain known additives as needed. Examples of additives include free radical polymerization inhibitors, antioxidants (e.g., phenidones), rust inhibitors (e.g., benzotriazoles and carboxybenzotriazoles), sensitizers, surfactants, plasticizers, heterocyclic compounds (e.g., triazoles), pyridines (e.g., isoniazid), and purine bases (e.g., adenine). Furthermore, other additives include, for example, metal oxide particles, chain transfer agents, antioxidants, dispersants, acid proliferators, development promoters, conductive fibers, ultraviolet absorbers, thickeners, crosslinking agents, organic or inorganic precipitation inhibitors, and paragraphs

[0165] to

[0184] of Japanese Patent Application Publication No. 2014-085643, the contents of which are incorporated herein by reference. Each additive can be used alone or in combination with two or more.

[0181] The photosensitive composition layer may contain free radical polymerization inhibitors. Examples of free radical polymerization inhibitors include the thermal polymerization inhibitors described in paragraph

[0018] of Japanese Patent No. 4502784. Among these, phenoxyphenol, phenoxy-acetylene, or 4-methoxyphenol are preferred. Other free radical polymerization inhibitors include naphthylamine, copper(I), aluminum N-nitrosophenylhydroxylamine, and diphenylnitrosamine. To avoid impairing the sensitivity of the photosensitive composition layer, aluminum N-nitrosophenylhydroxylamine is preferred as a free radical polymerization inhibitor. The content of the free radical polymerization inhibitor relative to the total mass of the polymerizable compound is preferably 0.005~5.0% by mass, more preferably 0.01~3.0% by mass, and even more preferably 0.01~1.0% by mass.

[0182] 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.

[0183] Examples of carboxylated benzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylene carboxylated benzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylene carboxylated benzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethyl carboxylated benzotriazole. Commercially available products such as CBT-1 (JOHOKU CHEMICAL CO.,LTD., trade name) can also be used as carboxylated benzotriazoles.

[0184] The combined content of benzotriazoles and carboxybenzotriazoles relative to the total mass of the photosensitive composition layer is preferably 0.01 to 3% by mass, and more preferably 0.05 to 1% by mass. When the content is 0.01% by mass or higher, the storage stability of the photosensitive composition layer is better. On the other hand, when the content is 3% by mass or lower, the maintenance of sensitivity and the suppression of dye decolorization are better.

[0185] 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.

[0186] Nonionic surfactants, fluorinated surfactants, or silicone surfactants are preferred as surfactants. Commercially available fluorinated surfactants include, for example, MEGAFACE F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, and F-7. 80. 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 (the above is DIC Fluorad FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by AGC Inc.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), Ftergent 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), U-120E (manufactured by UNICHEM CO.,LTD.), etc. Furthermore, fluorinated surfactants can also better utilize acrylic compounds, which have a molecular structure containing functional groups with fluorine atoms. When heated, the functional groups containing fluorine atoms are cleaved, causing the fluorine atoms to volatilize. Examples of such fluorinated surfactants include the MEGAFACE DS series manufactured by DIC Corporation (Chemical Industry Daily (February 22, 2016), Nikkei Industrial News (February 23, 2016)), such as MEGAFACE DS-21. Furthermore, as a fluorinated surfactant, polymers of fluorinated vinyl ether compounds with fluorinated alkyl or fluorinated alkyl ether groups and hydrophilic vinyl ether compounds are also preferred. Furthermore, as a fluorinated surfactant, it can also be used with end-capped polymers. Furthermore, as a fluorinated surfactant, fluorinated polymeric compounds can also be used more readily. These fluorinated polymeric compounds contain constituent units derived from (meth)acrylate compounds having fluorine atoms and constituent units derived from (meth)acrylate compounds having two or more (preferably five or more) alkoxy groups (preferably ethoxy or propoxy groups). Furthermore, as a fluorinated surfactant, it can also be used on fluorinated polymers with ethylene unsaturated bonds in the side chains. Examples include MEGAFACE RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0187] From the perspective of improving environmental adaptability, surfactants derived from compounds with straight-chain perfluoroalkyl groups having seven or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), are preferred as fluorinated surfactants. Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylated and propoxylated derivatives (e.g., glycerol propoxylated, glycerol ethoxylated, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitol fatty acid esters. 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), Solsperse 20000 (all manufactured by Lubrizol Japan Limited), NCW-101, NCW-1001, NCW-1002 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-1105, D-6112, D-6112-W, D-6315 (all manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (all manufactured by Nissin Chemical). Co., Ltd. (manufacturing), etc.

[0188] Examples of silicone-based surfactants include linear polymers composed of siloxane bonds and modified siloxane polymers with organic groups introduced into the side chains or ends.

[0189] 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, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray). (Manufactured by Co., Ltd.) and models X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002, KP-101, KP-103, KP-104. KP-105, KP-106, KP-109, KP-112, KP-120, KP-121, KP-124, KP-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 (the above are Shin-Etsu Silicone Co., Ltd. (manufacturer), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials Inc.), BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378 (all manufactured by BYK Chemie), etc.

[0190] Surfactants can be used alone or in combination with two or more. When the photosensitive composition layer contains a surfactant, the surfactant content relative to the total mass of the photosensitive composition layer 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.

[0191] From the perspective of improving reliability and lamination, the water content in the photosensitive composition layer is preferably 0.01 to 1.0% by mass relative to the total mass of the photosensitive composition layer, and even better is 0.05 to 0.5% by mass.

[0192] The thickness (film thickness) of the photosensitive component layer is generally 0.1~300μm, with 0.2~100μm being preferred, 0.5~50μm being even better, 0.5~15μm being further preferred, 0.5~10μm being particularly good, and 0.5~8μm being optimal. This improves the developability and resolution of the photosensitive component layer. Furthermore, in a single-state sample, 0.5~5μm is preferred, 0.5~4μm is even better, and 0.5~3μm is further preferred.

[0193] (Impurities, etc.) The photosensitive composition layer sometimes contains impurities. Examples of impurities include, for example, metallic impurities or their ions, halide ions, residual organic solvents, and residual monomers.

[0194] Examples of metallic impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, and their ions, as well as halide ions. From the perspective of ease of contamination, the following contents of sodium ions, potassium ions, and halide ions are preferred. Metal impurities are compounds that are different from the aforementioned particles (e.g., metal oxide particles) that can be contained in the transfer film.

[0195] The content of metallic impurities relative to the total mass of the photosensitive composition layer is preferably below 80 ppm by mass, more preferably below 10 ppm by mass, and further preferably below 2 ppm by mass. A lower limit of 1 ppb by mass or more is preferred, and 0.1 ppm by mass or more is even more preferred.

[0196] Methods for adjusting the content of impurities include, for example, selecting materials with low impurity content as raw materials for the photosensitive composition layer, as well as methods for preventing the contamination of impurities during the formation of the photosensitive composition layer and methods for cleaning and removing impurities. The content of impurities can be quantified using known methods such as ICP-based luminescence spectrometry, atomic absorption spectrometry, and ion chromatography.

[0197] Examples of residual organic solvents include benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane. The content of residual organic solvent relative to the total mass of the photosensitive composition layer is preferably 100 ppm or less, more preferably 20 ppm or less, and further preferably 4 ppm or less. The lower limit relative to the total mass of the photosensitive composition layer is preferably 10 ppb or more, and more preferably 100 ppb or more. One method for adjusting the content of residual organic solvents is to adjust the drying conditions in the manufacturing process of the transfer film, as described later. Furthermore, the content of residual organic solvents can be quantified, for example, by known methods such as gas chromatography analysis.

[0198] From the perspective of improving reliability and lamination, the water content in the photosensitive composition layer is preferably 0.01 to 1.0% by mass relative to the total mass of the photosensitive composition layer, and even better is 0.05 to 0.5% by mass.

[0199] [Middle Layer] It is preferable for the transfer film to have an intermediate layer between the pseudo-support and the photosensitive component layer. Examples of intermediate layers include water-soluble resin layers and oxygen barrier layers with oxygen barrier function described as "separation layers" in Japanese Patent Application Publication No. 5-072724. From the perspective of improving productivity by increasing sensitivity during exposure and reducing the time load of the exposure machine, an oxygen barrier layer is preferable as an intermediate layer. An oxygen barrier layer that exhibits low oxygen permeability and is dispersed or dissolved in water or alkaline aqueous solution (1% by mass aqueous solution of sodium carbonate at 22°C) is even better. The following describes the components that may be included in a water-soluble resin layer (intermediate layer).

[0200] The water-soluble resin layer (intermediate layer) contains resin. It is preferable that the above-mentioned resin includes water-soluble resin as part or all of it. Examples of resins that can be used as water-soluble resins include polyvinyl alcohol resins, polyvinylpyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof. Furthermore, copolymers of (meth)acrylic acid / vinyl compounds can also be used as water-soluble resins. 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 even better. When the water-soluble resin is a copolymer of (meth)acrylic acid / vinyl compound, the component ratio (moles%) is preferably 90 / 10 to 20 / 80, and more preferably 80 / 20 to 30 / 70.

[0201] As a lower limit for the weight average molecular weight of water-soluble resin, 5,000 or more is preferred, 7,000 or more is even more preferred, and 10,000 or more is even more preferred. As an upper limit, 200,000 or less is preferred, 100,000 or less is even more preferred, and 50,000 or less is even more preferred. The dispersion (Mw / Mn) of water-soluble resin is preferably 1~10, and even better if it is 1~5.

[0202] Water-soluble resins can be used alone or in combination with two or more. The content of water-soluble resin is not particularly limited, but from the viewpoint of further improving oxygen barrier properties and interlayer mixing inhibition ability, it is preferable that the content is 50% by mass or more relative to the total mass of the water-soluble resin layer (intermediate layer), more preferably 70% by mass or more, further preferably 80% by mass or more, and especially preferably 90% by mass or more. Furthermore, there are no particular limitations on the upper limit, for example, 99.9% by mass or less is preferable, and 99.8% by mass or less is further preferably preferred.

[0203] In addition to the water-soluble resin mentioned above, the intermediate layer may contain other components. As other components, polyols, polyol alkyl oxide adducts, phenolic derivatives, or acetamine compounds are preferred, with polyols, phenolic derivatives, or acetamine compounds being even more preferred. Furthermore, other components include, for example, well-known surfactants.

[0204] Examples of polyols include glycerol, diglycerol, and diethylene glycol. The number of hydroxyl groups in polyols is preferably 2 to 10. Examples of epoxide adducts of polyols include compounds that have undergone addition of ethoxy and propoxy groups to the aforementioned polyols. The average number of additions of alkoxy groups is preferably 1 to 100, more preferably 2 to 50, and even more preferably 2 to 20. Examples of phenolic derivatives include bisphenol A and bisphenol S. Examples of acetamide compounds include N-methylpyrrolidone.

[0205] The intermediate layer preferably comprises at least one selected from the group consisting of water-soluble cellulose derivatives, polyols, oxide adducts of polyols, polyether resins, phenolic derivatives and aceamine compounds.

[0206] For other components, a molecular weight of less than 5000 is preferred, below 4000 is even better, below 3000 is further preferred, below 2000 is particularly preferred, and below 1500 is optimal. A lower limit of 60 or above is preferred.

[0207] Other ingredients may be used alone or in combination with two or more ingredients. The content of other components relative to the total mass of the intermediate layer 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. The upper limit is preferably less than 30% by mass, more preferably less than 10% by mass, and even more preferably less than 5% by mass.

[0208] The intermediate layer may contain impurities. Examples of impurities include those contained in the aforementioned photosensitive composition layer.

[0209] The thickness of the water-soluble resin layer (intermediate layer) is not particularly limited, but 0.1~5μm is preferred, and 0.5~3μm is even better. If the thickness of the water-soluble resin layer (intermediate layer) is within the above range, the oxygen barrier properties will not decrease, and the interlayer mixing inhibition ability will be excellent. Furthermore, it can further suppress the increase in the removal time of the water-soluble resin layer (intermediate layer) during development.

[0210] [Protective film] Transfer films can have a protective film on the photosensitive component layer. As a protective film, resin films with heat resistance and solvent resistance can be used, such as polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films. Furthermore, as a protective film, a resin film made of the same material as the aforementioned pseudo-support can be used. Among them, polyolefin film is preferred as a protective film, polypropylene film or polyethylene film is even better, and polyethylene film is even better.

[0211] The thickness of the protective film is preferably 1~100μm, even better is 5~50μm, further better is 5~40μm, and best is 15~30μm. From the perspective of excellent mechanical strength, a protective film thickness of 1 μm or more is preferred; from the perspective of lower cost, a thickness of 100 μm or less is preferred.

[0212] Furthermore, in the protective film, it is preferable that the number of fisheyes with a diameter of 80μm or larger contained in the protective film is less than 5 per m2. In addition, "fisheye" refers to the process of heating and melting materials, mixing and extruding them, and then using methods such as biaxial stretching and casting to produce films, in which foreign matter, undissolved substances, and oxidized deteriorated substances are incorporated into the film.

[0213] The number of particles with a diameter of 3 μm or larger contained in the protective film is preferably 30 or less per mm², more preferably 10 or less per mm², and even more preferably 5 or less per mm². This allows for the suppression of defects caused by uneven transfer of particles contained in the protective film onto the photosensitive component layer or metal layer.

[0214] From the viewpoint of imparting rollability, it is preferable that the arithmetic mean roughness Ra of the surface of the protective film and the side opposite to the surface in contact with the photosensitive component layer is 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 preferable that it is 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, it is preferable that the surface roughness Ra of the surface of the protective film in contact with the photosensitive component layer is 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 preferable that it is less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0215] [Manufacturing method of transfer film] There are no particular restrictions on the manufacturing method of transfer film, and well-known methods can be cited. As a method for manufacturing the transfer film 10, for example, a method including the following steps can be described: coating an intermediate layer forming composition on the surface of the dummy support 11 to form a coating film, and further drying the coating film to form an intermediate layer 13; and coating a photosensitive composition on the surface of the intermediate layer 13 to form a coating film, and further drying the coating film to form a photosensitive composition layer 15.

[0216] When the transfer film 10 has a protective film 19, the protective film 19 can be pressed onto the constituent 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 manufacture the transfer film 10 having a dummy support 11, an intermediate layer 13, a photosensitive composition layer 15 and a protective film 19 by including the step of setting a protective film 19 in contact with the side of the composition layer 17 opposite to the side of the dummy support 11. After the transfer film 10 is manufactured by the above manufacturing method, a roll-shaped transfer film can be made and stored by winding the transfer film 10. The roll-shaped transfer film 10 can be provided in its original form for the subsequent roll-to-roll bonding step with the substrate.

[0217] Furthermore, the above-mentioned method for manufacturing the transfer film 10 can be a method of forming a constituent layer 17 on the protective film 19.

[0218] (Method for forming water-soluble resin composition and intermediate layer (water-soluble resin layer)) As a water-soluble resin composition, it is preferable to include various components and solvents that form the aforementioned intermediate layer (water-soluble resin layer). Furthermore, in the water-soluble resin composition, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the aforementioned water-soluble resin layer. As a solvent, it is not particularly limited as long as it can dissolve or disperse water-soluble resins, and it is preferred to be selected from at least one of the group including water and water-mixed organic solvents, with water or a mixture of water and water-mixed organic solvents being more preferred. Examples of water-mixable organic solvents include alcohols with 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerol, with alcohols having 1 to 3 carbon atoms being preferred, and methanol or ethanol being even more preferred. A single solvent can be used, or two or more solvents can be used. The solvent content is preferably 50 to 2500 parts by mass relative to 100 parts by mass of the total solids of the composition, more preferably 50 to 1900 parts by mass, and even more preferably 100 to 900 parts by mass.

[0219] 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-mentioned components. For example, well-known coating methods (slit coating, spin coating, curtain coating, and inkjet coating, etc.) can be cited.

[0220] (Photosensitive composition and method for forming photosensitive composition layer) From a productive point of view, it is preferable to form the photosensitive composition by coating using a photosensitive composition comprising the components constituting the aforementioned photosensitive composition layer (e.g., resin A, polymeric compound, polymerization initiator, and thermal crosslinking agent) and a solvent. As a method for manufacturing transfer film, it is preferable to coat a photosensitive component onto an intermediate layer to form a coating film, and then dry the coating film at a predetermined temperature to form a photosensitive component layer.

[0221] As a photosensitive composition, it is preferable to include various components and solvents that form the aforementioned photosensitive composition layer. Furthermore, in the photosensitive composition, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the aforementioned photosensitive composition layer. As a solvent, there are no particular restrictions as long as it can dissolve or disperse all components other than the solvent itself, and known solvents can be used. Specifically, examples include alkyl glycol ether solvents, alkyl glycol ether acetate solvents, alcohol solvents (such as methanol and ethanol), ketone solvents (such as acetone and methyl ethyl ketone), aromatic hydrocarbon solvents (such as toluene), aprotic polar solvents (such as N,N-dimethylformamide), cyclic ether solvents (such as tetrahydrofuran), ester solvents (such as n-propyl acetate), amide solvents, lactone solvents, and mixed solvents containing two or more of these.

[0222] As a solvent, it is preferable to include at least one selected from the group consisting of alkyl glycol ether solvents and alkyl glycol ether acetate solvents. More preferably, it is preferable to include a mixed solvent consisting of at least one selected from the group consisting of alkyl glycol ether solvents and alkyl glycol ether acetate solvents and at least one selected from the group consisting of ketone solvents and cyclic ether solvents. It is further preferable to include a mixed solvent consisting of at least three of these solvents: alkyl glycol ether, alkyl glycol ether acetate solvent, and ketone solvent.

[0223] Examples of solvents for alkyl glycol ethers include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers (such as propylene glycol monomethyl ether acetate), propylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers, and dipropylene glycol dialkyl ethers. Examples of solvents for alkyl glycol ether acetates 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 solvents described in paragraph

[0014] of Japanese Patent Application Publication No. 2018-177889 may be used, and such contents are incorporated in this specification. A single solvent can be used, or two or more solvents can be used. The solvent content is preferably 50 to 1900 parts by mass relative to 100 parts by mass of the total solids content of the composition, more preferably 100 to 1200 parts by mass, and even more preferably 100 to 900 parts by mass.

[0224] Methods for coating photosensitive components include, for example, printing, spraying, roller coating, bar coating, curtain coating, spin coating, and stencil coating (i.e., slot coating).

[0225] For the drying of coatings containing photosensitive components, heating drying and vacuum drying are preferred methods. As for the drying temperature, 90°C or above is preferred, 100°C or above is even better, and 110°C or above is further preferred. However, as for the upper limit, it is not particularly limited, but 130°C or below is preferred, and 120°C or below is even better. Furthermore, regarding drying time, 20 seconds or more is preferred, 40 seconds or more is even better, and 60 seconds or more is further preferred. While there is no particular upper limit, 450 seconds or less is preferred, and 300 seconds or less is even better. Regarding drying temperature, 80°C or more is preferred, and 90°C or more is even better. Furthermore, regarding upper limits, 130°C or less is preferred, and 120°C or less is even better. Drying can also be performed by continuously changing the temperature. Furthermore, regarding drying time, 20 seconds or more is preferred, 40 seconds or more is even better, and 60 seconds or more is further preferred. Also, while there is no particular limitation on the upper limit, 600 seconds or less is preferred, and 300 seconds or less is even better.

[0226] Furthermore, transfer films can be manufactured by attaching a protective film to a photosensitive component layer. There are no particular limitations on the method of attaching the protective film to the photosensitive component layer, and well-known methods can be cited. As a device for attaching a protective film to a photosensitive component layer, known laminators such as vacuum laminators and automatic cutting laminators can be cited. A laminator equipped with any heatable rollers, such as rubber rollers, and capable of applying pressure and heating is preferred. [Example]

[0227] The features of the present invention will be further described in detail below with examples and comparative examples. The materials, amounts, proportions, processing contents, and processing procedures shown in the following examples can be appropriately modified without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limited by the specific examples shown below. Furthermore, in the following embodiments, the weight-average molecular weight of the resin is the weight-average molecular weight calculated using polystyrene based on gel permeation chromatography (GPC). Also, the theoretical acid value was used.

[0228] Materials used in the production of transfer film The materials (photosensitive components and intermediate layer forming components) used in the fabrication of the transfer film used in the embodiments will be described.

[0229] (Components of the photosensitive compound) The photosensitive composition layer of the transfer film is formed using photosensitive components. The components used in the preparation of the photosensitive composition are as follows. The photosensitive compositions used in the examples or comparative examples were obtained by mixing the components shown below with the formulations shown in Tables 2-3 below. The values ​​of each component in Tables 2-3 are parts by mass. In addition, during the preparation of the photosensitive components, a mixed solvent comprising methyl ethyl ketone (manufactured by SANKYO CHEMICAL Co., Ltd., 60 parts by mass) and propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO KK, 40 parts by mass) was prepared, and each component was added to the mixed solvent according to the formulation shown in the table below. Furthermore, the solid content concentration of each photosensitive component was 13% by mass.

[0230] [Resin] Compounds 1-4: Resins (compounds) with the characteristics shown below, respectively. In addition, compounds 1 to 4 correspond to alkali-soluble resins.

[0231] [Table 1] composition Mw acid value (mgKOH / kg) Compound 1 Styrene / Methacrylamide / Methyl Methacrylate =32 / 28 / 40 (mass%) 40000 150 Compound 2 Styrene / Methacrylamide / Methyl Methacrylate =52 / 29 / 23 (mass%) 60000 189 Compound 3 Benzyl methacrylate / methacrylic acid =81 / 19 (mass%) 40000 170 Compound 4 Styrene / Methacrylamide / Glycidyl methacrylate / Methyl methacrylate =50 / 18 / 30 / 2 (mass%) 20000 124

[0232] In the table above, the “Composition” column shows the types of constituent units of each resin (compound), and the mass ratio of each constituent unit is shown in parentheses. As for the types of constituent units, the names of the monomers from which each constituent unit originates are shown. For example, compound 1 is a resin having styrene-based constituent units, methacrylic acid-based constituent units, and methyl methacrylate-based constituent units in a mass ratio of 32:28:40.

[0233] [Polymerizing compounds] • BPE-500: Ethoxylated Bisphenol A Dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. • BPE-200: Ethoxylated Bisphenol A Dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. • BPE-100: Ethoxylated Bisphenol A Dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. Polymerizable compound 1: a dimethacrylate of polyethylene glycol with an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide added to both ends of bisphenol A. • M-270: ARONIX M-270, polypropylene glycol diacrylate (n≈12), manufactured by TOAGOSEI CO.,LTD. • A-TMPT: Trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. SR454: Ethoxylated (3)trimethylolpropane trimethacrylate, manufactured by Arkema SA SR502: Ethoxylated (9) trimethylolpropane trimethacrylate, manufactured by Arkema SA • A-9300-CL1: Caprolactone-modified tri-(2-acryloyloxyethyl)isocyanurate, manufactured by Shin-Nakamura Chemical Co., Ltd.

[0234] [Thermal crosslinking agent] • SBB-70P: Duranate, manufactured by Asahi Kasei Corporation ·TPA-B80E: Duranate, manufactured by ASAHI KASEI CORPORATION

[0235] [Polymerization initiator] • B-CIM: 2,2'-Bis(2-chlorophenyl)-4,4',5,5'-Tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer), manufactured by KUROGANE KASEI Co., Ltd.

[0236] [additive] ·SB-PI 701: 4,4'-Bis(diethylamino)benzophenone, manufactured by Sanyo Trading Co., Ltd. • Colorless crystal violet: Manufactured by Tokyo Chemical Industry Co., Ltd. N-Phenylglycine: Manufactured by Tokyo Chemical Industry Co., Ltd. Bright Green: Manufactured by Tokyo Chemical Industry Co., Ltd. • CBT-1: Carboxybenzotriazole, manufactured by JOHOKU CHEMICAL CO.,LTD. • A 1:1 (mass ratio) mixture of 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole • Phenythia well: Manufactured by FUJIFILM Wako Pure Chemical Corporation Irganox 245: Manufactured by BASF • N-Nitrophenylhydroxylamine aluminum salt: Manufactured by FUJIFILM Wako Pure Chemical Corporation • Phenylidene (manufactured by Tokyo Chemical Industry Co., Ltd.) F-552: Fluorine-based surfactant, manufactured by DIC Corporation.

[0237] (Composition of the intermediate layer formation) The following components were mixed to prepare a composition for forming an intermediate layer. The amounts of each component are expressed in parts by mass. Ion-exchanged water: 38.12 parts by weight Methanol (manufactured by Mitsubishi Gas Chemical Company, Inc.): 57.17 parts by weight KURARAY POVAL 4-88LA (Polyvinyl alcohol, manufactured by Kuraray Co., Ltd.): 3.22 parts by weight Polyvinylpyrrolidone K-30 (manufactured by NIPPON SHOKUBAI CO.,LTD.): 1.49 parts by weight MEGAFACE F-444 (Fluoropolymer Surfactant, manufactured by DIC Corporation): 0.0035 parts by weight

[0238] <Making of Transfer Film> For Examples 1, 5-7 and Comparative Example 1, the transfer film was prepared using the following procedure. First, the photosensitive compositions of each example and comparative example were coated onto a pseudo-support (a 16 μm thick polyethylene terephthalate film (LUMIRROR 16KS40, manufactured by TORAY INDUSTRIES, INC.), haze: 0.6%) with the thickness shown in Tables 2-3 after drying using a bar coater. The film was then dried in an oven at 80°C to form a photosensitive composition layer (negative photosensitive composition layer). A transfer film was produced by laminating a 16 μm thick polyethylene terephthalate (16KS40, manufactured by TORAY INDUSTRIES, INC.) as a protective film onto the obtained photosensitive composition layer.

[0239] Furthermore, regarding Examples 2-4 and 8-10, the transfer film was prepared using the following procedure. First, the intermediate layer composition was coated onto the pseudo-support (a 16 μm thick polyethylene terephthalate film (LUMIRROR 16KS40, manufactured by TORAY INDUSTRIES, INC.), haze: 0.6%) with the thickness shown in Tables 2-3 after drying using a bar coater, and then dried in an oven at 90°C to form the intermediate layer. Furthermore, a photosensitive composition was applied to the intermediate layer using a bar coater to achieve the thickness shown in Tables 2-3 after drying, and then dried in an oven at 80°C to form a photosensitive composition layer (negative photosensitive composition layer). A transfer film was produced by laminating a 16 μm thick polyethylene terephthalate (16KS40, manufactured by TORAY INDUSTRIES, INC.) as a protective film onto the obtained photosensitive composition layer.

[0240] <Manufacturing of laminates> A PET substrate with a copper layer of 500 nm thickness was fabricated on a PET film (polyethylene terephthalate film) with a thickness of 200 μm by sputtering. The transfer film was cut into 10cm squares, and the protective film was peeled off. The photosensitive component layer was then laminated onto the copper layer on the PET substrate under lamination conditions of 90°C roller temperature, 0.8MPa linear pressure, and 3.0m / min linear speed to obtain a laminate. At this point in time, when the transfer film does not include the intermediate layer, the laminate has the structure of "PET film - copper layer - photosensitive component - pseudo support", and when the transfer film includes the intermediate layer, it has the structure of "PET film - copper layer - photosensitive component - intermediate layer - pseudo support". Next, the dummy support was peeled off from the resulting stack, and a photomask with a line (μm) / space (μm) pattern of 5 / 5 was brought into close contact with the exposed surface in the stack. The substrate was irradiated with light at an exposure dose of 50 mJ / cm² using a high-pressure mercury lamp exposure machine (MAP-1200L, manufactured by Japan Science Engineering Co., Ltd., main wavelength: 365 nm). The exposure dose was set to the exposure dose required to reproduce the line and spacer shape of the photoresist pattern obtained after development. Subsequently, a 1.0% sodium carbonate aqueous solution at 30°C was used as the developing solution. Specifically, during development, a 40-second spray treatment was performed, followed by an air knife treatment to remove the developing solution, then a 30-second spray treatment with pure water, and further air knife treatment. In this way, a stacked body with photoresist patterns of line and spacing was obtained.

[0241] Next, the laminate with photoresist pattern was heated under the heating conditions (“heating temperature and heating time”) described in Tables 2-3 below. Subsequently, the resulting laminate was immersed in a 10% by mass sulfuric acid aqueous solution (liquid temperature: 40°C) for 3 minutes.

[0242] Next, the resulting laminate was placed in a copper sulfate electroplating solution (copper sulfate 75 g / L, sulfuric acid 190 g / L, chloride ions 50 ppm by mass, manufactured by Meltex Inc., “Copper Glyme PCM”, 5 mL / L) and subjected to copper electroplating treatment at 1 A / dm². After washing and drying the copper-plated laminate, it was immersed in a 1% potassium hydroxide aqueous solution (pH=13.5) at 50°C to remove the photoresist pattern. Copper wiring patterns were obtained by removing the copper layer (seed layer) of the laminate after the photoresist pattern stripping stage using an aqueous solution containing 0.1% sulfuric acid and 0.1% hydrogen peroxide. The copper wiring patterns were observed using an optical microscope, and the shape of the conductor patterns was evaluated according to the following criteria. 1: No conductor pattern is formed, or the shape of the formed conductor pattern is significantly deformed. 2: The shape of the conductor pattern formed is roughly the desired shape, but deformation is observed in some parts. 3: The shape of the conductor pattern formed is the desired shape, without deformation.

[0243] In Tables 2-3, the "Heating Temperature and Heating Time" column records the temperature and time when heating the laminate with photoresist pattern. For example, in Example 1, it is recorded as "120°C for 20 minutes", which means heating at 120°C for 20 minutes. In Tables 2 and 3, the "Elastic Modulus X (GPa)" column represents the above-mentioned elastic modulus X (GPa), and the "Elastic Modulus X / Elastic Modulus Y" column represents the above-mentioned X / Y.

[0244] [Table 2] Comparative Example 1 Example 1 Example 2 Example 3 Example 4 resin Compound 1 - - - - - Compound 2 53.27 53.07 53.07 - - Compound 3 - - - - - Compound 4 - - - 53.07 53.07 Aggregation compound BPE-500 8.63 8.53 8.53 - - BPE-200 - - - - - BPE-100 25.89 25.79 25.79 35.22 35.22 Polymer compound 1 - - - - - M-270 3.84 3.74 3.74 2.84 2.84 A-TMPT - - - - - SR-454 - - - - - SR-502 - - - - - A-9300-CL1 - - - - - Thermal crosslinking agent SBB-70P - 0.50 0.50 0.50 - TPA-B80E - - - - 0.50 polymerization Initiator B-CIM 6.83 6.83 6.83 6.83 6.83 additive SB-PI 701 0.30 0.30 0.30 0.30 0.30 Colorless crystal violet 0.40 0.40 0.40 0.40 0.40 N-Phenylglycine 0.14 0.14 0.14 0.14 0.14 Bright green - - - - - CBT-1 0.10 0.10 0.10 0.10 0.10 Mixture 1 - - - - - Feisaikou Well 0.27 0.27 0.27 0.27 0.27 Irganox245 - - - - - N-Nitrophenylhydroxylamine aluminum salt - - - - - phenidone 0.01 0.01 0.01 0.01 0.01 F-552 0.32 0.32 0.32 0.32 0.32 condition Heating temperature and heating time none 120℃ for 20 minutes 120℃ for 20 minutes 120℃ for 20 minutes 145℃ for 20 minutes Thickness (μm) of the photosensitive component layer 3 3 3 3 3 Thickness of the intermediate layer (μm) none none 1 1 1 evaluate Shape evaluation 1 2 2 2 3 Elastic modulus X (GPa) 4.5 5.2 5.2 5.6 5.9 Elastic modulus X / Elastic modulus Y 1.35 1.08 1.08 1.05 1.05

[0245] [Table 3] Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 resin Compound 1 61.70 - - - - - Compound 2 - - 50.50 - - 49.50 Compound 3 - 58.70 - 51.50 51.50 - Compound 4 - - - - - - Aggregation compound BPE-500 - 27.00 15.00 7.40 7.40 36.20 BPE-200 20.00 - - 10.00 10.00 - BPE-100 - - - - - - Polymer compound 1 - - 10.00 - - - M-270 - - - - - 5.00 A-TMPT 6.00 - 5.00 10.00 10.00 - SR-454 9.00 - 5.00 15.00 15.00 - SR-502 - 4.00 - - - - A-9300-CL1 - 7.80 9.77 - - - Thermal crosslinking agent SBB-70P - - - 0.50 TPA-B80E 0.50 0.50 0.50 0.50 0.50 polymerization Initiator B-CIM 1.90 1.10 3.00 3.80 3.80 7.00 additive SB-PI 701 0.30 0.10 0.30 0.30 0.30 0.50 Colorless crystal violet 0.40 0.66 0.60 - - 0.40 N-Phenylglycine - - - 1.00 1.00 0.20 Bright green 0.05 - 0.02 0.05 0.05 - CBT-1 0.03 0.03 - 0.05 0.05 0.10 Mixture 1 - - 0.10 0.05 0.05 - Feisaikou Well - - - - - 0.30 Irganox245 0.10 0.10 0.20 0.20 0.20 - N-Nitrophenylhydroxylamine aluminum salt 0.02 0.01 0.01 0.01 0.01 - phenidone - - - 0.01 0.01 0.01 F-552 - - - 0.13 0.13 0.29 condition Heating temperature and heating time 145℃ for 20 minutes 145℃ for 20 minutes 145℃ for 20 minutes 120℃ for 20 minutes 120℃ for 20 minutes 145℃ for 20 minutes Thickness (μm) of the photosensitive component layer 10 10 10 3 3 3 Thickness of the intermediate layer (μm) none none none 1 1 1 evaluate Shape evaluation 2 2 2 2 2 2 Elastic modulus X (GPa) 5.6 5.6 5.3 5.3 5.4 5.3 Elastic modulus X / Elastic modulus Y 1.10 1.06 1.09 1.08 1.07 1.08

[0246] As shown in the table, the desired effect can be obtained by following the method of the present invention.

[0247] 10: Transfer film 11: Pseudo-support 13: Intermediate layer 15: Photosensitive constituent layer 17: Constituent Layers 19: Protective film

Claims

1. A method for manufacturing a laminate with a conductor pattern, comprising, in sequence: a bonding step, bonding the transfer film to the substrate such that the surface of the transfer film having a dummy support and a negative-type photosensitive composition layer opposite to the dummy support side is in contact with the metal layer of a substrate having a metal layer on its surface; an exposure step, exposing the photosensitive composition layer to a pattern; a developing step, developing the exposed photosensitive composition layer to form a photoresist pattern; a heating step, heating the photoresist pattern; a cleaning step, cleaning the heated photoresist pattern with an acidic solution; an electroplating step, electroplating the metal layer located in areas where the photoresist pattern is not disposed; a peeling step, peeling off the photoresist pattern; and a removal step, removing the metal layer exposed by the peeling step and the conductor pattern formed on the substrate, wherein a dummy support peeling step is further provided between the bonding step and the exposure step or between the exposure step and the developing step to peel off the dummy support. The aforementioned photosensitive component layer contains a thermal crosslinking agent.

2. The method for manufacturing a laminate with a conductor pattern as described in claim 1, wherein the elastic modulus of the surface of the photoresist pattern heated by the aforementioned heating step on the side opposite to the substrate side is 5.0 GPa or higher.

3. The method for manufacturing a laminate with a conductor pattern as described in claim 1 or claim 2, wherein the elastic modulus of the surface of the photoresist pattern heated by the aforementioned heating step on the side opposite to the substrate side is set as elastic modulus X, and the elastic modulus of the photoresist pattern near the aforementioned substrate side heated by the aforementioned heating step is set as elastic modulus Y, wherein X / Y ≤ 1.2 is satisfied.

4. A method for manufacturing a laminate having a conductor pattern as described in claim 1 or claim 2, wherein the aforementioned photosensitive composition layer comprises a polymerizable compound and a polymerization initiator.

5. A method for manufacturing a laminate with a conductor pattern as described in claim 4, wherein the aforementioned polymeric compound has an epoxide-modified bisphenol structure.

6. A method for manufacturing a laminate having a conductor pattern as described in claim 1 or claim 2, wherein the aforementioned thermal crosslinking agent comprises a capped isocyanate compound.

7. A method for manufacturing a laminate with a conductor pattern as described in claim 1 or claim 2, wherein the haze of the aforementioned dummy support is 1.0% or less.

8. A method for manufacturing a laminate with a conductor pattern as described in claim 1 or claim 2, wherein the thickness of the aforementioned dummy support is 50 μm or less.

9. A method for manufacturing a laminate with a conductor pattern as described in claim 1 or claim 2, wherein the aforementioned transfer film has an intermediate layer between the aforementioned dummy support and the aforementioned photosensitive composition layer.

10. A method for manufacturing a laminate with a conductor pattern as described in claim 9, wherein the aforementioned intermediate layer is a water-soluble resin layer.

11. A method for manufacturing a multilayer having a conductor pattern as described in claim 1 or claim 2, wherein the aforementioned exposure step is a step of exposing the pattern via a photomask.

12. A method for manufacturing a laminate with a conductor pattern as described in claim 1 or claim 2, wherein the aforementioned exposure step is a step of exposing the aforementioned photosensitive composition layer to a pattern using active light projecting an image of a photomask through a lens.

13. A method for manufacturing a laminate with a conductor pattern as described in claim 1 or claim 2, wherein a dummy support peeling step is provided between the aforementioned bonding step and the aforementioned exposure step, wherein the aforementioned exposure step is a step of exposing the aforementioned photosensitive composition layer to a pattern by bringing the surface exposed after peeling off the aforementioned dummy support into contact with a photomask.

14. A transfer film having a pseudo-support and a negative photosensitive composition layer, and having an intermediate layer between the pseudo-support and the photosensitive composition layer, wherein the photosensitive composition layer comprises a thermal crosslinking agent, a polymeric compound having an epoxy-modified bisphenol structure, and a polymerization initiator, and the haze of the pseudo-support is 1.0% or less.

15. The transfer film as described in claim 14, wherein the thickness of the aforementioned pseudo-support is less than 50 μm.

16. The transfer film as claimed in claim 14, wherein the aforementioned intermediate layer is a water-soluble resin layer.

Images