Method for manufacturing laminates, method for manufacturing circuit wiring, transfer film

Abstract

The present invention provides: a method for manufacturing a laminate including a pattern and exhibiting an excellent pattern shape and excellent pattern adhesiveness; a method for manufacturing circuit wiring; and a transfer film. A method for manufacturing a laminate according to the present invention includes: a sticking step for bringing, into contact with a substrate, the surface at the side opposite to a middle layer side of a photosensitive composition layer in a transfer film which has a temporary support, a middle layer, and the photosensitive composition layer in the stated order, and sticking the transfer film and the substrate together; a releasing step for releasing the temporary support between the temporary support and the middle layer; an exposure step for pattern-exposing the photosensitive composition layer; and a development step for developing the exposed photosensitive composition layer by using a developer and forming a pattern. An elastic modulus X calculated through measurement X is 1.0-10.0 Gpa.

Description

[Technical Field]

[0001] The present invention relates to a method for manufacturing a laminate, a method for manufacturing circuit wiring, and a transfer film. [Background technology]

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

[0003] For example, Patent Document 1 discloses a photosensitive resin laminate in which an intermediate layer and a photosensitive resin layer are sequentially laminated on a support film. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2008-175957 [Overview of the project] [Problems that the invention aims to solve]

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

[0006] On the other hand, there was a need for the pattern obtained by transferring the photosensitive composition layer in the transfer film to the substrate, and then exposing and developing the photosensitive composition layer, to be less likely to peel off the substrate and to have excellent pattern adhesion. In particular, there was a need for superior adhesion of higher-resolution patterns.

[0007] Therefore, the object of the present invention is to provide a method for manufacturing a laminate containing a pattern that is excellent in both pattern shape and pattern adhesion. Furthermore, the present invention also aims to provide a method for manufacturing circuit wiring and a transfer film. [Means for solving the problem]

[0008] As a result of diligent research into the above problems, the inventors have found that the above problems can be solved by the following configuration.

[0009] [1] A bonding step in which a transfer film having a temporary support, an intermediate layer, and a photosensitive composition layer in this order is brought into contact with a substrate on the surface of the photosensitive composition layer opposite to the intermediate layer, and the transfer film and the substrate are bonded together. Between the above-mentioned temporary support and the above-mentioned intermediate layer, a peeling step is performed to peel off the above-mentioned temporary support, An exposure step of pattern exposure of the above photosensitive composition layer, The process includes a developing step in which the exposed photosensitive composition layer is developed using a developing solution to form a pattern, A method for manufacturing a laminate, wherein the elastic modulus X, determined by measurement X described later, is between 1.0 and 10.0 GPa. [2] The method for manufacturing a laminate according to [1], wherein the elastic modulus Y determined by the measurement Y described later is 3.5 MPa or less. [3] The method for manufacturing a laminate according to [2], wherein the ratio of the elastic modulus X to the elastic modulus Y is 1500 to 10000. [4] A method for producing a laminate according to any one of [1] to [3], wherein the content of double bonds in the photosensitive composition layer is 1.0 to 3.0 mmol / g. [5] The above photosensitive composition layer contains a resin, A method for manufacturing a laminate according to any one of [1] to [4], wherein the glass transition temperature Tg of the above resin is 90 to 150°C. [6] A method for producing a laminate according to any one of [1] to [5], wherein the acid value of the photosensitive composition layer is 50 to 100 mg KOH / g. [7] The above photosensitive composition layer comprises a bifunctional or polymerizable compound and a resin, A method for producing a laminate according to any one of [1] to [6], wherein the mass ratio of the content of the above-mentioned bifunctional or higher polymerizable compound to the content of the above-mentioned resin is 0.60 to 1.00. [8] A method for producing a laminate according to any one of [1] to [7], wherein the intermediate layer comprises at least one selected from the group consisting of polyhydric alcohols, oxide adducts of polyhydric alcohols, phenol derivatives, amide compounds, water-soluble cellulose derivatives, polyether resins, and polyamide resins. 〔9〕 The method for manufacturing a laminate according to any one of 〔1〕 to 〔8〕, wherein the thickness of the photosensitive composition layer is 1 to 20 μm. 〔10〕 The method for manufacturing a laminate according to any one of 〔1〕 to 〔9〕, wherein the thickness of the intermediate layer is 3.0 μm or less. 〔11〕 The method for manufacturing a laminate according to any one of 〔1〕 to 〔10〕, wherein the exposure step is an exposure step of pattern exposure by bringing the exposed intermediate layer into contact with a mask. 〔12〕 A bonding step of bringing the surface of the photosensitive composition layer of the transfer film having a temporary support, an intermediate layer, and a photosensitive composition layer in this order, on the side opposite to the intermediate layer side of the photosensitive composition layer, into contact with a substrate having a conductive layer, and bonding the transfer film and the substrate; A peeling step of peeling the temporary support between the temporary support and the intermediate layer; An exposure step of pattern exposure of the photosensitive composition layer; A development step of developing the exposed photosensitive composition layer with a developer to form a pattern; An etching step of etching the conductive layer in a region where the pattern is not disposed, and having a circuit wiring manufacturing method, wherein the elastic modulus X obtained by measurement X described later is 1.0 to 10.0 GPa. The method for manufacturing a circuit wiring, wherein the elastic modulus X obtained by measurement X described later is 1.0 to 10.0 GPa. 〔13〕 A transfer film having a temporary support, an intermediate layer, and a photosensitive composition layer in this order, wherein an exposure step of pattern exposure of the photosensitive composition layer is performed, and the elastic modulus X obtained by measurement X described later is 1.0 to 10.0 GPa. The transfer film, wherein the elastic modulus X obtained by measurement X described later is 1.0 to 10.0 GPa. 〔14〕 The transfer film according to 〔13〕, wherein the elastic modulus Y obtained by measurement Y described later is 3.5 MPa or less. 〔15〕 The transfer film according to 〔14〕, wherein the ratio of the elastic modulus X to the elastic modulus Y is 1500 to 10000. 〔16〕 The transfer film according to any one of 〔13〕 to 〔15〕, wherein the content of double bonds in the photosensitive composition layer is 1.0 to 3.0 mmol / g. 〔17〕 The photosensitive composition layer contains a resin, The transfer film according to any one of

[13] to

[16] , wherein the glass transition temperature Tg of the resin is 90 to 150 °C. 〔18〕 The transfer film according to any one of

[13] to

[17] , wherein the acid value of the photosensitive composition layer is 50 to 100 mgKOH / g. 〔19〕 The photosensitive composition layer contains a polymerizable compound having two or more functional groups and a resin, The transfer film according to any one of

[13] to

[18] , wherein the mass ratio of the content of the polymerizable compound having two or more functional groups to the content of the resin is 0.60 to 1.00. 〔20〕 The transfer film according to any one of

[13] to

[19] , wherein the intermediate layer contains at least one selected from the group consisting of polyhydric alcohols, oxide adducts of polyhydric alcohols, phenol derivatives, amide compounds, water-soluble cellulose derivatives, polyether resins and polyamide resins. 〔21〕 The transfer film according to any one of

[13] to

[20] , wherein the thickness of the photosensitive composition layer is 1 to 20 μm. 〔22〕 The transfer film according to any one of

[13] to

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

Advantages of the Invention

[0010] According to the present invention, it is possible to provide a method for manufacturing a laminate including a pattern, which is excellent in pattern shape and also excellent in pattern adhesion. Further, according to the present invention, it is also possible to provide a method for manufacturing a circuit wiring and a transfer film.

Brief Description of the Drawings

[0011] [Figure 1] It is a schematic view showing an example of a flare shape. [Figure 2] It is a schematic view showing an example of the configuration of a transfer film.

Embodiments for Carrying Out the Invention

[0012] Hereinafter, the present invention will be described in detail. In this specification, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. In this specification, in numerical ranges described in stages, the upper or lower limit described in one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in numerical ranges described in this specification, the upper or lower limit described in one numerical range may be replaced with the values ​​shown in the examples.

[0013] In this specification, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes, as long as their intended purpose is achieved.

[0014] In this specification, "transparent" means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more, and preferably 90% or more. In this specification, the average transmittance of visible light is a value measured using a spectrophotometer, which can be measured using, for example, a Hitachi U-3310 spectrophotometer.

[0015] In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are calculated using polystyrene as the standard substance, measured by a gel permeation chromatography (GPC) analyzer using TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all product names of Tosoh Corporation) as columns, THF (tetrahydrofuran) as the eluent, a differential refractometer as the detector, and polystyrene as the standard substance. In this specification, unless otherwise specified, the molecular weight of a compound with a molecular weight distribution is the weight-average molecular weight (Mw). In this specification, unless otherwise specified, the content of metallic elements is measured using an inductively coupled plasma (ICP) spectrometer. In this specification, unless otherwise specified, the refractive index is the value measured using an ellipsometer at a wavelength of 550 nm. In this specification, unless otherwise specified, hue values ​​are those measured using a colorimeter (CR-221, manufactured by Minolta).

[0016] In this specification, "(meth)acrylic" is a concept that encompasses both acrylic and methacrylic, and "(meth)acryloxy group" is a concept that encompasses both acryloxy group and methacryloxy group.

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

[0018] In this specification, "water-soluble" means that the solubility in 100g of water at a pH of 7.0 at a liquid temperature of 22°C is 0.1g or more. For example, a water-soluble resin refers to a resin that satisfies the solubility conditions described above.

[0019] In this specification, "solids" of a composition means the components that form the composition layers (photosensitive composition layer, intermediate layer, and thermoplastic resin layer) formed using the composition, and if the composition contains a solvent (organic solvent, water, etc.), it means all components excluding the solvent. Furthermore, any liquid components that form a composition layer are also considered to be solids.

[0020] [Method for manufacturing laminates] The present invention provides a method for manufacturing a laminate, comprising a bonding step of bringing the surface of a transfer film having a temporary support, an intermediate layer, and a photosensitive composition layer in that order, on the side of the photosensitive composition layer opposite to the intermediate layer, into contact with a substrate, thereby bonding the transfer film and the substrate. Between the temporary support and the intermediate layer, a peeling step is performed to peel off the temporary support, An exposure step in which a photosensitive composition layer is pattern-exposed, The process includes a developing step in which an exposed photosensitive composition layer is developed using a developer to form a pattern, The elastic modulus X obtained from measurement X is between 1.0 and 10.0 GPa. One preferred embodiment of the method for manufacturing a laminate is one in which the above-mentioned bonding step, peeling step, exposure step, and developing step are performed in this order.

[0021] A notable feature of the present invention's method for manufacturing laminates is that the elastic modulus X, determined by measurement X described later, is between 1.0 and 10.0 GPa. Although the detailed mechanism by which the method for manufacturing the laminate of the present invention achieves the desired effect is not clear, the inventors speculate as follows. The inventors of this invention have found that when the elastic modulus X is less than 1.0 GPa, the strength of the pattern (cured layer) obtained by exposing the photosensitive composition layer is too low, resulting in a flared shape at the base due to swelling and dissolution of the pattern when developed with a developer. Furthermore, when the elastic modulus X is greater than 10.0 GPa, the strength of the pattern (cured layer) obtained by exposing the photosensitive composition layer is too high, resulting in poor adhesion between the cured layer and the transfer target. In light of the above, we hypothesize that by adjusting the elastic modulus X within a predetermined range, the manufacturing method of the laminate of the present invention can achieve both excellent pattern shape and excellent pattern adhesion. Hereinafter, the effect of the present invention is also referred to as being superior if at least one of the following effects is obtained: superior pattern shape and superior pattern adhesion.

[0022] In the following, the method for manufacturing the laminate of the present invention will be described in detail for each step. While the descriptions of the constituent elements below may be based on a typical embodiment of the present invention, the present invention is not limited to such embodiments.

[0023] [Module of elasticity] <Elastic modulus X> In the method for manufacturing a laminate of the present invention, the elastic modulus X determined by measurement X is 1.0 to 10.0 GPa, and from the viewpoint of achieving superior effects of the present invention, 1.0 to 8.0 GPa is preferred, 2.0 to 8.0 GPa is more preferred, 3.0 to 6.0 GPa is even more preferred, and 4.0 to 6.0 GPa is particularly preferred.

[0024] The modulus of elasticity X is a value obtained by the following measurement X. Measurement X involves contacting the substrate with the side of the photosensitive composition layer of the transfer film opposite to the intermediate layer, bonding the transfer film and the substrate, peeling the temporary support from the intermediate layer to the resulting laminate, exposing the entire photosensitive composition layer from the exposed intermediate layer side, peeling off the exposed intermediate layer, and then measuring the elastic modulus of the exposed cured layer, which is defined as the elastic modulus X. The exposure conditions (type of light source, exposure amount, etc.) for the full-surface exposure described above are the same as those used in the exposure process described later. In other words, the full-surface exposure performed in measurement X corresponds to the exposure performed in the exposure process described later, but with the exposure range changed to the entire photosensitive composition layer. For example, the modulus of elasticity can be measured using a rheometer DFR-2 manufactured by T.A. Instruments, under the following conditions: set temperature of 20-125°C, heating rate of 5°C / min, frequency of 1Hz, and strain of 0.5%. Methods for peeling off the exposed intermediate layer include, for example, known peeling methods, with tape peeling being preferred. If the transfer film has a protective film, measurement X should be performed after peeling the protective film off the transfer film. The substrate used in measurement X is the same substrate used in the manufacturing method of the laminate, which will be described in detail later.

[0025] <elastic modulus Y> The elastic modulus Y obtained by measurement Y is preferably 10.0 MPa or less, more preferably 5.0 MPa or less, even more preferably 3.5 MPa or less, particularly preferably 1.0 MPa or less, and most preferably 0.8 MPa or less, from the standpoint of excellent suppression of developing residue. The lower limit is preferably 0.1 MPa or more.

[0026] The elastic modulus Y is determined by measuring the elastic modulus of the photosensitive composition layer of the transfer film. In other words, the elastic modulus Y corresponds to the elastic modulus of the unexposed portion of the photosensitive composition layer that has not undergone exposure treatment. One example of a method for measuring the modulus of elasticity is the method used for measuring the modulus of elasticity X as described above. Measurement Y may be performed after peeling the intermediate layer from the transfer film. Examples of methods for peeling the intermediate layer include known peeling methods, with tape peeling being preferred. Furthermore, if the transfer film has a protective film, the measurement Y is performed after peeling off the protective film from the transfer film.

[0027] The ratio of the elastic modulus X to the elastic modulus Y (elastic modulus X / elastic modulus Y) is preferably 100 or more, more preferably 200 to 10000, even more preferably 1000 to 10000, particularly preferably 1500 to 10000, and most preferably 3000 to 8000, from the standpoint of excellent suppression of development residue.

[0028] Methods for adjusting elastic moduli X and Y include, for example, changing the type and content of resin contained in the photosensitive composition layer. Specifically, the methods include using a resin in which the weight-average molecular weight, acid value, and Tg (glass transition temperature) are adjusted to the preferred configurations described later; using a resin synthesized using a monomer with three or more functions and / or a monomer having an aromatic hydrocarbon group in the preferred configurations; and methods combining these.

[0029] [Lamination process] The lamination process involves bringing the surface of the photosensitive composition layer of the transfer film, which has a temporary support, an intermediate layer, and a photosensitive composition layer in that order, on the side opposite to the intermediate layer, into contact with the substrate, thereby laminating the transfer film and the substrate. If the transfer film has a protective film, the lamination process may be carried out after peeling off the protective film.

[0030] In the lamination process, the surface of the photosensitive composition layer of the transfer film opposite to the intermediate layer is brought into contact with the substrate and pressed down. Examples of bonding methods include known transfer methods and lamination methods. In particular, as a method of bonding, it is preferable to place the surface of the photosensitive composition layer of the transfer film opposite to the intermediate layer side onto the substrate and apply pressure and heat using a roll or the like. Lamination methods include those using known laminators such as vacuum laminators and auto-cut laminators. A lamination temperature of 70 to 130°C is preferred.

[0031] A substrate having a conductive layer is preferred as the substrate. A substrate having a conductive layer may have any other layers formed on it as needed. In other words, a conductive substrate is preferred, which has at least a conductive layer disposed on it. Examples of substrates include resin substrates, glass substrates, and semiconductor substrates. As a substrate, paragraph

[0140] of International Publication No. 2018 / 155193 is preferred, and the contents of this publication are incorporated herein. As the material for the resin substrate, cycloolefin polymers or polyimides are preferred. The thickness of the resin substrate is preferably 5 to 200 μm, and more preferably 10 to 100 μm.

[0032] As the conductive layer, at least one conductive layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer is preferred from the viewpoint of conductivity and fine wire formation. The substrate may have only one conductive layer, or it may have two or more conductive layers. When two or more conductive layers are arranged, it is preferable that the conductive layers are made of different materials. As the conductive layer, paragraph

[0141] of International Publication No. 2018 / 155193 is preferred, and the contents of this publication are incorporated herein.

[0033] [Peeling process] The peeling process is the process of peeling the temporary support away from the intermediate layer. Examples of methods for peeling off the temporary support include known peeling methods. Specifically, the cover film peeling mechanism described in paragraphs

[0161] to

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

[0034] [Exposure process] The exposure process involves pattern exposure of the photosensitive composition layer. "Pattern exposure" refers to a method of exposure that involves a pattern of exposure, meaning that there are areas that are exposed and areas that are not. The positional relationship between the exposed and unexposed areas in pattern exposure is not particularly limited and can be adjusted as appropriate.

[0035] The direction of exposure is not particularly limited, but exposure may be performed from the intermediate layer side of the photosensitive composition layer, or from the opposite side (substrate side) of the photosensitive composition layer.

[0036] In the exposure process, it is preferable to bring the intermediate layer exposed by the peeling process described above into contact with the mask and perform pattern exposure. By performing pattern exposure in contact with the mask, a high-resolution pattern can be obtained. Specifically, it is preferable to place a mask having predetermined openings in close contact with the intermediate layer exposed by peeling off the temporary support and then perform pattern exposure. By performing an exposure process that brings the above-mentioned intermediate layer into contact with the mask, a curing reaction of the components contained in the photosensitive composition layer can occur in the exposed region of the photosensitive composition layer (the position corresponding to the opening of the mask). After exposure, an alkaline development process is performed to remove the unexposed region of the photosensitive composition layer, thereby forming a pattern. The manufacturing method for the laminate preferably includes a peeling step between the exposure step and the development step, in which the mask used in the exposure step is peeled off.

[0037] As a light source for pattern exposure, any light source capable of irradiating with light in a wavelength range sufficient to cure the photosensitive composition layer (e.g., 365 nm and 405 nm) can be appropriately selected and used. In particular, the dominant wavelength of the exposure light for pattern exposure is preferably 365 nm. The dominant wavelength refers to the wavelength with the highest intensity.

[0038] Examples of light sources include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps. The exposure dose is 5-200 mJ / cm². 2 Preferably, 10-200 mJ / cm² 2 This is preferable. Examples of light sources, exposure amounts, and exposure methods are given in paragraphs

[0146] to

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

[0039] [Development process] The developing process involves developing the exposed photosensitive composition layer using a developer solution to form a pattern. By developing with an alkaline developer (alkaline aqueous solution), the unexposed areas of the photosensitive composition layer are removed, and a pattern is formed with the openings of the mask as convex parts.

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

[0041] Examples of development methods include well-known development methods. Specifically, these include paddle development, shower development, spin development, and dip development. As for the development method, the development method described in paragraph

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

[0042] [Post-exposure process and post-bake process] The method for manufacturing a laminate of the present invention may further include a step of exposing the pattern obtained by the development step to light (hereinafter also referred to as the "post-exposure step") and / or a step of heating (hereinafter also referred to as the "post-bake step"). If the method for manufacturing the laminate includes both a post-exposure step and a post-bake step, it is preferable to perform the post-exposure step first, followed by the post-bake step. The exposure dose in the post-exposure process is 100-5000 mJ / cm². 2 Preferably, 200-3000 mJ / cm² 2 This is preferable. In the post-bake process, the post-bake temperature is preferably 80 to 250°C, and more preferably 90 to 160°C. In the post-bake process, the post-bake time is preferably 1 to 180 minutes, and more preferably 10 to 60 minutes.

[0043] The position and size of the pattern formed on the substrate obtained by the manufacturing method of the laminate are not particularly limited. In particular, a fine linear pattern is preferred. Specifically, the width of the pattern is preferably 20 μm or less, more preferably 15 μm or less, even more preferably 10 μm or less, and especially preferably 5 μm or less. The lower limit is preferably 1 μm or more, and more preferably 3 μm or more.

[0044] [Applications of laminates] The laminate produced by the manufacturing method of the present invention can be applied to various devices. Examples of devices equipped with the laminate include input devices, preferably touch panels, and more preferably capacitive touch panels. The input device can be applied to display devices such as organic EL (organic electroluminescent) displays and liquid crystal displays.

[0045] [Method of manufacturing circuit wiring] The present invention's method for manufacturing circuit wiring includes an etching step in which, when a conductive substrate is used as the substrate, the conductive layer in a region of the laminate having a pattern manufactured by the above-described method for manufacturing a laminate is etched.

[0046] In the following, the method for manufacturing circuit wiring according to the present invention will be described in detail for each step. While the following descriptions of constituent elements may be based on a typical embodiment of the present invention, the present invention is not limited to such embodiments.

[0047] [Etching process] The etching process is a process of etching the conductive layer in areas where no pattern is placed. Specifically, in the etching process, the pattern obtained from the photosensitive composition layer by the development process in the manufacturing method of the laminate is used as an etching resist, and the conductive layer is etched. The substrate is the same as the substrate in the manufacturing method of the laminate described above, and the preferred embodiment is also the same.

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

[0209] to

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

[0048] to

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

[0049] For wet etching, the etching solution used can be appropriately selected as either acidic or alkaline depending on the object being etched. Examples of acidic etching solutions include acidic aqueous solutions containing one or more acidic compounds, and acidic mixed aqueous solutions of an acidic compound and at least one salt selected from the group consisting of ferric chloride, ammonium fluoride, and potassium permanganate. The acidic compound (a compound that dissolves in water and exhibits acidity) contained in the acidic aqueous solution is preferably at least one acidic compound selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid. Examples of alkaline etching solutions include alkaline aqueous solutions containing one or more alkaline compounds, and alkaline aqueous solutions of alkaline compounds and salts (e.g., potassium permanganate). As the alkaline compound (a compound that dissolves in water and exhibits alkalinity) contained in the alkaline aqueous solution, at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (for example, tetramethylammonium hydroxide, etc.) is preferred.

[0050] [Removal process] The method for manufacturing circuit wiring according to the present invention may include a removal step for removing any remaining patterns. The removal process is preferably carried out after the etching process described above. Methods for removing remaining patterns include, for example, removal by chemical treatment, and a method using a removal solution is preferred. The temperature of the removal solution is preferably 30 to 80°C, and more preferably 50 to 80°C. One preferred embodiment of the removal method is, for example, immersing a substrate having the pattern to be removed in a removal solution that is being stirred and has a liquid temperature of 50 to 80°C for 1 to 30 minutes. Methods for removing remaining patterns include, for example, using a removal solution and removing them by known methods such as the spray method, shower method, and paddle method.

[0051] Examples of removal solutions include those obtained by dissolving an alkaline inorganic compound or an alkaline organic compound in at least one solution selected from the group consisting of water, dimethyl sulfoxide, N-methylpyrrolidone, and mixed solutions thereof. Examples of alkaline inorganic compounds include sodium hydroxide and potassium hydroxide. Examples of alkaline organic compounds include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

[0052] [Other processes] The method for manufacturing circuit wiring may include other steps in addition to those described above. Other steps include, for example, the step of reducing the visible light reflectance as described in paragraph

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

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

[0053] <Process to reduce visible light reflectance> A method for manufacturing circuit wiring may include a step of performing a treatment to reduce the visible light reflectance of some or all of the multiple conductive layers on the substrate. One example of a treatment to reduce visible light reflectivity is oxidation. If the substrate has a conductive layer containing copper, the copper can be oxidized to copper oxide, which blackens the conductive layer and reduces its visible light reflectivity. Examples of treatments for reducing visible light reflectance include paragraphs

[0017] to

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

[0041] ,

[0042] ,

[0048] and

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

[0054] <Steps for forming an insulating film, and for forming a new conductive layer on the surface of the insulating film> A method for manufacturing circuit wiring may include the steps of forming an insulating film on the surface of the circuit wiring and forming a new conductive layer on the surface of the insulating film. Through the above process, a first electrode pattern and an insulated second electrode pattern can be formed. For example, a known method for forming a permanent film can be used as a step in forming the insulating film. Alternatively, an insulating film with a desired pattern may be formed by photolithography using an insulating photosensitive composition. As a step in forming a new conductive layer on the surface of an insulating film, for example, a new conductive layer with a desired pattern may be formed by photolithography using a conductive photosensitive composition.

[0055] In the method for manufacturing circuit wiring, it is also preferable to use a substrate having multiple conductive layers on both surfaces of the substrate, and to form circuit wiring sequentially or simultaneously on the conductive layers formed on both surfaces of the substrate. With the above configuration, a touch panel circuit wiring can be formed in which a first conductive pattern is formed on one substrate surface and a second conductive pattern is formed on the other substrate surface. It is also preferable to form the touch panel circuit wiring with the above configuration from both sides of the substrate using a roll-to-roll method.

[0056] [Applications of circuit wiring] Circuit wiring manufactured by this method can be applied to various devices. Examples of devices equipped with the above-mentioned circuit wiring include input devices, touch panels are preferred, and capacitive touch panels are more preferred. The above-mentioned input device can be applied to display devices such as organic EL displays and liquid crystal displays.

[0057] [Transfer film] The transfer film of the present invention comprises a temporary support, an intermediate layer, and a photosensitive composition layer in that order, and is subjected to an exposure step in which the photosensitive composition layer is pattern-exposed, wherein the elastic modulus X determined by measurement X is 1.0 to 10.0 GPa. The elastic modulus X, elastic modulus Y, and the ratio of elastic modulus X to elastic modulus Y in the transfer film are the same as those described in the above-mentioned method for manufacturing the laminate, and the preferred ranges are also the same.

[0058] The transfer film may have other layers besides the photosensitive composition layer and the intermediate layer. Other layers include, for example, a thermoplastic resin layer, which will be described later. Furthermore, the transfer film may have a protective film, described later, on top of the photosensitive composition layer.

[0059] The embodiment of the transfer film is not particularly limited, but for example, the following configurations are possible. (1) "Temporary support / intermediate layer / photosensitive composition layer / protective film" (2) "Temporary support / thermoplastic resin layer / intermediate layer / photosensitive composition layer / protective film" In each of the above configurations, a negative-type photosensitive composition layer is preferred as the photosensitive composition layer. A colored resin layer is also preferred as the photosensitive composition layer.

[0060] From the viewpoint of suppressing bubble generation in the lamination process described above, the maximum width of the waviness of the transfer film is preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 60 μm or less. The lower limit is preferably 0 μm or more, more preferably 0.1 μm or more, and even more preferably 1 μm or more. The maximum width of the waviness in the transfer film is the value measured by the following procedure. First, the transfer film is cut perpendicular to the main surface to a size of 20 cm x 20 cm to prepare a test sample. If the transfer film has a protective film, the protective film is peeled off from the transfer film. Next, the test sample is placed on a smooth and horizontal stage with the surface of the temporary support facing the stage. After placement, a 3D surface image is obtained by scanning the surface of the test sample in a 10 cm square area in the center of the sample with a laser microscope (e.g., Keyence VK-9700SP), and the minimum concave height is subtracted from the maximum convex height observed in the obtained 3D surface image. The above operation is performed for 10 test samples, and the arithmetic mean is taken as the maximum waviness width of the transfer film.

[0061] For superior adhesion, the transmittance of light at a wavelength of 365 nm in the photosensitive composition layer is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more. There is no particular upper limit, but 99.9% or less is preferred.

[0062] An example of an embodiment of the transfer film will be described. The transfer film 10 shown in Figure 1 comprises, in this order, a temporary support 11, a composition layer 17 including an intermediate layer 13 and a photosensitive composition layer 15, and a protective film 19. Although the transfer film 10 shown in Figure 1 has a protective film 19 placed on it, the protective film 19 does not necessarily have to be placed on it. In Figure 1, each layer except for the protective film 19 that can be placed on the temporary support 11 is also referred to as a composition layer 17. Furthermore, the transfer film may have a thermoplastic resin layer in addition to the above-mentioned layer, and it is preferable that the thermoplastic resin layer be placed between the temporary support 11 and the intermediate layer 13.

[0063] In the following, the transfer film of the present invention will be described in detail, including each component and element. While the following descriptions of constituent elements may be based on typical embodiments of the present invention, the present invention is not limited to such embodiments.

[0064] [Temporary support] The transfer film has a temporary support. The temporary support is a component that supports the photosensitive composition layer and is ultimately removed by a peeling process.

[0065] The temporary support may have a single-layer or multi-layer structure. A film is preferred as the temporary support, and a resin film is more preferred. Furthermore, a film that is flexible and does not undergo significant deformation, shrinkage, or stretching under pressure or under pressure and / or heating is also preferred as the temporary support, and a film that is free from deformation such as wrinkles and scratches is also preferred. Examples of films include polyethylene terephthalate film (e.g., biaxially oriented polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film, with polyethylene terephthalate film being preferred.

[0066] The temporary support is preferably highly transparent so that pattern exposure can be performed through it. Specifically, the transmittance of the temporary support at a wavelength of 365 nm is preferably 60% or more, and more preferably 70% or more. The upper limit is preferably less than 100%. From the viewpoint of pattern formation during pattern exposure via the temporary support and the transparency of the temporary support, it is preferable that the haze of the temporary support be small. Specifically, the haze of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less. The lower limit is preferably 0% or more.

[0067] From the standpoint of pattern formation during pattern exposure via a temporary support and the transparency of the temporary support, it is preferable to have a small number of fine particles, foreign matter, and defects in the temporary support. Specifically, the number of fine particles (e.g., fine particles with a diameter of 1 μm), foreign matter, and defects in the temporary support should be 50 per 10 mm. 2 The following is preferable: 10 pieces / 10mm 2 The following is more preferable: 3 pieces / 10mm 2 The following is even more preferable: 0 pieces / 10mm2 is particularly preferred.

[0068] The thickness of the temporary support is preferably 5 to 200 μm, more preferably 5 to 150 μm, still more preferably 5 to 50 μm, and particularly preferably 5 to 25 μm from the viewpoints of ease of handling and versatility. The thickness of the temporary support is calculated as the average value of any five points measured by cross-sectional observation using SEM (Scanning Electron Microscope).

[0069] From the viewpoint of handling properties, the temporary support may have a layer containing fine particles (lubricant layer) on one or both surfaces of the temporary support. The diameter of the fine particles contained in the lubricant layer is preferably 0.05 to 0.8 μm. The thickness of the lubricant layer is preferably 0.05 to 1.0 μm.

[0070] From the viewpoint of improving the adhesion between the temporary support and the photosensitive composition layer, the surface of the temporary support in contact with the photosensitive composition layer may be surface-modified. Examples of the surface modification treatment include treatments using UV irradiation, corona discharge, plasma, and the like. The exposure amount in UV irradiation is preferably 10 to 2 2000 mJ / cm and more preferably 50 to 2 1000 mJ / cm. If the exposure amount is within the above range, the lamp output and illuminance are not particularly limited. Examples of the light source in UV irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes (LEDs) that emit light in the wavelength band of 150 to 450 nm.

[0071] Examples of the temporary support include biaxially stretched polyethylene terephthalate films with a thickness of 16 μm, biaxially stretched polyethylene terephthalate films with a thickness of 12 μm, and biaxially stretched polyethylene terephthalate films with a thickness of 9 μm. Furthermore, examples of provisional supports include paragraphs

[0017] to

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

[0019] to

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

[0041] to

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

[0029] to

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

[0072] [Photosensitive composition layer] The transfer film of the present invention has a photosensitive composition layer. In display devices equipped with touch panels such as capacitive input devices (e.g., organic EL display devices and liquid crystal display devices), conductive layer patterns such as electrode patterns corresponding to sensors in the viewing area, peripheral wiring areas, and output wiring areas are provided inside the touch panel. Generally, a method is widely employed to form patterned layers by providing a negative-type photosensitive composition layer on a substrate using a transfer film or the like, exposing the photosensitive layer through a mask having the desired pattern, and then developing it. Therefore, a negative-type photosensitive composition layer is preferred as the photosensitive composition layer. When the photosensitive composition layer is a negative-type photosensitive composition layer, the formed pattern corresponds to the cured layer.

[0073] The photosensitive composition layer preferably contains a resin, a polymerizable compound, and a polymerization initiator, as described later. Furthermore, as described later, the photosensitive composition layer may also contain an alkali-soluble resin (such as a resin that is an alkali-soluble resin). In other words, the photosensitive composition layer preferably contains a resin including an alkali-soluble resin, a polymerizable compound, and a polymerization initiator. The photosensitive composition layer preferably contains 10 to 90% by mass of resin, 5 to 70% by mass of polymerizable compound, and 0.01 to 20% by mass of polymerization initiator, based on the total mass of the photosensitive composition layer.

[0074] <Resin> The photosensitive composition layer may contain a resin. Alkali-soluble resins are preferred as the resin. As the resin, an alkali-soluble resin used in the thermoplastic resin layer described later may be used.

[0075] To suppress line width thickening and resolution deterioration when the focal position shifts during exposure, it is preferable that the resin contains constituent units derived from monomers having aromatic hydrocarbon groups. Examples of the above-mentioned aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The content of constituent units derived from monomers having aromatic hydrocarbon groups in the resin is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, based on the total mass of the resin. The upper limit is preferably 80% by mass or less, more preferably 60% by mass or less, even more preferably 55% by mass or less, and particularly preferably 45% by mass or less, based on the total mass of the resin. When the photosensitive composition layer contains multiple resins, it is preferable that the average value of the content of constituent units derived from monomers having aromatic hydrocarbon groups falls within the above range. The above average value is calculated using the mass average value.

[0076] Examples of monomers having aromatic hydrocarbon groups include monomers having aralkyl groups, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimers, and styrene trimers). Monomers having aralkyl groups or styrene are preferred, and styrene is more preferred. When the monomer having an aromatic hydrocarbon group in the resin is styrene, the content of constituent units derived from styrene is preferably 10 to 80% by mass, more preferably 10 to 60% by mass, even more preferably 20 to 60% by mass, particularly preferably 20 to 55% by mass, and most preferably 30 to 45% by mass, relative to the total mass of the resin. Furthermore, if the photosensitive composition layer contains multiple resins, it is preferable that the average content of constituent units having aromatic hydrocarbon groups falls within the above range. The above average value is calculated using the mass average.

[0077] Examples of aralkyl groups include substituted or unsubstituted phenylalkyl groups (excluding benzyl groups) and substituted or unsubstituted benzyl groups, with substituted or unsubstituted benzyl groups being preferred.

[0078] Examples of monomers having a phenylalkyl group include phenylethyl (meth)acrylate.

[0079] Examples of monomers having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; and vinyl monomers having a benzyl group, such as vinyl benzyl chloride and vinylbenzyl alcohol. Among these, benzyl (meth)acrylate is preferred. When the monomer component having an aromatic hydrocarbon group in the resin is benzyl (meth)acrylate, the content of constituent units derived from benzyl (meth)acrylate is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, even more preferably 70 to 90% by mass, and particularly preferably 75 to 90% by mass, based on the total mass of the resin.

[0080] Resins containing constituent units derived from monomers having aromatic hydrocarbon groups are preferably obtained by polymerizing a monomer having aromatic hydrocarbon groups with at least one of the first monomers described later and / or at least one of the second monomers described later.

[0081] Resins that do not contain constituent units derived from monomers having aromatic hydrocarbon groups are preferably obtained by polymerizing at least one of the first monomers described later, and more preferably by copolymerizing at least one of the first monomers with at least one of the second monomers described later.

[0082] The first monomer is a monomer that has a carboxyl group in its molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid semiester, with (meth)acrylic acid being preferred. The content of constituent units derived from the first monomer in the resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 30% by mass, based on the total mass of the resin. When the above content is 5% by mass or more, excellent developability and edge fusing control can be achieved. When the above content is 50% by mass or less, high resolution of the resist pattern, control of the tail shape, and high chemical resistance of the resist pattern can be achieved.

[0083] The second monomer is non-acidic and has at least one polymerizable unsaturated group in its molecule. Examples of the second monomer include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; vinyl alcohol esters such as vinyl acetate; and (meth)acrylonitrile. Among these, methyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or n-butyl (meth)acrylate are preferred, and methyl (meth)acrylate or ethyl (meth)acrylate are more preferred. The content of constituent units derived from the second monomer in the resin is preferably 5 to 80% by mass, more preferably 15 to 60% by mass, even more preferably 20 to 60% by mass, particularly preferably 20 to 48% by mass, and most preferably 30 to 48% by mass, relative to the total mass of the resin.

[0084] When the resin contains constituent units derived from monomers having aralkyl groups and / or constituent units derived from styrene, line width thickening and deterioration of resolution when the focal position shifts during exposure can be suppressed. Preferably, the resin is a copolymer containing constituent units derived from methacrylic acid, methyl methacrylate, and styrene; a copolymer containing constituent units derived from methacrylic acid, methyl methacrylate, ethyl methacrylate, and styrene; or a copolymer containing constituent units derived from methacrylic acid and benzyl methacrylate. One preferred embodiment of the resin is one in which the resin contains 30 to 60% by mass of constituent units derived from a monomer having an aromatic hydrocarbon group, 10 to 40% by mass of constituent units derived from a first monomer, and 20 to 48% by mass of constituent units derived from a second monomer. Another preferred embodiment of the resin is one in which 70 to 90% by mass of constituent units derived from monomers having aromatic hydrocarbon groups and 10 to 25% by mass of constituent units derived from the first monomer.

[0085] The resin may have a linear structure, a branched structure, or an alicyclic structure in its side chains. By using monomers containing a group with a branched structure in its side chain or a group with an alicyclic structure in its side chain, branched and alicyclic structures can be introduced into the side chains of the resin. The group with the alicyclic structure may be monocyclic or polycyclic. Examples of monomers containing a group with a branched structure in its side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, tert-amyl (meth)acrylate, sec-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and tert-octyl (meth)acrylate. Among these, isopropyl (meth)acrylate, isobutyl (meth)acrylate, or tert-butyl methacrylate are preferred, and isopropyl methacrylate or tert-butyl methacrylate are more preferred. Examples of monomers containing a group with an alicyclic structure in its side chain include monomers having a monocyclic aliphatic hydrocarbon group and monomers having a polycyclic aliphatic hydrocarbon group. Also, (meth)acrylates having an alicyclic hydrocarbon group with 5 to 20 carbon atoms are also examples. Specifically, (meth)acrylic acid (bicyclo[2.2.1]heptyl-2), (meth)acrylic acid-1-adamantyl, (meth)acrylic acid-2-adamantyl, (meth)acrylic acid-3-methyl-1-adamantyl, (meth)acrylic acid-3,5-dimethyl-1-adamantyl, (meth)acrylic acid-3-ethyladamantyl, (meth)acrylic acid-3-methyl-5-ethyl-1-adamantyl, (meth)acrylic acid-3,5,8-triethyl-1-adamantyl, (meth)acrylic acid-3,5-dimethyl-8-ethyl-1-adamantyl, (meth)acrylic acid-2-methyl-2-adamantyl, (meth)acrylic acid-2-ethyl-2-adamantyl, (meth)acrylic acid-3-hydroxy- Examples include 1-adamantyl, octahydro-4,7-menthanoinden-5-yl (meth)acrylate, octahydro-4,7-menthanoinden-1-ylmethyl (meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl (meth)acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fentyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, and cyclohexyl (meth)acrylate. Among these, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fentyl (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecane (meth)acrylate are preferred, and cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate are more preferred.

[0086] The Tg of the resin is preferably 30 to 150°C, more preferably 60 to 150°C, even more preferably 90 to 150°C, particularly preferably 100 to 150°C, and most preferably 100 to 120°C.

[0087] The acid value of the resin is preferably 220 mgKOH / g or less, more preferably less than 200 mgKOH / g, even more preferably less than 190 mgKOH / g, and particularly preferably less than 170 mgKOH / g, from the viewpoint of achieving superior effects of the present invention. The lower limit is preferably 10 mgKOH / g or more, more preferably 50 mgKOH / g or more, even more preferably 70 mgKOH / g or more, and particularly preferably 90 mgKOH / g or more, from the viewpoint of achieving superior effects of the present invention. The acid value (mgKOH / g) is the mass (mg) of potassium hydroxide required to neutralize 1 g of the sample. The acid value can be determined, for example, according to the method described in JIS K0070:1992. The acid value of a resin can be adjusted by the type of constituent units the resin possesses and / or the content of constituent units containing acid groups.

[0088] The weight-average molecular weight of the resin is preferably 5,000 to 500,000, more preferably 10,000 to 100,000, even more preferably 20,000 to 50,000, and particularly preferably 20,000 to 40,000. When the weight-average molecular weight is 500,000 or less, resolution and developability can be improved. Also, when the weight-average molecular weight is 5,000 or more, the properties of the developed aggregates and the properties of the unexposed film, such as edge fusing and cut-tip properties of the transfer film, can be controlled. Edge fusing refers to the degree to which the photosensitive composition layer tends to protrude from the edge of the roll when the transfer film is wound into a roll. Cut-tip properties refer to the degree to which chips tend to fly off when the unexposed film is cut with a cutter. If these chips adhere to the upper surface of the transfer film, they can be transferred to the mask in subsequent exposure processes, causing defective products. The degree of dispersion of the resin is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

[0089] The photosensitive composition layer may contain other resins in addition to the resins described above. Other resins include, for example, acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0090] The resin may be used individually or in combination of two or more types. When using two or more types of resins, it is preferable to use a mixture of two resins containing constituent units derived from monomers having aromatic hydrocarbon groups, or to use a mixture of a resin containing constituent units derived from monomers having aromatic hydrocarbon groups and a resin that does not contain constituent units derived from monomers having aromatic hydrocarbon groups. In the latter case, the content of the resin containing constituent units derived from monomers having aromatic hydrocarbon groups is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of the resin. The upper limit is preferably 100% by mass or less.

[0091] The resin content is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, even more preferably 30 to 70% by mass, and particularly preferably 40 to 60% by mass, relative to the total mass of the photosensitive composition layer. When the resin content is 90% by mass or less relative to the total mass of the photosensitive composition layer, the development time can be controlled. Furthermore, when the resin content is 10% by mass or more relative to the total mass of the photosensitive composition layer, the edge fusing resistance can be improved.

[0092] One method for synthesizing the resin is to dilute one or more of the above-mentioned monomers with a solvent such as acetone, methyl ethyl ketone, and isopropanol, add an appropriate amount of a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile to the solution, and then heat and stir. The mixture may also be synthesized by adding a portion of it dropwise to the reaction solution. After the reaction is complete, the solvent may be further added to adjust the concentration to the desired level. In addition to the above, other methods for synthesizing resins include bulk polymerization, suspension polymerization, and emulsion polymerization.

[0093] <Polymerizable compound> The photosensitive composition layer preferably contains a polymerizable compound having polymerizable groups. In this specification, "polymerizable compound" means a compound that polymerizes under the action of a polymerization initiator described later, and is different from the resin described above.

[0094] The polymerizable groups in polymerizable compounds are not particularly limited as long as they are groups that participate in polymerization reactions, but examples include groups having ethylenically unsaturated groups such as vinyl groups, acryloyl groups, methacryloyl groups, styryl groups, and maleimide groups; and groups having cationic polymerizable groups such as epoxy groups and oxetane groups. In particular, polymerizable groups are preferably groups having an ethylenically unsaturated group, and acryloyl groups or methacryloyl groups are more preferred.

[0095] As polymerizable compounds, compounds having one or more ethylenically unsaturated groups (ethylenically unsaturated compounds) are preferred in that they provide superior photosensitivity to the photosensitive composition layer, and compounds having two or more ethylenically unsaturated groups in one molecule (polyfunctional ethylenically unsaturated compounds) are more preferred. Furthermore, in terms of superior resolution and exfoliation properties, the number of ethylenically unsaturated groups in one molecule of the ethylenically unsaturated compound is preferably 1 to 6, more preferably 1 to 3, even more preferably 2 to 3, and particularly preferably 3.

[0096] In terms of achieving a better balance between photosensitivity, resolution, and peelability of the photosensitive composition layer, the polymerizable compound preferably contains a difunctional or trifunctional ethylenically unsaturated compound having two or three ethylenically unsaturated groups in one molecule, and more preferably contains a trifunctional ethylenically unsaturated compound having three ethylenically unsaturated groups in one molecule. The elastic modulus X can be adjusted by including the above-mentioned trifunctional ethylenically unsaturated compound.

[0097] The content of the difunctional ethylenically unsaturated compound is preferably 20% by mass or more, more preferably over 40% by mass, even more preferably 55% by mass or more, and particularly preferably 90% by mass or more, relative to the total mass of the polymerizable compound, from the viewpoint of excellent peelability. There is no particular upper limit, but 100% by mass or less is preferred. In other words, all polymerizable compounds contained in the photosensitive composition layer may be difunctional ethylenically unsaturated compounds. The content of the trifunctional ethylenically unsaturated compound is preferably 10% by mass or more, and more preferably 20% by mass or more, relative to the total mass of the polymerizable compound, in order to adjust the elastic modulus X. There is no particular upper limit, but it is preferably 100% by mass or less, more preferably 80% by mass or less, and even more preferably 50% by mass or less. In other words, all polymerizable compounds contained in the photosensitive composition layer may be trifunctional ethylenically unsaturated compounds. Furthermore, as an ethylenically unsaturated compound, a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group is preferred.

[0098] (Polymerizable compound B1) The photosensitive composition layer may also preferably contain polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups. Polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule, selected from the polymerizable compound B described above.

[0099] Examples of aromatic rings in polymerizable compound B1 include aromatic hydrocarbon rings such as benzene rings, naphthalene rings, and anthracene rings; aromatic heterocycles such as thiophene rings, furan rings, pyrrole rings, imidazole rings, triazole rings, and pyridine rings; and fused rings thereof. Aromatic hydrocarbon rings are preferred, and benzene rings are more preferred. The above aromatic ring may have substituents. Polymerizable compound B1 may have only one aromatic ring, or it may have two or more aromatic rings.

[0100] Polymerizable compound B1 is preferably a bisphenol structure because it suppresses swelling of the photosensitive composition layer by the developer, thereby improving resolution. Examples of bisphenol structures include the bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), the bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and the bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), with the bisphenol A structure being preferred.

[0101] Examples of polymerizable compounds B1 having a bisphenol structure include compounds having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. The two polymerizable groups at both ends of the bisphenol structure may be directly bonded, or they may be bonded via one or more alkylene oxy groups. The alkylene oxy groups added to both ends of the bisphenol structure are preferably ethylene oxy groups or propylene oxy groups, with ethylene oxy groups being more preferred. The number of alkylene oxy groups added to the bisphenol structure is not particularly limited, but 4 to 16 per molecule is preferred, and 6 to 14 are more preferred. For polymerizable compound B1 having a bisphenol structure, see paragraphs

[0072] to

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

[0102] As polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferred, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferred. Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and 2,2-bis(4-(methacryloxydodecae Examples include toxictetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and ethoxylated (10)bisphenol A diacrylate (NK ester A-BPE-10, manufactured by Shin Nakamura Chemical Industry Co., Ltd.).

[0103] As the polymerizable compound B1, the compound represented by formula (B1) is also preferred.

[0104] [ka]

[0105] In formula (B1), R1 and R2 each independently represent a hydrogen atom or a methyl group. A represents C2H4. B represents C3H6. n1 and n3 each independently represent an integer from 1 to 39. n1 + n3 is an integer from 2 to 40. n2 and n4 each independently represent an integer from 0 to 29. n2 + n4 is an integer from 0 to 30. The arrangement of the constituent units -(AO)- and -(BO)- may be random or in a block. If it is in a block, either -(AO)- or -(BO)- may be on the bisphenyl group side. For n1+n2+n3+n4, values ​​between 2 and 20 are preferred, more preferably between 2 and 16, and even more preferably between 4 and 12. Also, for n2+n4, values ​​between 0 and 10 are preferred, more preferably between 0 and 4, even more preferably between 0 and 2, and particularly preferred when 0 is used.

[0106] Polymerizable compound B1 may be used alone or in combination of two or more types. The content of polymerizable compound B1 is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 25% by mass or more, relative to the total mass of the photosensitive composition layer, from the viewpoint of superior resolution. There is no particular upper limit, but from the viewpoint of transferability and edge fusion (the phenomenon in which the photosensitive composition seeps out from the edges of the transfer member), it is preferably 70% by mass or less, and more preferably 60% by mass or less.

[0107] The content of polymerizable compound B1 is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 55% by mass or more, and particularly preferably 60% by mass or more, relative to the total mass of polymerizable compounds, from the viewpoint of superior resolution. There is no particular upper limit, but from the viewpoint of peelability, it is preferably 100% by mass or less, more preferably 99% by mass or less, even more preferably 95% by mass or less, particularly preferably 90% by mass or less, and most preferably 85% by mass or less.

[0108] (Other polymerizable compounds) The photosensitive composition layer may contain other polymerizable compounds in addition to the polymerizable compound B1 described above. Other polymerizable compounds are not particularly limited, but can be appropriately selected from known polymerizable compounds. Examples include compounds having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compounds), difunctional ethylenically unsaturated compounds without aromatic rings, and trifunctional or more ethylenically unsaturated compounds.

[0109] Examples of monofunctional ethylenically unsaturated compounds include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate.

[0110] Examples of bifunctional ethylenically unsaturated compounds that do not have an aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate. Examples of alkylene glycol di(meth)acrylates include tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), tricyclodecanedimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate. Examples of polyalkylene glycol di(meth)acrylates include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate. Examples of urethane di(meth)acrylates include propylene oxide-modified urethane di(meth)acrylate and ethylene oxide and propylene oxide-modified urethane di(meth)acrylate. Examples of commercially available products include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., Ltd.).

[0111] Examples of ethylenically unsaturated compounds with three or more functions include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide modified products thereof. Here, "(tri / tetra / penta / hexa)(meth)acrylate" is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, while "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate.

[0112] Examples of alkylene oxide modified products of ethylenically unsaturated compounds with three or more functions include caprolactone-modified (meth)acrylate compounds (such as KAYARAD® DPCA-20 manufactured by Nippon Kayaku Co., Ltd. and A-9300-1CL manufactured by Shin Nakamura Chemical Industry Co., Ltd.), alkylene oxide-modified (meth)acrylate compounds (such as KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin Nakamura Chemical Industry Co., Ltd., and EBECRYL® 135 manufactured by Daicel Ornex Co., Ltd.), ethoxylated glycerin triacrylate (such as A-GLY-9E manufactured by Shin Nakamura Chemical Industry Co., Ltd.), Aronics® TO-2349 (manufactured by Toagosei Co., Ltd.), Aronics M-520 (manufactured by Toagosei Co., Ltd.), and Aronics M-510 (manufactured by Toagosei Co., Ltd.).

[0113] Furthermore, the polymerizable compound may be a polymerizable compound having an acidic group (such as a carboxyl group). The above acidic group may form an acid anhydride group. Examples of polymerizable compounds having an acidic group include Arronix® TO-2349 (manufactured by Toagosei Co., Ltd.), Arronix® M-520 (manufactured by Toagosei Co., Ltd.), and Arronix® M-510 (manufactured by Toagosei Co., Ltd.). Examples of polymerizable compounds having an acidic group include the polymerizable compounds having an acidic group described in paragraphs

[0025] to

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

[0114] The molecular weight (or weight-average molecular weight if a molecular weight distribution exists) of the polymerizable compound (including polymerizable compound B1) is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.

[0115] Polymerizable compounds may be used individually or in combination of two or more. The polymerizable compound content is preferably 10 to 70% by mass, more preferably 15 to 70% by mass, and even more preferably 20 to 70% by mass, based on the total mass of the photosensitive composition layer.

[0116] The mass ratio of the content of bifunctional or higher polymerizable compounds to the resin content (content of bifunctional or higher polymerizable compounds / resin content) is preferably 0.10 to 1.00, more preferably 0.50 to 1.00, even more preferably 0.60 to 1.00, and particularly preferably 0.60 to 0.80, from the viewpoint of achieving superior effects of the present invention.

[0117] The photosensitive composition layer may preferably contain the polymerizable compound B1 described above and a trifunctional or greater ethylenically unsaturated compound, and more preferably contain the polymerizable compound B1 described above and two or more trifunctional or greater ethylenically unsaturated compounds. The mass ratio of the polymerizable compound B1 to the mass of the trifunctional or more ethylenically unsaturated compound is preferably 1.0 to 5.0, more preferably 1.2 to 4.0, and even more preferably 1.5 to 3.0. Furthermore, the photosensitive composition layer preferably contains the polymerizable compound B1 and a trifunctional ethylenically unsaturated compound described above.

[0118] <Polymerization initiator> The photosensitive composition layer may also preferably contain a polymerization initiator. Polymerization initiators are selected according to the type of polymerization reaction, and examples include thermal polymerization initiators and photopolymerization initiators. The polymerization initiator may be either a radical polymerization initiator or a cationic polymerization initiator.

[0119] The photosensitive composition layer preferably contains a photopolymerization initiator. A photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound upon exposure to active light such as ultraviolet light, visible light, and X-rays. While there are no particular limitations on the photopolymerization initiator, known photopolymerization initiators can be used. Examples of photopolymerization initiators include photoradical polymerization initiators and photocationic polymerization initiators, with photoradical polymerization initiators being preferred.

[0120] Examples of photo-radical polymerization initiators include photopolymerization initiators having an oxime ester structure, photopolymerization initiators having an α-aminoalkylphenone structure, photopolymerization initiators having an α-hydroxyalkylphenone structure, photopolymerization initiators having an acylphosphine oxide structure, and photopolymerization initiators having an N-phenylglycine structure.

[0121] Furthermore, the photosensitive composition layer preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and their derivatives as a photoradical polymerization initiator, from the viewpoint of photosensitivity, visibility of exposed and unexposed areas, and resolution. The two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different. Examples of derivatives of the 2,4,5-triarylimidazole dimer include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0122] Examples of photoradical polymerization initiators include those described in paragraphs

[0031] to

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

[0064] to

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

[0123] Examples of photoradical polymerization initiators include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (product name: manufactured by Midori Chemical Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (product name: manufactured by Midori Chemical Co., Ltd.), 1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyl oxime) (product name: IRGACURE® OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyloxime) (product name: IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), and IRGACURE OXE-04 (BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (product name: Omnirad 379EG, IGM Resins BV), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (product name: Omnirad 907, IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (product name: Omnirad 127, IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (product name: Omnirad 369, IGM Resins (Manufactured by BV), 2-hydroxy-2-methyl-1-phenylpropan-1-one (Trade name: Omnirad 1173, manufactured by IGM Resins BV), 1-hydroxycyclohexyl phenyl ketone (Trade name: Omnirad 184, 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-trimethylbenzolyl-diphenylphosphine oxide (Trade name: Omnirad TPO H, manufactured by IGM Resins BV)(Manufactured by) Bis(2,4,6-trimethylbenzolyl)phenylphosphine oxide (trade name: Omnirad 819, manufactured by IGM Resins BV), oxime ester-based photopolymerization initiator (trade name: Lunar 6, manufactured by DKSH Japan), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (trade name: B-CIM, manufactured by Hampford), 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyl oxime) (trade name: TR-PBG-305, manufactured by Changzhou Qiang Examples include 1,2-propanedione,3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazole-3-yl]-,2-(O-acetyloxime) (trade name: TR-PBG-326, manufactured by Changzhou Strong Electronic Materials Co., Ltd.) and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazole-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, manufactured by Changzhou Strong Electronic Materials Co., Ltd.).

[0124] A photocationic polymerization initiator (photoacid generator) is a compound that generates acid upon receiving active light. Preferred photocationic polymerization initiators are compounds that are sensitive to active light with a wavelength of 300 nm or higher (preferably 300-450 nm) and generate acid. Furthermore, photocationic polymerization initiators that are not directly sensitive to active light with a wavelength of 300 nm or higher can also be preferably used in combination with a sensitizer, provided they become sensitive to active light with a wavelength of 300 nm or higher and generate acid. As the photocationic polymerization initiator, a photocationic polymerization initiator that generates an acid with a pKa of 4 or less is preferred, a photocationic polymerization initiator that generates an acid with a pKa of 3 or less is more preferred, and a photocationic polymerization initiator that generates an acid with a pKa of 2 or less is particularly preferred. There is no specific lower limit for the pKa, but -10.0 or higher is preferred.

[0125] Examples of photocationic polymerization initiators include ionic photocationic polymerization initiators and nonionic photocationic polymerization initiators. Examples of ionic photocationic polymerization initiators include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, as well as quaternary ammonium salts. Examples of ionic photocationic polymerization initiators include those described in paragraphs

[0114] to

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

[0126] Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triazines, diazomethane compounds, imidosulfonate compounds, and oximesulfonate compounds. Examples of trichloromethyl-s-triazines, diazomethane compounds, and imidosulfonate compounds include those described in paragraphs

[0083] to

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

[0084] to

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

[0127] Polymerization initiators may be used individually or in combination of two or more. The content of the polymerization initiator (preferably a photopolymerization initiator) is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more, based on the total mass of the photosensitive composition layer. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, based on the total mass of the photosensitive composition layer.

[0128] <Dye> The photosensitive composition layer preferably contains a dye (also called "dye N") whose maximum absorption wavelength in the wavelength range of 400 to 780 nm during color development is 450 nm or higher, and whose maximum absorption wavelength changes with the presence of an acid, base, or radical, from the viewpoint of visibility of the exposed and unexposed areas, as well as pattern visibility and resolution after development. When dye N is included, although the detailed mechanism is unknown, adhesion to adjacent layers (e.g., water-soluble resin layers) is improved and resolution is further enhanced.

[0129] In this specification, the phrase "the maximum absorption wavelength of a dye changes due to an acid, base, or radical" may mean any of the following: a dye in a colored state is decolorized by an acid, base, or radical; a dye in a decolorized state is colored by an acid, base, or radical; or a dye in a colored state changes to a colored state of another hue. Specifically, the dye N may be a compound that changes from a decolorized state to a colored state upon exposure, or a compound that changes from a colored state to a decolorized state upon exposure. In the above case, the dye may change its colored or decolorized state due to the generation and action of acids, bases, or radicals within the photosensitive composition layer upon exposure, or the dye may change its colored or decolorized state due to a change in the state (e.g., pH) within the photosensitive composition layer caused by acids, bases, or radicals. Furthermore, the dye may change its colored or decolorized state upon direct stimulation by acids, bases, or radicals without the need for exposure.

[0130] In particular, from the viewpoint of visibility and resolution of the exposed and unexposed areas, the dye N is preferably a dye whose maximum absorption wavelength changes with acid or radicals, and more preferably a dye whose maximum absorption wavelength changes with radicals. The photosensitive composition layer preferably contains both a dye N whose maximum absorption wavelength changes due to radicals and a photoradical polymerization initiator, from the viewpoint of visibility and resolution of the exposed and unexposed areas. Furthermore, from the viewpoint of visibility between the exposed and unexposed areas, it is preferable that the dye N is a dye that develops color in response to an acid, base, or radical.

[0131] One example of a color development mechanism for dye N is to add a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator), or a photobase generator to a photosensitive composition layer, and after exposure, the radical-reactive dye, acid-reactive dye, or base-reactive dye (e.g., leuco dye) develops color due to the radicals, acids, or bases generated from the photoradical polymerization initiator, photocationic polymerization initiator, or photobase generator.

[0132] From the viewpoint of visibility of the exposed and unexposed areas, the maximum absorption wavelength of the dye N in the wavelength range of 400 to 780 nm during color development is preferably 550 nm or higher, more preferably 550 to 700 nm, and even more preferably 550 to 650 nm. Furthermore, the pigment N may have only one maximum absorption wavelength in the wavelength range of 400-780 nm during color development, or it may have two or more. If the pigment N has two or more maximum absorption wavelengths in the wavelength range of 400-780 nm during color development, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths should be 450 nm or higher.

[0133] The maximum absorption wavelength of dye N can be measured in an atmospheric environment using a UV3100 spectrophotometer (Shimadzu Corporation) to measure the transmission spectrum of a solution containing dye N (at a temperature of 25°C) in the range of 400 to 780 nm, and then detecting the wavelength at which the light intensity is minimum (maximum absorption wavelength).

[0134] Examples of dyes that develop or decolorize upon exposure include leuco compounds. Examples of dyes that decolorize upon exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes. As for the dye N, a leuco compound is preferred from the viewpoint of visibility between the exposed and unexposed areas.

[0135] Examples of leuco compounds include leuco compounds having a triarylmethane skeleton (triarylmethane dyes), leuco compounds having a spiropyran skeleton (spiropyran dyes), leuco compounds having a fluorane skeleton (fluorane dyes), leuco compounds having a diarylmethane skeleton (diarylmethane dyes), leuco compounds having a rhodamine lactam skeleton (rhodamine lactam dyes), leuco compounds having an indolylphthalide skeleton (indolylphthalide dyes), and leuco compounds having a leucoauramine skeleton (leucoauramine dyes). Among these, triarylmethane-based dyes or fluorane-based dyes are preferred, and leuco compounds having a triphenylmethane skeleton (triphenylmethane-based dyes) or fluorane-based dyes are more preferred.

[0136] From the viewpoint of visibility between the exposed and unexposed areas, the leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring. This allows the lactone ring, sultine ring, or sultone ring of the leuco compound to react with radicals generated from a photoradical polymerization initiator or acids generated from a photocationic polymerization initiator, thereby changing the leuco compound to a closed state and decolorizing it, or changing the leuco compound to an open state and developing color. As the leuco compound, a compound having a lactone ring, a sultine ring, or a sultone ring that develops color when the lactone ring, sultine ring, or sultone ring opens in response to radicals or acids is preferred, and a compound having a lactone ring that develops color when the lactone ring opens in response to radicals or acids is more preferred.

[0137] Examples of pigment N include dyes and leuco compounds. Examples of dyes include Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuchsine, Methyl Violet 2B, Quinaldine Red, Rose Bengal, Methanyl Yellow, Thymol Sulfophthalein, Xylenol Blue, Methyl Orange, Paramethyl Red, Congo Red, Benzopulpurine 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Parafuchsine, Victoria Pure Blue - Naphthalene Sulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Co., Ltd.), Oil Pink #312 (manufactured by Orient Chemical Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Co., Ltd.), Oil Scarlet #308 (manufactured by Orient Chemical Co., Ltd.) Examples include: Oil Red OG (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Industry Co., Ltd.), Oil Green #502 (manufactured by Orient Chemical Industry Co., Ltd.), Spiron Red BEH Special (manufactured by Hodogaya Chemical Industry Co., Ltd.), m-Cresol Purple, Cresol Red, Rhodamine B, Rhodamine 6G, Sulforhodamine B, Auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethiaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-pN,N-bis(hydroxyethyl)aminophenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0138] Examples of leuco compounds include p,p',p''-hexamethyltriaminotriphenylmethane (leucocrystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoylleucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(Np-tolyl-N-ethyl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluorane, 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, and 3-(N-cyclohexyl-N-methylamino)- 6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-xylidinofluorane, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorane, 3-(N,N-diethylamino)-6-methoxy-7-aminofluorane, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluorane, 3-(N,N-diethylamino)-7-chlorofluorane, 3-(N,N-di Ethylamino)-7-benzylaminofluorane, 3-(N,N-diethylamino)-7,8-benzofluorane, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluorane, 3-(N,N-dibutylamino)-6-methyl-7-xylidinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3,3-bis(1-ethyl-2-methylindole-3-yl)phthalide, 3,3-bis(1-n-butyl-2 Examples include methylindole-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-zaphthalide, 3'-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)phthalide, and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthene-3-one.

[0139] Dye N is preferably a dye whose maximum absorption wavelength changes due to radicals, and more preferably a dye that develops color due to radicals, in order to have excellent visibility of exposed and unexposed areas, as well as pattern visibility and resolution after development. As the dye N, leucocrystal violet, crystal violet lactone, brilliant green, or Victoria Pure Blue naphthalene sulfonate are preferred.

[0140] Dye N may be used alone or in combination of two or more types. The content of dye N is preferably 0.1% by mass or more, more preferably 0.1 to 10% by mass, even more preferably 0.1 to 5% by mass, and particularly preferably 0.1 to 1% by mass, based on the total mass of the photosensitive composition layer, in order to obtain excellent visibility of the exposed and unexposed areas, and the pattern visibility and resolution after development.

[0141] The content of dye N refers to the amount of dye N present in the total mass of the photosensitive composition layer when all of the dye N is in a colored state. The following describes a method for quantifying the content of dye N, using a dye that develops color via radicals as an example. Solutions were prepared by dissolving 0.001 g and 0.01 g of dye N in 100 mL of methyl ethyl ketone. A photoradical polymerization initiator (Irgacure OXE01, BASF Japan) was added to each solution, and radicals were generated by irradiating with light of a wavelength of 365 nm, causing all of the dye N to develop color. Subsequently, under an atmospheric environment, the absorbance of each solution at a liquid temperature of 25°C was measured using a spectrophotometer (UV3100, Shimadzu Corporation), and a calibration curve was created. Next, the absorbance of the solution in which all the dyes have developed is measured using the same method as above, except that 3 g of the photosensitive composition layer is dissolved in methyl ethyl ketone instead of dye N. From the absorbance of the obtained solution containing the photosensitive composition layer, the amount of dye N contained in the photosensitive composition layer is calculated based on the calibration curve. Note that 3g of the photosensitive composition layer is equivalent to 3g of the total solids in the photosensitive resin composition.

[0142] <Thermal crosslinkable compound> The photosensitive composition layer may contain a thermally crosslinkable compound, in terms of the strength of the resulting cured film and the tackiness of the resulting uncured film. In this specification, thermally crosslinkable compounds having ethylenically unsaturated groups, as described later, will not be treated as polymerizable compounds, but rather as thermally crosslinkable compounds. Examples of thermally crosslinkable compounds include methylol compounds and blocked isocyanate compounds. Among these, blocked isocyanate compounds are preferred in terms of the strength of the resulting cured film and the tackiness of the resulting uncured film. Blocked isocyanate compounds react with hydroxyl and carboxyl groups, for example, resins and / or polymerizable compounds react with at least one hydroxyl and carboxyl group. When this property is present, the hydrophilicity of the formed film tends to decrease, and the function of the film, when the photosensitive composition layer is cured and used as a protective film, tends to be enhanced. Furthermore, a blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of an isocyanate is protected (so-called masked) with a blocking agent."

[0143] The dissociation temperature of the blocked isocyanate compound is preferably 100 to 160°C, and more preferably 130 to 150°C. The dissociation temperature of blocked isocyanates refers to "the temperature of the endothermic peak associated with the deprotection reaction of blocked isocyanates, as measured by differential scanning calorimetry (DSC) analysis using a differential scanning calorimeter." As a differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Corporation can be suitably used. However, the differential scanning calorimeter is not limited to this.

[0144] Examples of blocking agents with a dissociation temperature of 100-160°C include active methylene compounds (malonic acid diesters (e.g., dimethyl malonate, diethyl malonate, di-n-butyl malonate, and di-2-ethylhexyl malonate)) and oxime compounds (compounds having a structure represented by -C(=N-OH)- in the molecule, such as formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime). In particular, as a blocking agent with a dissociation temperature of 100 to 160°C, at least one selected from oxime compounds is preferred, for example, from the viewpoint of storage stability.

[0145] Blocked isocyanate compounds are preferably configured to have an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the film and enhancing adhesion to the transfer target. Blocked isocyanate compounds having an isocyanurate structure can be obtained, for example, by isocyanurating and protecting hexamethylene diisocyanate. In particular, as a blocked isocyanate compound having an isocyanurate structure, a compound having an oxime structure obtained by using an oxime compound as a blocking agent is preferred because it makes it easier to set the dissociation temperature within a favorable range compared to compounds without an oxime structure, and also makes it easier to reduce development residue.

[0146] The blocked isocyanate compound may have polymerizable groups. There are no particular restrictions on the polymerizable group; known polymerizable groups can be used, and radical polymerizable groups are preferred. Polymerizable groups include ethylenically unsaturated groups such as (meth)acryloxy groups, (meth)acrylamide groups, and styryl groups, as well as epoxy groups such as glycidyl groups. Among the polymerizable groups, ethylenically unsaturated groups are preferred, (meth)acryloxy groups are more preferred, and acryloxy groups are even more preferred.

[0147] Examples of blocked isocyanate compounds include Karenz® AOI-BM, Karenz® MOI-BM, Karenz® MOI-BP, etc. (all manufactured by Showa Denko Corporation), and the block-type Duranate series (for example, Duranate® TPA-B80E, Duranate® WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation). Examples of blocked isocyanate compounds include compounds with the following structure.

[0148] [ka]

[0149] The thermally crosslinkable compound may be used alone or in combination of two or more types. When the photosensitive composition layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass, relative to the total mass of the photosensitive composition layer.

[0150] <Pigments> The photosensitive composition layer may be a colored resin layer containing a pigment. In recent electronic devices, liquid crystal display windows may have a cover glass attached to the back edge of a transparent glass substrate or similar material to protect the liquid crystal display window. This cover glass has a black, frame-shaped light-shielding layer formed on the back edge. A colored resin layer may be used to form such a light-shielding layer. The pigment can be selected appropriately according to the desired hue, and can be chosen from black pigment, white pigment, and pigments of other chromatic colors besides black and white. Among these, black pigment is preferably selected when forming black patterns.

[0151] (Black pigment) As the black pigment, any known black pigment (organic pigment or inorganic pigment, etc.) can be appropriately selected, as long as it does not impair the effects of the present invention. In particular, from the viewpoint of optical density, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, or graphite are preferred as black pigments, with carbon black being more preferred. As for carbon black, from the viewpoint of surface resistance, carbon black in which at least a portion of the surface is coated with resin is preferred.

[0152] The particle size (number-average particle size) of the black pigment is preferably 0.001 to 0.1 μm, and more preferably 0.01 to 0.08 μm, from the viewpoint of dispersion stability. Particle size refers to the diameter of a circle with the same area as the pigment particle, calculated from a photograph of the pigment particle taken with an electron microscope. Number-average particle size is the average value obtained by calculating the above particle size for any 100 particles and averaging the resulting particle sizes of those 100 particles.

[0153] Examples of white pigments include inorganic pigments and the white pigments described in paragraphs

[0015] and

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

[0154] Furthermore, if the photosensitive composition layer is a colored resin layer, it is preferable for the photosensitive composition layer to contain chromatic pigments other than black and white pigments, from the viewpoint of transferability. When chromatic pigments are included, the particle size of the chromatic pigments is preferably 0.1 μm or less, and more preferably 0.08 μm or less, from the viewpoint of superior dispersibility. The lower limit is preferably 10 nm or more. Examples of chromatic pigments include Victoria Pure Blue BO (Color Index (CI) 42595), Auramine (CI 41000), Fat Black HB (CI 26150), Monolight Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11), Fastel Pink B Spray (CI Pigment Red 81), and Monastral First Blue (CI Pigment Blue 15). Examples include Monolight First Black B (CI Pigment Black 1) and Carbon, CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red 215, CI Pigment Green 7, CI Pigment Blue 15:1, CI Pigment Blue 15:4, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64, and CI Pigment Violet 23, with CI Pigment Red 177 being preferred.

[0155] Pigments may be used individually or in combination of two or more types. When the photosensitive composition layer contains a pigment, the pigment content is preferably more than 3% by mass and 40% by mass or less, more preferably more than 3% by mass and 35% by mass or less, even more preferably more than 5% by mass and 35% by mass or less, and particularly preferably 10 to 35% by mass or less, based on the total mass of the photosensitive composition layer.

[0156] When the photosensitive composition layer contains pigments other than black pigment (white pigment and chromatic pigment), the content of pigments other than black pigment is preferably 30% by mass or less, more preferably 1 to 20% by mass, and even more preferably 3 to 15% by mass, relative to the total mass of black pigment.

[0157] If the photosensitive composition layer contains a black pigment, it is preferable that the black pigment (preferably carbon black) be introduced into the photosensitive composition in the form of a pigment dispersion. The dispersion may also be prepared by pre-mixing a mixture of black pigment and a pigment dispersant, adding the mixture to an organic solvent (or vehicle), and dispersing it in a disperser. The pigment dispersant can be selected according to the pigment and solvent; for example, commercially available dispersants can be used. The vehicle refers to the medium that disperses the pigment in the pigment dispersion, and is liquid in form, containing a binder component that holds the black pigment in a dispersed state and a solvent component (organic solvent) that dissolves and dilutes the binder component.

[0158] Examples of known dispersers include kneaders, roll mills, attritors, super mills, dissolvers, homomixers, and sand mills. Alternatively, the material may be finely ground using frictional force through mechanical grinding. Examples of dispersers and fine grinders can be found in, for example, the "Dictionary of Pigments" (by Kunizo Asakura, 1st edition, Asakura Shoten, 2000, pp. 438, 310).

[0159] <Other additives> The photosensitive composition layer may contain, in addition to the above components, known additives (other additives) as needed. Other additives include, for example, radical polymerization inhibitors, benzotriazoles, carboxybenzotriazoles, sensitizers, surfactants, plasticizers, heterocyclic compounds (such as triazoles), pyridines (such as isonicotinamides), and purine bases (such as adenine). Other additives include metal oxide particles, antioxidants, dispersants, acid growth agents, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic precipitation inhibitors, as described in paragraphs

[0165] to

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

[0160] (Radical polymerization inhibitor) Examples of radical polymerization inhibitors include the thermal polymerization inhibitors described in paragraph

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

[0161] (Benzotriazoles) Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.

[0162] (Carboxybenzotriazoles) Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole. A specific example of a carboxybenzotriazole is CBT-1 (a trade name of Johoku Chemical Industry Co., Ltd.).

[0163] The total content of radical polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles is preferably 0.01 to 3% by mass, and more preferably 0.05 to 1% by mass, relative to the total mass of the photosensitive composition layer. When the above content is 0.01% by mass or more, the storage stability of the photosensitive composition layer is better. On the other hand, when the above content is 3% by mass or less, the maintenance of sensitivity and suppression of dye decolorization are better.

[0164] (Sensitizer) Examples of sensitizers include known sensitizers, dyes, and pigments. Examples of sensitizers include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

[0165] When the photosensitive composition layer contains a sensitizer, the sensitizer content is preferably 0.01 to 5% by mass, and more preferably 0.05 to 1% by mass, relative to the total mass of the photosensitive composition layer, from the viewpoint of improving sensitivity to the light source and improving the curing speed by balancing the polymerization rate and chain transfer.

[0166] (Surfactants) Examples of surfactants include those described in paragraph

[0017] of Japanese Patent No. 4502784 and paragraphs

[0060] to

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

[0167] As the surfactant, nonionic surfactants, fluorinated surfactants, or silicone surfactants are preferred. Examples of fluorine-based surfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, and EXP.M. FS-330, EXP.MFS-578, EXP.MFS-578-2, EXP.MFS-579, EXP.MFS-586, EXP.MFS-587, EXP.MFS-628, EXP.MFS-631, EXP.MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94 and DS-21 (all manufactured by DIC); Florard FC430, FC431 and FC171 (all manufactured by Sumitomo 3M); Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393 and KH-40 (all manufactured by AGC); PolyFox PF636, PF656, PF6320, PF6520 and PF7002 (all manufactured by OMNOVA); Futtergent Examples include 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681 and 683 (all manufactured by NEOS Corporation); and U-120E (Unichem Corporation).

[0168] Furthermore, as fluorine-based surfactants, acrylic compounds having a molecular structure with a functional group containing a fluorine atom, in which the fluorine-containing functional group is cleaved when heat is applied and the fluorine atom volatilizes, are also preferred. Examples of such fluorinated surfactants include the Megafac DS series manufactured by DIC Corporation (Chemical Daily (February 22, 2016) and Nikkei Sangyo Shimbun (February 23, 2016)). Furthermore, as a fluorine-based surfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. In addition, block polymers can also be used as fluorine-based surfactants. Furthermore, as a fluorine-based surfactant, a fluorine-containing polymer compound is also preferred, which includes a structural unit derived from a (meth)acrylate compound having a fluorine atom and a structural unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkylene oxy groups (preferably ethylene oxy groups, propylene oxy groups). Furthermore, as fluorine-based surfactants, for example, fluorine-containing polymers having ethylenically unsaturated bond-containing groups in their side chains can also be used, such as Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0169] As for fluorine-based surfactants, from the viewpoint of improving environmental suitability, surfactants derived from alternative materials of compounds having linear perfluoroalkyl groups with 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), are preferred.

[0170] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters; Pluronic® L10, L31, L61, L62, 10R5, 17R2 and 25R2 (all manufactured by BASF); Tetronic 304, 701, 704, 901, 904 and 150R1, HYDROPALAT WE 3323 (all manufactured by BASF); Solspers Examples include 20000 (manufactured by Lubrizol Nippon Co., Ltd.); NCW-101, NCW-1001 and NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.); Paionin D-1105, D-6112, D-6112-W and D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.); and Orfin E1010, Surfinol 104, 400 and 440 (manufactured by Nisshin Chemical Industry Co., Ltd.).

[0171] Examples of silicone-based surfactants include linear polymers consisting of siloxane bonds, and modified siloxane polymers in which organic groups are introduced into the side chains and / or terminals.

[0172] Specifically, silicone-based surfactants include EXP.S-309-2, EXP.S-315, EXP.S-503-2, EXP.S-505-2 (all manufactured by DIC Corporation), DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Toray Dow Corning); X-22-4952, X-22-4272, X-22-6266, K F-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001 and KF-6002, KP-101, KP-103, KP-104, KP-105, KP-106, KP-109, KP-109, KP-112, KP-120, KP-121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626 and KP-652 (all manufactured by Shin-Etsu Silicone Co., Ltd.); F-4440, TSF-4300, TSF-4445, TSF-4460 and TSF-4452 (all manufactured by Momentive Puff) Examples include BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, and BYK323 (all manufactured by BICK CHEMMY).

[0173] If the photosensitive composition layer contains a surfactant, the surfactant content is preferably 0.01 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, and even more preferably 0.05 to 0.8% by mass, relative to the total mass of the photosensitive composition layer.

[0174] Examples of plasticizers and heterocyclic compounds include those described in paragraphs

[0097] to

[0103] and paragraphs

[0111] to

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

[0175] <Impurities> The photosensitive composition layer may contain impurities. Examples of impurities include metal impurities or their ions, halide ions, residual organic solvents, residual monomers, and water.

[0176] (Metal impurities and halide ions) Examples of metallic impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, and their ions, as well as halide ions. Among these, sodium ions, potassium ions, and halide ions are particularly prone to contamination, so it is preferable to have the following content levels. Metallic impurities are compounds different from the aforementioned particles (e.g., metal oxides).

[0177] The content of metal impurities is preferably 80 ppm by mass or less, more preferably 10 ppm by mass or less, and even more preferably 2 ppm by mass or less, relative to the total mass of the photosensitive composition layer. There is no particular lower limit, but it is preferably 1 ppb by mass or more, and more preferably 0.1 ppm by mass or more, relative to the total mass of the photosensitive composition layer.

[0178] Methods for adjusting the impurity content include, for example, selecting raw materials with a low impurity content for the photosensitive composition layer, preventing the inclusion of impurities during the formation of the photosensitive composition layer, and removing them by washing. The impurity content can be quantified by known methods such as ICP emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0179] (Residual organic solvent) Examples of residual organic solvents include benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane. The residual organic solvent content is preferably 100 ppm by mass or less, more preferably 20 ppm by mass or less, and even more preferably 4 ppm by mass or less, relative to the total mass of the photosensitive composition layer. There is no particular lower limit, but it is preferably 10 ppb by mass or more, and more preferably 100 ppb by mass or more. The content of residual organic solvents can be prepared by the same method as for metal impurities. Furthermore, the content of residual organic solvents can be quantified by known methods, such as gas chromatography analysis.

[0180] (Remaining monomers) The photosensitive composition layer may contain residual monomers of each of the constituent units of the resin described above. From the viewpoint of patternability and reliability, the residual monomer content is preferably 5000 ppm by mass or less, more preferably 2000 ppm by mass or less, and even more preferably 500 ppm by mass or less, relative to the total mass of the resin. There is no particular lower limit, but it is preferably 1 ppm by mass or more, and more preferably 10 ppm by mass or more, relative to the total mass of the resin. The residual monomers of each constituent unit of the alkali-soluble resin are preferably 3000 ppm by mass or less, more preferably 600 ppm by mass or less, and even more preferably 100 ppm by mass or less, relative to the total mass of the photosensitive composition layer, from the viewpoint of patternability and reliability. There is no particular lower limit, but it is preferably 0.1 ppm by mass or more, and more preferably 1 ppm by mass or more, relative to the total mass of the photosensitive composition layer.

[0181] It is preferable that the amount of residual monomers when synthesizing alkali-soluble resins by polymer reactions be within the above range. For example, when synthesizing alkali-soluble resins by reacting glycidyl acrylate with a carboxylic acid side chain, it is preferable that the content of glycidyl acrylate be within the above range. The amount of residual monomers can be measured by known methods such as liquid chromatography and gas chromatography.

[0182] From the viewpoint of improving reliability and laminating property, the water content in the photosensitive composition layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass.

[0183] 〔Properties of the photosensitive composition layer〕 The thickness (film thickness) of the photosensitive composition layer is often 0.1 to 300 μm, preferably 0.2 to 100 μm, more preferably 0.5 to 50 μm, still more preferably 0.5 to 30 μm, and particularly preferably 1 to 20 μm. Thereby, the developability of the photosensitive composition layer is improved and the resolution can be improved.

[0184] The content of double bonds in the photosensitive composition layer is preferably 0.8 to 3.0 mmol / g, more preferably 1.0 to 3.0 mmol / g, still more preferably 1.2 to 2.0 mmol / g.

[0185] The acid value of the photosensitive composition layer is preferably 10 to 150 mgKOH / g, more preferably 40 to 100 mgKOH / g, still more preferably 50 to 100 mgKOH / g, particularly preferably 50 to 90 mgKOH / g, and most preferably 70 to 90 mgKOH / g from the point that the effects of the present invention are more excellent. Examples of the method for measuring the above acid value include the method for measuring the acid value in the above-described resin and the method for calculating from the content of a resin having a known acid value. <00​​​​​​​​​When the transfer film has an oxygen barrier layer, the polymerization reaction proceeds more smoothly when the photosensitive composition layer of the transfer film is exposed, and the elastic modulus X of the cured layer can be within a suitable range. As a result, the resulting pattern shape is improved. The oxygen barrier layer can be appropriately selected from known layers described in the above-mentioned publications, etc. In particular, an oxygen barrier layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (a 1% by mass aqueous solution of sodium carbonate at 22°C) is preferred. The following describes the various components that the water-soluble resin layer (intermediate layer) may contain.

[0187] <Water-soluble resin> The intermediate layer preferably contains a water-soluble resin. Examples of water-soluble resins include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, polyether-based resins, gelatin, and polyamide resins.

[0188] Examples of cellulose-based resins include water-soluble cellulose derivatives. Examples of water-soluble cellulose derivatives include hydroxyethylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, methylcellulose, and ethylcellulose.

[0189] Examples of polyether resins include polyethylene glycol, polypropylene glycol and alkylene oxide adducts thereof, as well as vinyl ether resins. Examples of polyamide resins include acrylamide resins, vinylamide resins, and allylamide resins. Among these, water-soluble cellulose derivatives or polyamide resins are preferred as water-soluble resins.

[0190] Furthermore, as a water-soluble resin, for example, a copolymer of (meth)acrylic acid / vinyl compound can be mentioned. As the copolymer of (meth)acrylic acid / vinyl compound, a copolymer of (meth)acrylic acid / (meth)acrylate is preferred, and a copolymer of methacrylic acid / methacrylate is more preferred. When the water-soluble resin is a copolymer of (meth)acrylic acid / vinyl compound, the composition ratio (mol%) is preferably 90 / 10~20 / 80, and more preferably 80 / 20~30 / 70.

[0191] The weight-average molecular weight (Mw) of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and even more preferably 10,000 or more. The upper limit is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less. The dispersion degree (Mw / Mn) of the water-soluble resin is preferably 1 to 10, and more preferably 1 to 5.

[0192] Water-soluble resins may be used individually or in combination of two or more types. The water-soluble resin content is preferably 50% by mass or more, and more preferably 70% by mass or more, relative to the total mass of the intermediate layer, from the viewpoint of achieving superior effects of the present invention and / or superior oxygen barrier ability. The upper limit is preferably 100% by mass or less, more preferably 99.9% by mass or less, even more preferably 99.8% by mass or less, and particularly preferably 99% by mass or less.

[0193] <Other ingredients> The intermediate layer may contain other components in addition to the resin mentioned above. The molecular weight of the other components is preferably less than 5,000, more preferably 4,000 or less, even more preferably 3,000 or less, particularly preferably 2,000 or less, and most preferably 1,500 or less. The lower limit is preferably 60 or more.

[0194] Other preferred components include polyhydric alcohols, alkylene oxide adducts of polyhydric alcohols, phenol derivatives, or amide compounds, with polyhydric alcohols, phenol derivatives, or amide compounds being more preferred.

[0195] Examples of the polyhydric alcohols include glycerin, diglycerin, and diethylene glycol. The number of hydroxyl groups contained in the polyhydric alcohols is preferably 2 to 10. Examples of the alkylene oxide adducts of the polyhydric alcohols include compounds obtained by adding ethylene oxide, propylene oxide, or the like to the above-described polyhydric alcohols. The average addition number is preferably 1 to 100, more preferably 2 to 50, and still more preferably 2 to 20. Examples of the phenol derivatives include bisphenol A and bisphenol S. [[ID=ll]]Examples of the amide compound include N-methylpyrrolidone.

[0196] The intermediate layer preferably contains at least one selected from the group consisting of polyhydric alcohols, oxide adducts of polyhydric alcohols, phenol derivatives, amide compounds, water-soluble cellulose derivatives, polyether resins, and polyamide resins.

[0197] The thickness of the intermediate layer is preferably 3.0 μm or less, more preferably 2.0 μm or less. The lower limit is preferably 1.0 μm or more.

[0198] The other components may be used alone or in combination of two or more. The content of the other components is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1% by mass or more with respect to the total mass of the intermediate layer. The upper limit is preferably less than 30% by mass, more preferably 10% by mass or less, and still more preferably 5% by mass or less.

[0199] 〔Thermoplastic resin layer〕 The transfer film of the present invention may have a thermoplastic resin layer. The thermoplastic resin layer is typically placed between the temporary support and the photosensitive composition layer. The inclusion of a thermoplastic resin layer in the transfer film improves its conformability to the substrate during the lamination process, suppressing the inclusion of air bubbles between the substrate and the transfer film. As a result, adhesion between the thermoplastic resin layer and adjacent layers (e.g., the temporary support) can be ensured. Furthermore, examples of thermoplastic resin layers include paragraphs

[0189] to

[0193] of Japanese Patent Publication No. 2014-085643, the contents of which are incorporated herein by reference.

[0200] The thickness of the thermoplastic resin layer is preferably 1 μm or more, and more preferably 2 μm or more, from the viewpoint of adhesion with adjacent layers. The upper limit is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 8 μm or less, from the viewpoint of developability and resolution.

[0201] <Thermoplastic resin> The thermoplastic resin layer preferably contains a thermoplastic resin. Alkali-soluble resins are preferred as thermoplastic resins. Examples of alkali-soluble resins include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycol.

[0202] As the alkali-soluble resin, acrylic resin is preferred from the viewpoint of developability and adhesion to adjacent layers. Here, acrylic resin means a resin having at least one constituent unit selected from the group consisting of constituent units derived from (meth)acrylic acid, constituent units derived from (meth)acrylic acid esters, and constituent units derived from (meth)acrylamide. In acrylic resins, the total content of constituent units derived from (meth)acrylic acid, (meth)acrylic acid ester, and (meth)acrylamide is preferably 50% by mass or more, relative to the total mass of the acrylic resin. The upper limit is preferably 100% by mass or less, relative to the total mass of the acrylic resin. In particular, the total content of constituent units derived from (meth)acrylic acid and constituent units derived from (meth)acrylic acid esters is preferably 30 to 100% by mass, and more preferably 50 to 100% by mass, relative to the total mass of the acrylic resin.

[0203] As the alkali-soluble resin, a polymer having an acidic group is preferred. Examples of acidic groups include carboxyl groups, sulfol groups, phosphate groups, and phosphonic acid groups, with carboxyl groups being preferred. The acid value of the alkali-soluble resin is preferably 60 mg KOH / g or higher from the viewpoint of developability. The upper limit is preferably 300 mg KOH / g or less, more preferably 250 mg KOH / g or less, even more preferably 200 mg KOH / g or less, and particularly preferably 150 mg KOH / g or less. Among these, alkali-soluble resins with an acid value of 60 mg KOH / g or higher are preferred, and carboxyl group-containing acrylic resins with an acid value of 60 mg KOH / g or higher are more preferred.

[0204] The carboxyl group-containing acrylic resin with an acid value of 60 mgKOH / g or higher is not particularly limited, but can be appropriately selected from known resins. For example, examples include alkali-soluble resins that are carboxyl group-containing acrylic resins with an acid value of 60 mgKOH / g or more among the polymers described in paragraph

[0025] of Japanese Patent Publication No. 2011-095716, carboxyl group-containing acrylic resins with an acid value of 60 mgKOH / g or more among the polymers described in paragraphs

[0033] to

[0052] of Japanese Patent Publication No. 2010-237589, and carboxyl group-containing acrylic resins with an acid value of 60 mgKOH / g or more among the resins described in paragraphs

[0053] to

[0068] of Japanese Patent Publication No. 2016-224162. The copolymerization ratio of the carboxyl group-containing structural units in the above-mentioned carboxyl group-containing acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 12 to 30% by mass, based on the total mass of the acrylic resin. As for alkali-soluble resins, acrylic resins having constituent units derived from (meth)acrylic acid are particularly preferred from the viewpoint of developability and adhesion to adjacent layers.

[0205] Alkali-soluble resins may have reactive groups. The reactive group can be any group that can undergo addition polymerization, and examples include ethylenically unsaturated groups; polycondensable groups such as hydroxyl groups and carboxyl groups; and polyaddition reactive groups such as epoxy groups and (blocked) isocyanate groups.

[0206] The weight-average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and even more preferably 20,000 to 50,000.

[0207] Alkali-soluble resins may be used individually or in combination of two or more types. From the viewpoint of developability and adhesion to adjacent layers, the content of alkali-soluble resin is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, even more preferably 40 to 80% by mass, and particularly preferably 50 to 75% by mass, relative to the total mass of the thermoplastic resin layer.

[0208] <Dye> The thermoplastic resin layer preferably contains a dye (hereinafter also simply referred to as "dye B") whose maximum absorption wavelength in the wavelength range of 400 to 780 nm during color development is 450 nm or higher, and whose maximum absorption wavelength changes due to an acid, base, or radical. The preferred embodiment of dye B is the same as the preferred embodiment of dye N described above, except for the points described later.

[0209] As for dye B, a dye whose maximum absorption wavelength changes with acid or radicals is preferred from the viewpoint of visibility and resolution of the exposed and unexposed areas, and a dye whose maximum absorption wavelength changes with acid is more preferred. From the viewpoint of visibility and resolution of the exposed and unexposed areas, the thermoplastic resin layer preferably contains both a dye whose maximum absorption wavelength changes with an acid as dye B and a compound that generates an acid with light, as described later.

[0210] Pigment B may be used alone or in combination of two or more types. From the viewpoint of visibility between the exposed and unexposed areas, the content of dye B is preferably 0.2% by mass or more, more preferably 0.2 to 6.0% by mass, even more preferably 0.2 to 5.0% by mass, and particularly preferably 0.25 to 3.0% by mass, relative to the total mass of the thermoplastic resin layer.

[0211] Here, the content of pigment B refers to the amount of pigment B present in the thermoplastic resin layer when all of the pigment B is in a colored state. Below, we will explain how to quantify the content of pigment B using a pigment that develops color through radicals as an example. Solutions were prepared by dissolving 0.001 g and 0.01 g of dye B in 100 mL of methyl ethyl ketone. A photoradical polymerization initiator (Irgacure OXE01, BASF Japan) was added to each solution, and radicals were generated by irradiating with light of a wavelength of 365 nm, causing all dye B to develop color. Subsequently, under an atmospheric environment, the absorbance of each solution at a liquid temperature of 25°C was measured using a spectrophotometer (UV3100, Shimadzu Corporation), and a calibration curve was created. Next, the absorbance of the solution in which all the dyes have developed is measured, using the same method as above, except that 0.1 g of the thermoplastic resin layer is dissolved in methyl ethyl ketone instead of dye B. From the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of dye B contained in the thermoplastic resin layer is calculated based on the calibration curve. Note that 3g of the thermoplastic resin layer is equivalent to 3g of the solid content of the composition.

[0212] <Compounds that generate acids, bases, or radicals upon exposure to light> The thermoplastic resin layer may contain a compound that generates an acid, base, or radical upon exposure to light (hereinafter also simply referred to as "compound C"). As compound C, a compound that generates an acid, base, or radical upon exposure to active light such as ultraviolet light and visible light is preferred. Examples of compound C include known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators).

[0213] (Photoacid generator) The thermoplastic resin layer may contain a photoacid generator for the sake of resolution. Examples of photoacid generators include photocationic polymerization initiators that may be included in the photosensitive composition layer described above, and the preferred embodiments are the same except for the points described later.

[0214] As a photoacid generator, it is preferable that it contains at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds, from the viewpoint of sensitivity and resolution, and it is more preferable that it contains an oxime sulfonate compound, from the viewpoint of sensitivity, resolution and adhesion. Furthermore, photoacid generators having the following structure are also preferred as photoacid generators.

[0215] [ka]

[0216] (Photoradical polymerization initiator) The thermoplastic resin layer may contain a photoradical polymerization initiator. Examples of photoradical polymerization initiators include photoradical polymerization initiators that can be contained in the photosensitive composition layer described above, and the preferred embodiments are the same.

[0217] (Photobase Generator) The thermoplastic resin composition may contain a photobase generator. Examples of photobase generators include well-known photobase generators. Specifically, 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)-1-benzyl-1-dimethyl Examples include minopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt(III)tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2,6-dimethyl-3,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine, and 2,6-dimethyl-3,5-diacetyl-4-(2,4-dinitrophenyl)-1,4-dihydropyridine.

[0218] Compound C may be used alone or in combination of two or more compounds. From the viewpoint of visibility and resolution of the exposed and unexposed areas, the content of compound C is preferably 0.1 to 10% by mass, and more preferably 0.5 to 5% by mass, relative to the total mass of the thermoplastic resin layer.

[0219] <Plasticizer> The thermoplastic resin layer preferably contains a plasticizer, from the viewpoint of resolution, adhesion to adjacent layers, and developability. The plasticizer is preferably smaller in molecular weight (or weight-average molecular weight if it is an oligomer or polymer with a molecular weight distribution) than the alkali-soluble resin. The molecular weight (weight-average molecular weight) of the plasticizer is preferably 200 to 2,000. The plasticizer is not particularly limited as long as it is a compound that is compatible with the alkali-soluble resin and exhibits plasticity. However, from the viewpoint of imparting plasticity, the plasticizer preferably has an alkylene oxy group in its molecule, and polyalkylene glycol compounds are more preferred. The alkylene oxy group contained in the plasticizer is more preferably a polyethylene oxy structure or a polypropylene oxy structure.

[0220] Furthermore, the plasticizer preferably contains a (meth)acrylate compound from the viewpoint of resolution and storage stability. From the viewpoint of compatibility, resolution, and adhesion to adjacent layers, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound. Examples of (meth)acrylate compounds used as plasticizers include the (meth)acrylate compounds described above as polymerizable compounds that can be included in the photosensitive composition layer. In transfer films, when a thermoplastic resin layer and a photosensitive composition layer are laminated in direct contact, it is preferable that both the thermoplastic resin layer and the photosensitive composition layer contain the same (meth)acrylate compound. This is because the inclusion of the same (meth)acrylate compound in both the thermoplastic resin layer and the photosensitive composition layer suppresses the diffusion of components between layers, thereby improving storage stability.

[0221] When the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, it is preferable that the (meth)acrylate compound does not polymerize in the exposed area after exposure, from the viewpoint of adhesion between the thermoplastic resin layer and the adjacent layer. Furthermore, as the (meth)acrylate compound used as a plasticizer, a polyfunctional (meth)acrylate compound having two or more (meth)acryloyl groups in one molecule is preferred from the viewpoint of resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability. Furthermore, as the (meth)acrylate compound used as a plasticizer, (meth)acrylate compounds having an acid group or urethane (meth)acrylate compounds are also preferred.

[0222] The plasticizer may be used alone or in combination of two or more types. The plasticizer content is preferably 1 to 70% by mass, more preferably 10 to 60% by mass, and even more preferably 20 to 50% by mass, relative to the total mass of the thermoplastic resin layer, from the viewpoint of resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability.

[0223] <Sensitizer> The thermoplastic resin layer may contain a sensitizer. The sensitizer is not particularly limited, but examples include sensitizers that may be included in the photosensitive composition layer described above.

[0224] The sensitizer may be used alone or in combination of two or more types. The sensitizer content is preferably 0.01 to 5% by mass, and more preferably 0.05 to 1% by mass, relative to the total mass of the thermoplastic resin layer, from the viewpoint of improving sensitivity to the light source and visibility of the exposed and unexposed areas.

[0225] <Other additives> The thermoplastic resin layer may contain other additives as needed, in addition to the components mentioned above. Other additives include, for example, other additives that may be included in the photosensitive composition layer described above.

[0226] <Impurities> The thermoplastic resin layer may contain impurities. Examples of impurities include those that may be present in the photosensitive composition layer described above.

[0227] [Other components] The transfer film of the present invention may have other components in addition to those described above. Other components include, for example, protective films.

[0228] (Protective film) As protective films, resin films having heat resistance and solvent resistance can be used. Examples include polyolefin films such as polypropylene film and polyethylene film, polyester films such as polyethylene terephthalate film, polycarbonate film, and polystyrene film. Alternatively, a resin film made of the same material as the temporary support described above may be used as the protective film. Among these, polyolefin film is preferred as the protective film, polypropylene film or polyethylene film is more preferred, and polyethylene film is even more preferred.

[0229] The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, even more preferably 5 to 40 μm, and particularly preferably 15 to 30 μm. The thickness of the protective film is preferably 1 μm or more for superior mechanical strength, and 100 μm or less for relatively low cost.

[0230] The protective film contains 5 fisheyes with a diameter of 80 μm or more per square meter. 2 The following is preferable: "Fish eye" refers to a condition where foreign matter, undissolved material, or oxidatively degraded material is incorporated into the film during the manufacturing process, such as by thermal melting, kneading, extrusion, biaxial stretching, and casting.

[0231] The number of particles with a diameter of 3 μm or larger contained in the protective film is 30 particles / mm². 2 The following is preferable: 10 pieces / mm 2 The following is more preferable: 5 pieces / mm 2 The following is even more preferable. The lower limit is 0 pieces / mm 2 The above is preferable. Within these ranges, defects caused by irregularities resulting from particles contained in the protective film being transferred to the photosensitive composition layer or conductive layer can be suppressed.

[0232] From the standpoint of providing windability, the arithmetic mean roughness Ra of the surface of the protective film opposite to the surface in contact with the photosensitive composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. The upper limit is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less. The surface roughness Ra of the surface of the protective film that contacts the photosensitive composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more, from the viewpoint of suppressing defects during transfer. The upper limit is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0233] [Method for manufacturing transfer film] The method for manufacturing the transfer film is not particularly limited, but known methods can be used. Examples of methods for manufacturing the transfer film 10 include the steps of: applying a water-soluble resin composition to the surface of a temporary support 11 to form a coating film, and then drying this coating film to form an intermediate layer 13; and applying a photosensitive composition to the surface of the intermediate layer 13 to form a coating film, and then drying this coating film to form a photosensitive composition layer 15. Furthermore, the process may include a step of applying a thermoplastic resin composition to the surface of the temporary support 11 to form a coating film before the step of forming the intermediate layer 13, and then drying this coating film to form a thermoplastic resin layer.

[0234] A transfer film 10 is manufactured by pressing a protective film 19 onto the photosensitive composition layer 15 of the laminate manufactured by the manufacturing method described above. As a method for manufacturing the transfer film, it is preferable to manufacture a transfer film 10 comprising a temporary support 11, an intermediate layer 13, a photosensitive composition layer 15, and a protective film 19 by including a step of providing a protective film 19 so as to contact the side of the photosensitive composition layer 15 opposite to the side having the temporary support 11. Alternatively, as a method for manufacturing the transfer film, it may be a transfer film comprising a temporary support 11, a thermoplastic resin layer, an intermediate layer 13, a photosensitive composition layer 15, and a protective film 19 by including a step of providing a protective film 19 so as to contact the side of the photosensitive composition layer 15 opposite to the side having the temporary support 11. After manufacturing the transfer film 10 using the above manufacturing method, the transfer film 10 may be wound up to produce and store a roll of transfer film. The roll of transfer film can be provided in its original form for the lamination process with the substrate using the roll-to-roll method described later.

[0235] Furthermore, as a method for manufacturing the transfer film 10, a photosensitive composition layer 15 and an intermediate layer 13 may be formed on the protective film 19, and then a thermoplastic resin layer may be formed on the surface of the intermediate layer 13.

[0236] [Photosensitive composition and method for forming a photosensitive composition layer] It is preferable to form the photosensitive composition layer by a coating method using a photosensitive composition containing the components that constitute the photosensitive composition layer described above (for example, a resin, a polymerizable compound, and a polymerization initiator, etc.) and a solvent. A preferred method for manufacturing the transfer film is to apply a photosensitive composition onto an intermediate layer to form a coating, and then dry this coating at a predetermined temperature to form a photosensitive composition layer. The amount of residual solvent is adjusted by the drying treatment of the coating.

[0237] The photosensitive composition preferably contains the various components that form the photosensitive composition layer described above, and a solvent. In the photosensitive composition, the preferred range of the content of each component relative to the total solid content of the photosensitive composition is the same as the preferred range of the content of each component relative to the total mass of the photosensitive composition layer described above. The solvent is not particularly limited as long as it can dissolve or disperse each component other than the solvent, but known solvents can be used. Specifically, examples include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol and ethanol, etc.), ketone solvents (acetone and methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aprotic polar solvents (N,N-dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents (n-propyl acetate, etc.), amide solvents, lactone solvents, and mixed solvents containing two or more of these.

[0238] The solvent preferably contains at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. In particular, a mixed solvent comprising at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, and at least one selected from the group consisting of ketone solvents and cyclic ether solvents is more preferred, and a mixed solvent comprising at least three types: at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, a ketone solvent, and a cyclic ether solvent is even more preferred.

[0239] Examples of alkylene glycol ether solvents include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether (e.g., propylene glycol monomethyl ether acetate), propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether. Examples of alkylene glycol ether acetate solvents include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate. Examples of solvents include those described in paragraphs

[0092] to

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

[0014] of Japanese Patent Application Publication No. 2018-177889, the details of which are incorporated herein by reference. The solvent may be used individually or in combination of two or more types. The solvent content is preferably 50 to 1900 parts by mass, more preferably 100 to 1200 parts by mass, and even more preferably 100 to 900 parts by mass, per 100 parts by mass of the total solids content of the composition.

[0240] Methods for applying photosensitive compositions include, for example, printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (slit coating).

[0241] For drying the photosensitive composition coating, heat drying and reduced-pressure drying are preferred methods. The drying temperature is preferably 90°C or higher, more preferably 100°C or higher, and even more preferably 110°C or higher. The upper limit is preferably 130°C or lower, and more preferably 120°C or lower. Drying can also be performed by continuously changing the temperature. The drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. The upper limit is preferably 600 seconds or less, more preferably 450 seconds or less, and even more preferably 300 seconds or less.

[0242] Furthermore, a transfer film may be manufactured by laminating a protective film onto a photosensitive composition layer. For example, known methods can be used to bond a protective film to a photosensitive composition layer. Examples of devices for laminating a protective film onto a photosensitive composition layer include known laminators such as vacuum laminators and auto-cut laminators. The laminator is preferably equipped with a heat-sensitive roller, such as a rubber roller, and capable of applying pressure and heating.

[0243] [Water-soluble resin composition and method for forming an intermediate layer (water-soluble resin layer)] The water-soluble resin composition preferably contains the various components that form the intermediate layer (water-soluble resin layer) described above, as well as a solvent. In the water-soluble resin composition, the preferred range of content of each component relative to the total solid content of the composition is the same as the preferred range of content of each component relative to the total mass of the water-soluble resin layer described above. The solvent is not particularly limited as long as it can dissolve or disperse the water-soluble resin, but at least one selected from the group consisting of water and water-miscible organic solvents is preferred, and water or a mixed solvent of water and a water-miscible organic solvent is more preferred. Examples of water-miscible organic solvents include C1-C3 alcohols, acetone, ethylene glycol, and glycerin, with C1-C3 alcohols being preferred, and methanol or ethanol being more preferred. The solvent may be used individually or in combination of two or more types. The solvent content is preferably 50 to 2500 parts by mass, more preferably 50 to 1900 parts by mass, and even more preferably 100 to 900 parts by mass, per 100 parts by mass of the total solids content of the composition.

[0244] The method for forming the water-soluble resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components, but examples include known coating methods (slit coating, spin coating, curtain coating, and inkjet coating).

[0245] [Composition for forming a thermoplastic resin layer and method for forming a thermoplastic resin layer] The method for forming a thermoplastic resin layer on a temporary support is not particularly limited, but known methods can be used. For example, it can be formed by applying a thermoplastic resin layer-forming composition to the temporary support and drying it as necessary. The composition for forming a thermoplastic resin layer preferably contains the various components for forming the thermoplastic resin layer described above and a solvent. In the composition for forming a thermoplastic resin layer, the preferred range of content of each component relative to the total solid content of the composition is the same as the preferred range of content of each component relative to the total mass of the thermoplastic resin layer described above. The solvent is not particularly limited as long as it can dissolve or disperse each component other than the solvent, but known solvents can be used. Examples of solvents include those similar to those contained in the photosensitive composition described later, and the preferred embodiments are also the same. The solvent content is preferably 50 to 1900 parts by mass, and more preferably 100 to 900 parts by mass, per 100 parts by mass of the total solids content of the composition.

[0246] The method for forming the thermoplastic resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components, but examples include known coating methods (slit coating, spin coating, curtain coating, and inkjet coating, etc.). [Examples]

[0247] The present invention will be described in more detail below based on examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the examples shown below. Unless otherwise specified, "parts" and "%" are based on mass. Furthermore, in the following examples, the weight-average molecular weight of the resin is the weight-average molecular weight (Mw) obtained by the gel permeation chromatography (GPC) method described above, converted to polystyrene equivalent. The theoretical acid value was used.

[0248] 〔resin〕 <Synthesis of resin A1> 67.0 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) was placed in a three-necked flask and heated to 90°C under a nitrogen atmosphere. A solution containing MAA (20.0 parts by mass), St (52.0 parts by mass), MMA (28.0 parts by mass), V-601 (4.0 parts by mass), and PGMEA (33.0 parts by mass) was added dropwise to the flask solution maintained at 90°C ± 2°C over 2 hours. After the addition was complete, the solution in the flask was stirred at 90°C ± 2°C for 1 hour. A solution containing V-601 (1.0 part by mass) and PGMEA (33.0 parts by mass) was added dropwise to the flask solution maintained at 90°C ± 2°C over 30 minutes. After the addition was complete, the solution in the flask was stirred at 90°C ± 2°C for 1 hour, and PGMEA (100.0 parts by mass) was added to dilute the solution, yielding resin A1 (solid content concentration 30.0% by mass). Furthermore, resins A2 to A6 (all with a solid content concentration of 30.0% by mass) were obtained by referring to the synthesis method of resin A1 described above.

[0249] Table 1 below shows the resins A1 to A6. In Table 1, the abbreviations of the monomers that form each constituent unit (mass %) are shown. Resins A1 to A6 are alkali-soluble resins.

[0250] [Table 1]

[0251] In Table 1, each entry has the following meaning: MAA: Methacrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) MMA: Methyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) EMA: Ethyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) St: Styrene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) BzMA: Benzyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0252] [Photosensitive composition] Each photosensitive composition with the components and formulations shown in Table 2 below was prepared. In Table 2, the values ​​listed in each component column represent the content (parts by mass) of each component. However, the amount of each resin in the "Resin" column refers to the amount of resin solution (solid content concentration 30% by mass).

[0253] [Table 2]

[0254] <Polymerizable compound> Ethoxylated bisphenol A dimethacrylate Ethoxylated (3) Trimethylolpropane Triacrylate 4-n-octylphenoxypentaethylene glycol monopropylene glycol acrylate Ethylene oxide propylene oxide modified urethane dimethacrylate

[0255] <Photopolymerization initiator> 2-(o-chlorophenyl)-4,5-diphenylimidazole

[0256] <Sensitizer> 4,4-Bis(diethylamino)benzophenone

[0257] <Coloring agent> Leucocrystal violet

[0258] <Solvent> acetone toluene methanol

[0259] [Composition for forming intermediate layer] Intermediate layer-forming composition 1 was prepared using the following components. • 4-88 LA (67.86% by mass): Polyvinyl alcohol, manufactured by Kuraray Co., Ltd. • PVP K30 (31.06% by mass): Manufactured by Fujifilm Corporation, polyvinylpyrrolidone • Metroze 60SH03 (1.00% by mass): Manufactured by Shin-Etsu Chemical Co., Ltd., a water-soluble cellulose derivative. • F444 (0.08% by mass): Manufactured by DIC Corporation, surfactant

[0260] [Transfer film] Transfer films were prepared, each consisting of a temporary support, an intermediate layer, and a photosensitive composition layer, to have the configuration shown in Table 3. Specifically, they were as follows: First, the intermediate layer-forming composition 1 described above was applied to a temporary support (a polyethylene terephthalate film with a thickness of 16 μm (Lumirror 16KS40, manufactured by Toray Industries)) using a bar coater so that the thickness after drying was 1.0 μm, and the intermediate layer was formed by drying it in an oven at 90°C. Furthermore, a photosensitive composition for forming the photosensitive composition layer shown in Table 3 was applied to the intermediate layer using a bar coater to the thickness shown in Table 3 after drying, and dried in an oven at 80°C to form a negative-type photosensitive composition layer. A 16 μm thick layer of polyethylene terephthalate (16KS40, manufactured by Toray Industries, Inc.) was pressed onto the obtained negative-type photosensitive composition layer to prepare transfer films for the examples and comparative examples.

[0261] [Measurement and Evaluation] <modulus of elasticity> The elastic moduli X and Y were measured using the method described above.

[0262] <Pattern shape (flared hem)> The protective film of the transfer film prepared above was peeled off, and the surface of the exposed photosensitive composition layer was laminated onto a substrate having a conductive layer with Ni plating (thickness 100 nm) on glass (lamination conditions: substrate temperature 80°C, rubber roller temperature 110°C, linear pressure 3 N / cm, transport speed 2 m / min) to obtain a laminate. Next, the temporary support was peeled off the resulting laminate, and a photomask having a line (μm) / space (μm) pattern of 1 / 1 was placed in close contact with the surface of the intermediate layer of the resulting laminate. Light was irradiated using a high-pressure mercury lamp exposure machine (MAP-1200L, manufactured by Dainippon Kaken Co., Ltd., main wavelength: 365 nm) to expose the photosensitive composition layer to 100 mJ / cm². 2 The images were exposed to light. Subsequently, a pattern was formed by shower development for 30 seconds using a sodium carbonate aqueous solution at a liquid temperature of 25°C. The cross-sectional shape of the obtained patterns was observed using a scanning electron microscope, and the length of the portion that extended beyond the top surface of the pattern (the side opposite to the substrate side) (the flared base portion in Figure 1) on the side of each pattern was defined as the base length. The longest base length was used to evaluate the pattern shape according to the following evaluation criteria. A: The hem length is 0.3 μm or less. B: Hem length is greater than 0.3 μm and less than or equal to 0.5 μm. C: Hem length is greater than 0.5 μm

[0263] <Pattern adhesion> The protective film of the transfer film prepared as described above was peeled off, and the surface of the exposed photosensitive composition layer was laminated onto a conductive substrate that had been Ni-plated (100 nm thick) on glass (lamination conditions: substrate temperature 80°C, rubber roller temperature 110°C, linear pressure 3 N / cm, transport speed 2 m / min) to obtain a laminate. Next, the temporary support was peeled off the resulting laminate, and a photomask having a line (μm) / space (μm) pattern of 1 / 1 was placed in close contact with the surface of the intermediate layer of the resulting laminate. Light was irradiated using a high-pressure mercury lamp exposure machine (MAP-1200L, manufactured by Dainippon Kaken Co., Ltd., main wavelength: 365 nm) to expose the photosensitive composition layer to 100 mJ / cm². 2 The images were exposed to light. Subsequently, a pattern was formed by shower development for 30 seconds using a sodium carbonate aqueous solution at a liquid temperature of 25°C. The resulting patterns were observed with a scanning electron microscope, and the minimum line width without pattern peeling or lifting at the edges was evaluated as pattern adhesion (μm).

[0264] <Resolution> The protective film of the transfer film prepared as described above was peeled off, and the surface of the exposed photosensitive composition layer was laminated onto a conductive substrate that had been Ni-plated (100 nm thick) on glass (lamination conditions: substrate temperature 80°C, rubber roller temperature 110°C, linear pressure 3 N / cm, transport speed 2 m / min) to obtain a laminate. Next, the temporary support was peeled off the resulting laminate, and a photomask having a line (μm) / space (μm) pattern of 1 / 1 was placed in close contact with the surface of the intermediate layer of the resulting laminate. Light was irradiated using a high-pressure mercury lamp exposure machine (MAP-1200L, manufactured by Dainippon Kaken Co., Ltd., main wavelength: 365 nm) to expose the photosensitive composition layer to 100 mJ / cm². 2 The images were exposed to light. Subsequently, a pattern was formed by shower development for 30 seconds using a sodium carbonate aqueous solution at a liquid temperature of 25°C. The resolution (μm) was defined as the minimum line width that the resulting pattern could resolve, and the resolution was evaluated.

[0265] <Development residue suppression property> Similar to the above-mentioned resolution, a pattern was formed, and the resulting line / space pattern was evaluated for the development residue suppression performance by measuring the thickness of the residue in the space area using a scanning electron microscope and by visual observation, according to the following criteria. A: The residue thickness in the space is 50 nm or less, and no residue is visible to the naked eye. B: The residue thickness in the space is 50 nm or less, and the residue is visible to the naked eye. C: Residual thickness in the space area exceeds 50nm

[0266] Table 3 shows the evaluation results. In Table 3, each entry is as follows: The "M / B" column indicates the mass ratio of the content of bifunctional or higher polymerizable compounds to the resin content (content of bifunctional or higher polymerizable compounds / resin content). The "X / Y" column shows the ratio of the modulus of elasticity X to the modulus of elasticity Y (modulus of elasticity X / modulus of elasticity Y). "Tg" indicates the Tg of the resin contained in the photosensitive composition layer. "M / B", "Double bond content", and "Acid value" represent the respective values ​​for the photosensitive composition layer.

[0267] [Table 3]

[0268] The results in Table 3 confirm that the manufacturing method for laminates according to the present invention provides excellent pattern shape and excellent pattern adhesion. It was confirmed that when the elastic modulus Y obtained from the measurement Y described above is 3.5 MPa or less, the development residue suppression performance is superior (comparison between Example 2 and Example 1). It was confirmed that when the ratio of the elastic modulus X to the elastic modulus Y is between 1500 and 10000, the suppression of development residue is superior (comparison between Example 2 and Example 1). It was confirmed that the pattern shape was superior when the double bond content in the photosensitive composition layer was 1.0 to 3.0 mmol / g (comparison between Examples 1-2 and Example 5). It was confirmed that the pattern shape is superior when the glass transition temperature (Tg) of the resin is between 90 and 150°C (comparison between Examples 1-2 and Example 6). It was confirmed that the pattern shape was superior when the acid value of the photosensitive composition layer was 50-90 mgKOH / g (comparison between Examples 1-2 and Example 4). It was confirmed that the pattern shape was superior when the mass ratio of the content of bifunctional or higher polymerizable compounds to the resin content was 0.60 to 1.00 (comparison between Examples 1-2 and Example 3). [Explanation of symbols]

[0269] 1 circuit board 2 patterns (hardened layer) 3. Flared hem 10 Transfer film 11 Temporary support 13. Middle Class 15 Photosensitive composition layer 17 Composition layer 19 Protective film

Claims

1. A bonding step is performed by bringing the surface of the photosensitive composition layer opposite to the intermediate layer side of a transfer film having a temporary support, an intermediate layer, and a photosensitive composition layer in this order into contact with a substrate, thereby bonding the transfer film and the substrate. Between the temporary support and the intermediate layer, a peeling step is performed to peel off the temporary support, An exposure step of pattern exposure of the photosensitive composition layer, The process includes a developing step in which the exposed photosensitive composition layer is developed using a developing solution to form a pattern, The acid value of the photosensitive composition layer is 50 to 90 mg KOH / g. A method for manufacturing a laminate, wherein the elastic modulus X determined by measurement X is between 4.0 and 10.0 GPa. Measurement X: The surface of the photosensitive composition layer of the transfer film opposite to the intermediate layer side is brought into contact with the substrate, the transfer film and the substrate are bonded together, the temporary support is peeled off from the resulting laminate between the temporary support and the intermediate layer, the entire photosensitive composition layer is exposed from the exposed intermediate layer side, the exposed intermediate layer is peeled off, and then the elastic modulus of the exposed cured layer is measured and defined as the elastic modulus X.

2. The method for manufacturing a laminate according to claim 1, wherein the elastic modulus Y determined by measurement Y is 3.5 MPa or less. Measurement Y: The elastic modulus of the photosensitive composition layer of the transfer film is measured and defined as the elastic modulus Y.

3. The method for manufacturing a laminate according to claim 2, wherein the ratio of the elastic modulus X to the elastic modulus Y is 1500 to 10000.

4. A method for producing a laminate according to any one of claims 1 to 3, wherein the content of double bonds in the photosensitive composition layer is 1.0 to 3.0 mmol / g.

5. The photosensitive composition layer comprises a resin, A method for manufacturing a laminate according to any one of claims 1 to 4, wherein the glass transition temperature Tg of the resin is 90 to 150°C.

6. The photosensitive composition layer comprises a bifunctional or higher polymerizable compound and a resin, A method for producing a laminate according to any one of claims 1 to 5, wherein the mass ratio of the content of the bifunctional or more polymerizable compound to the content of the resin is 0.60 to 1.

00.

7. A method for producing a laminate according to any one of claims 1 to 6, wherein the intermediate layer comprises at least one selected from the group consisting of polyhydric alcohols, oxide adducts of polyhydric alcohols, phenol derivatives, amide compounds, water-soluble cellulose derivatives, polyether resins, and polyamide resins.

8. A method for manufacturing a laminate according to any one of claims 1 to 7, wherein the thickness of the photosensitive composition layer is 1 to 20 μm.

9. A method for manufacturing a laminate according to any one of claims 1 to 8, wherein the thickness of the intermediate layer is 3.0 μm or less.

10. The method for manufacturing a laminate according to any one of claims 1 to 9, wherein the exposure step is an exposure step in which the exposed intermediate layer and a mask are brought into contact to perform pattern exposure.

11. A bonding step is performed by bringing the surface of the photosensitive composition layer opposite to the intermediate layer side of a transfer film having a temporary support, an intermediate layer, and a photosensitive composition layer in that order, into contact with a substrate having a conductive layer, thereby bonding the transfer film and the substrate. Between the temporary support and the intermediate layer, a peeling step is performed to peel off the temporary support, An exposure step of pattern exposure of the photosensitive composition layer, A developing step in which the exposed photosensitive composition layer is developed using a developer to form a pattern, The process includes an etching step of etching the conductive layer in areas where the aforementioned pattern is not arranged, The acid value of the photosensitive composition layer is 50 to 90 mg KOH / g. A method for manufacturing circuit wiring, wherein the elastic modulus X determined by measurement X is between 4.0 and 10.0 GPa. Measurement X: The surface of the photosensitive composition layer of the transfer film opposite to the intermediate layer side is brought into contact with the substrate, the transfer film and the substrate are bonded together, the temporary support is peeled off from the resulting laminate between the temporary support and the intermediate layer, the entire photosensitive composition layer is exposed from the exposed intermediate layer side, the exposed intermediate layer is peeled off, and then the elastic modulus of the exposed cured layer is measured and defined as the elastic modulus X.

12. It has a temporary support, an intermediate layer, and a photosensitive composition layer in this order, A transfer film subjected to an exposure step in which the photosensitive composition layer is pattern-exposed, The acid value of the photosensitive composition layer is 50 to 90 mg KOH / g. A transfer film whose elastic modulus X, determined by measurement X, is between 4.0 and 10.0 GPa. Measurement X: The surface of the photosensitive composition layer of the transfer film opposite to the intermediate layer side is brought into contact with the substrate, the transfer film and the substrate are bonded together, the temporary support is peeled off from the resulting laminate between the temporary support and the intermediate layer, the entire photosensitive composition layer is exposed from the exposed intermediate layer side, the exposed intermediate layer is peeled off, and then the elastic modulus of the exposed cured layer is measured and defined as the elastic modulus X.

13. The transfer film according to claim 12, wherein the elastic modulus Y determined by measurement Y is 3.5 MPa or less. Measurement Y: The elastic modulus of the photosensitive composition layer of the transfer film is measured and defined as the elastic modulus Y.

14. The transfer film according to claim 13, wherein the ratio of the elastic modulus X to the elastic modulus Y is 1500 to 10000.

15. The transfer film according to any one of claims 12 to 14, wherein the content of double bonds in the photosensitive composition layer is 1.0 to 3.0 mmol / g.

16. The photosensitive composition layer comprises a resin, The transfer film according to any one of claims 12 to 15, wherein the glass transition temperature Tg of the resin is 90 to 150°C.

17. The photosensitive composition layer comprises a bifunctional or higher polymerizable compound and a resin, The transfer film according to any one of claims 12 to 16, wherein the mass ratio of the content of the bifunctional or higher polymerizable compound to the content of the resin is 0.60 to 1.

00.

18. The transfer film according to any one of claims 12 to 17, wherein the intermediate layer comprises at least one selected from the group consisting of polyhydric alcohols, oxide adducts of polyhydric alcohols, phenol derivatives, amide compounds, water-soluble cellulose derivatives, polyether resins, and polyamide resins.

19. The transfer film according to any one of claims 12 to 18, wherein the thickness of the photosensitive composition layer is 1 to 20 μm.

20. The transfer film according to any one of claims 12 to 19, wherein the thickness of the intermediate layer is 3.0 μm or less.

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