Laminate manufacturing method, circuit wiring manufacturing method, and transfer film

Abstract

The present invention addresses the problem of providing a method for manufacturing a laminate including a pattern having an excellent pattern shape, a method for manufacturing circuit wiring, and a transfer film. This method for manufacturing a laminate comprises: a bonding step for bringing the surface on the opposite side to the intermediate layer side of a photosensitive composition layer of a transfer film having a temporary support, an intermediate layer, and the photosensitive composition layer in this order into contact with a substrate, and bonding the transfer film and the substrate; a peeling step for peeling the temporary support between the temporary support and the intermediate layer; an exposure step for subjecting the photosensitive composition layer to pattern exposure; and a developing step for developing the exposed photosensitive composition layer using an alkaline developer and forming a pattern. A difference between a contact angle X obtained by measurement X and a contact angle Y obtained by measurement Y is 20 degrees or less.

Description

[Technical Field]

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

[0002] Because the number of steps required to obtain a predetermined pattern is small, a method is widely used in which a photosensitive composition layer is placed on any substrate using a transfer film, and the photosensitive composition layer is exposed to light through a mask and then developed.

[0003] For example, Patent Document 1 discloses a method for producing a laminate using a photosensitive resin laminate obtained by sequentially laminating a predetermined intermediate layer and a predetermined photosensitive resin layer on a support film. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2008-175957 Summary of the Invention [Problem to be solved by the invention]

[0005] The present inventors have investigated conventional laminate manufacturing methods using transfer films, such as those described in Patent Document 1, and found that the resulting pattern shape is prone to defects. They found that this problem is particularly likely to occur when a temporary support is peeled off and exposed to light to obtain a higher-resolution pattern. Specifically, a transfer film is attached to a substrate, the temporary support is peeled off, and the resulting pattern is exposed to light 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 flared, with the width of the pattern increasing as it approaches the substrate from the side opposite the substrate. In other words, a flared shape refers to a pattern shape in which the length of the lower base (on the substrate side) is longer than the length of the upper base (opposite the substrate). More specifically, as shown in Figure 1, a problem occurred in a pattern 2 arranged on a substrate 1, where a flared portion 3, as indicated by the dashed line, occurs. Hereinafter, the fact that the obtained pattern is less likely to have a flared shape is also referred to as "excellent pattern shape."

[0006] Therefore, an object of the present invention is to provide a method for producing a pattern-containing laminate that has an excellent pattern shape. Another object of the present invention is to provide a method for manufacturing circuit wiring and a transfer film. [Means for solving the problem]

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

[0008] [1] a lamination step of bringing a surface of a transfer film having a temporary support, an intermediate layer, and a photosensitive composition layer in this order, opposite to the intermediate layer side of the photosensitive composition layer, into contact with a substrate, and laminating 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-exposing the photosensitive composition layer; a developing step of developing the exposed photosensitive composition layer with an alkaline developer to form a pattern, A method for producing a laminate, in which the difference between a contact angle X determined by measurement X described below and a contact angle Y determined by measurement Y described below is 20 degrees or less. [2] The method for producing a laminate according to [1], wherein the contact angle X is 50 to 80 degrees. [3] The method for producing a laminate according to [1] or [2], wherein the contact angle Y is more than 70 degrees and not more than 90 degrees. [4] The 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 photosensitive composition layer contains a resin, The method for producing a laminate according to any one of [1] to [4], wherein the resin has an I / O value of 0.50 to 0.70. [6] The method for producing a laminate according to any one of [1] to [5], wherein the photosensitive composition layer has an acid value of 50 to 100 mgKOH / g. [7] The photosensitive composition layer contains a difunctional or higher functional polymerizable compound and a resin, The method for producing a laminate according to any one of [1] to [6], wherein the mass ratio of the content of the difunctional or higher functional polymerizable compound to the content of the resin is 0.60 to 1.00. [8] The method for producing a laminate according to any one of [1] to [7], wherein the intermediate layer contains at least one selected from the group consisting of polyhydric alcohols, oxide adducts of polyhydric alcohols, phenol derivatives, water-soluble cellulose derivatives, polyether resins, and polyamide resins. [9] The method for producing a laminate according to any one of [1] to [8], wherein the photosensitive composition layer has a thickness of 1 to 20 μm.

[10] The method for producing 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 producing a laminate according to any one of [1] to

[10] , wherein the exposure step is a step of bringing the exposed intermediate layer into contact with a mask and performing pattern exposure.

[12] a lamination step of bringing a surface of a transfer film having a temporary support, an intermediate layer, and a photosensitive composition layer in this order, opposite to the intermediate layer side of the photosensitive composition layer, into contact with a substrate having a conductive layer, and laminating 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-exposing the photosensitive composition layer; a developing step of developing the exposed photosensitive composition layer with an alkaline developer to form a pattern; an etching step of etching the conductive layer in an area where the pattern is not arranged, A method for manufacturing circuit wiring, wherein the difference between a contact angle X determined by measurement X (described later) and a contact angle Y determined by measurement Y (described later) is 20 degrees or less.

[13] A temporary support, an intermediate layer, and a photosensitive composition layer in this order, A transfer film that is subjected to a development step in which the film is developed using an alkaline developer after the exposure treatment to form a pattern, A transfer film in which the difference between a contact angle X determined by measurement X (described later) and a contact angle Y determined by measurement Y (described later) is 20 degrees or less.

[14] The transfer film according to

[13] , wherein the contact angle X is 50 to 80 degrees.

[15] The transfer film according to

[13] or

[14] , wherein the contact angle Y is greater than 70 degrees and equal to or less than 90 degrees.

[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 resin has an I / O value of 0.5 to 0.7.

[18] The transfer film according to any one of

[13] to

[17] , wherein the photosensitive composition layer has an acid value of 50 to 100 mgKOH / g.

[19] The photosensitive composition layer contains a difunctional or higher functional polymerizable compound and a resin, The transfer film according to any one of

[13] to

[18] , wherein the mass ratio of the content of the difunctional or higher polymerizable compound 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, water-soluble cellulose derivatives, polyether resins, and polyamide resins.

[21] The transfer film according to any one of

[13] to

[20] , wherein the photosensitive composition layer has a thickness of 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. [Effects of the Invention]

[0009] According to the present invention, a method for producing a pattern-containing laminate with an excellent pattern shape can be provided. The present invention also provides a circuit wiring manufacturing method and a transfer film. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 10 is a schematic diagram showing an example of a flared shape. [Figure 2] FIG. 2 is a schematic diagram illustrating an example of the configuration of a transfer film. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In the present specification, in the numerical ranges described in stages, the upper or lower limit described in a certain numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in the numerical ranges described in the present specification, the upper or lower limit described in a certain numerical range may be replaced with a value shown in the examples.

[0012] In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.

[0013] In this specification, the term "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, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

[0014] In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​measured by a gel permeation chromatography (GPC) analyzer using TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation) as a column, THF (tetrahydrofuran) as an eluent, a differential refractometer as a detector, and polystyrene as a standard substance, and converted using polystyrene as the standard substance. In this specification, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight (Mw). In this specification, unless otherwise specified, the content of metal elements is a value measured using an inductively coupled plasma (ICP) spectroscopic analyzer. In this specification, unless otherwise specified, the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm. In this specification, unless otherwise specified, the hue is a value measured using a color difference meter (CR-221, manufactured by Minolta Co., Ltd.).

[0015] 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.

[0016] In this specification, "alkali-soluble" means that the solubility in 100 g of a 1% by mass aqueous solution of sodium carbonate at 22°C is 0.1 g or more.

[0017] As used herein, "water-soluble" means that the solubility in 100 g of water having a pH of 7.0 and a liquid temperature of 22° C. is 0.1 g or more. For example, a water-soluble resin refers to a resin that satisfies the above-mentioned solubility conditions.

[0018] In this specification, the "solid content" of a composition refers to components that form a composition layer (such as a photosensitive composition layer, an intermediate layer, or a thermoplastic resin layer) formed using the composition, and when the composition contains a solvent (such as an organic solvent or water), refers to all components excluding the solvent. Furthermore, liquid components that form a composition layer are also considered to be solid content.

[0019] [Method of manufacturing laminate] The method for producing the laminate of the present invention includes a lamination step of bringing a surface of a transfer film having a temporary support, an intermediate layer, and a photosensitive composition layer in this order, opposite to the intermediate layer side of the photosensitive composition layer, into contact with a substrate, and laminating 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-exposing the photosensitive composition layer; a developing step of developing the exposed photosensitive composition layer with an alkaline developer to form a pattern, The difference between the contact angle X determined by measurement X (described later) and the contact angle Y determined by measurement Y (described later) is 20 degrees or less. One preferred embodiment of the method for producing a laminate includes the above-mentioned laminating step, peeling step, exposure step, and development step in this order.

[0020] A feature of the method for producing a laminate of the present invention is that the difference between contact angle X determined by measurement X (described later) and contact angle Y determined by measurement Y (described later) is 20 degrees or less. Although the details of the mechanism by which the method for producing a laminate of the present invention achieves the desired effects are not clear, the present inventors speculate as follows. It is presumed that when the difference between the contact angle X and the contact angle Y described above is within a predetermined range, the layer (cured layer) obtained by exposing the photosensitive composition layer to light has low affinity for an alkaline developer, and therefore, when developed using an alkaline developer, swelling and dissolution of the pattern are suppressed, making it less likely for the pattern to flare out, resulting in an excellent pattern shape. Hereinafter, an excellent pattern shape is also referred to as an excellent effect of the present invention.

[0021] Each step of the method for producing a laminate of the present invention will be described in detail below. Note that the following description of the constituent elements may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

[0022] [Contact angle X and contact angle Y] In the method for producing a laminate of the present invention, the difference between the contact angle X determined by measurement X and the contact angle Y determined by measurement Y is 20 degrees or less, preferably 1 to 20 degrees, and more preferably 10 to 20 degrees. Here, the difference is a numerical value obtained by subtracting the smaller of the contact angles X and Y from the larger one. For example, if contact angle Y is larger than contact angle X, the difference is obtained by "contact angle Y - contact angle X." If contact angle X and contact angle Y are the same numerical value, the difference is considered to be 0.

[0023] The contact angle X is preferably from 10 to 170 degrees, more preferably from 30 to 100 degrees, still more preferably from 50 to 80 degrees, particularly preferably from 50 to 70 degrees, and most preferably from 50 to 64 degrees. The contact angle X is a value determined by the following measurement X. Measurement X is a measurement in which the surface of the photosensitive composition layer of the transfer film opposite to the intermediate layer side is brought into contact with a substrate, the transfer film and the substrate are laminated together, the temporary support is peeled off from the resulting laminate between the temporary support and the intermediate layer, the photosensitive composition layer is exposed entirely from the exposed intermediate layer side, and then the photosensitive composition layer is brought into contact with the alkaline developer used in the development step, and the water contact angle of the exposed surface of the cured layer is measured and defined as contact angle X. The exposure conditions (type of light source, exposure dose, etc.) for the entire surface exposure are the same as those for the exposure step described below. In other words, the entire surface exposure performed in measurement X corresponds to an exposure in which the exposure range of the pattern exposure performed in the exposure step described below is changed to the entire surface of the photosensitive composition layer. The water contact angle is measured, for example, by dropping 2 to 10 μL of ion-exchanged water onto the exposed surface of the cured layer at room temperature (25°C), and measuring the angle at which the water droplet contacts the surface of the cured layer (water contact angle) using a contact angle meter (DSA25S, manufactured by KRUSS). This measurement is performed 10 times (n=10), and the average of the obtained contact angle values ​​is used as the contact angle X. When the transfer film has a protective film, the measurement X is carried out after peeling the protective film from the transfer film.

[0024] The contact angle Y is preferably 10 to 170 degrees, more preferably 50 to 120 degrees, more preferably more than 70 degrees to 120 degrees or less, even more preferably more than 70 degrees to 90 degrees or less, and particularly preferably more than 70 degrees to less than 80 degrees. The contact angle Y is a value determined by the following measurement Y. In Measurement Y, the surface of the photosensitive composition layer of the transfer film opposite to the intermediate layer side is brought into contact with a 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 surface of the photosensitive composition layer is exposed from the exposed intermediate layer side, and then the photosensitive composition layer is brought into contact with water, and the water contact angle of the exposed surface of the cured layer is measured, which is the contact angle Y. In other words, Measurement Y is a measurement method similar to Measurement X, except that the alkaline developer in Measurement X is changed to water. The method for measuring the water contact angle may be, for example, the method for measuring the water contact angle used for the contact angle X described above. The exposure conditions (type of light source, exposure dose, etc.) for the entire surface exposure are the same as those for the exposure step described below. In other words, the entire surface exposure performed in measurement Y corresponds to an exposure in which the exposure range of the pattern exposure performed in the exposure step described below is changed to the entire surface of the photosensitive composition layer. When the transfer film has a protective film, measurement Y is carried out after peeling the protective film from the transfer film.

[0025] The contact angle X and the contact angle Y can be adjusted, for example, by changing the type and content of the resin contained in the photosensitive composition layer. Specifically, examples of such methods include a method using a resin whose weight-average molecular weight, acid value, and Tg (glass transition temperature) are adjusted to the respective preferred modes described below, a method using a resin synthesized using a tri- or higher functional monomer, and a method combining these methods.

[0026] [Lamination process] The lamination process is a process in which the surface of a transfer film having a temporary support, an intermediate layer, and a photosensitive composition layer in this order opposite the intermediate layer side of the photosensitive composition layer is brought into contact with a substrate, and the transfer film and the substrate are laminated together. When the transfer film has a protective film, the laminating step may be carried out after peeling off the protective film.

[0027] In the laminating step, the surface of the transfer film opposite to the intermediate layer side of the photosensitive composition layer is brought into contact with the substrate and pressed against it. Examples of the pressure-bonding method include known transfer methods and lamination methods. In particular, the preferred pressure bonding method is to place the surface of the transfer film opposite to the intermediate layer side of the photosensitive composition layer on the substrate, and then apply pressure and heat with a roll or the like. Examples of the lamination method include lamination methods using a known laminator such as a vacuum laminator or an autocut laminator. The lamination temperature is preferably 70 to 130°C.

[0028] The substrate is preferably a substrate having a conductive layer. The substrate having a conductive layer may have any layer other than the conductive layer formed thereon as necessary. In other words, the substrate is preferably a conductive substrate having at least a conductive layer disposed thereon. Examples of the substrate include a resin substrate, a glass substrate, and a semiconductor substrate. As the substrate, paragraph

[0140] of International Publication No. 2018 / 155193 is preferred, the contents of which are incorporated herein by reference. The resin substrate is preferably made of a cycloolefin polymer or polyimide. The thickness of the resin substrate is preferably 5 to 200 μm, more preferably 10 to 100 μm.

[0029] The conductive layer is preferably 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, from the viewpoints of conductivity and fine line formability. Only one conductive layer may be disposed on the substrate, or two or more conductive layers may be disposed on the substrate. When two or more conductive layers are disposed, it is preferable that the two or more conductive layers be made of different materials. As the conductive layer, paragraph

[0141] of WO 2018 / 155193 is preferred, the contents of which are incorporated herein by reference.

[0030] [Peeling process] The peeling step is a step of peeling the temporary support between the temporary support and the intermediate layer. The method for peeling off the temporary support may be, for example, a known peeling method, specifically the cover film peeling mechanism described in paragraphs

[0161] to

[0162] of JP-A No. 2010-072589.

[0031] [Exposure process] The exposure step is a step of pattern-exposing the photosensitive composition layer. "Pattern exposure" refers to a form of pattern-wise exposure, that is, exposure in a form in which exposed areas and non-exposed areas exist. The positional relationship between the exposed and unexposed regions in the pattern exposure is not particularly limited and can be adjusted as appropriate.

[0032] The direction of exposure is not particularly limited, and the photosensitive composition layer may be exposed from the intermediate layer side or from the side opposite to the intermediate layer side (substrate side).

[0033] In the exposure step, it is preferable to bring the intermediate layer exposed by the peeling step into contact with a mask and perform pattern exposure. By bringing the intermediate layer into contact with the mask and performing pattern exposure, a high-definition 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 carrying out an exposure step in which the intermediate layer is brought into contact with a mask, a curing reaction of the components contained in the photosensitive composition layer can occur in the exposed regions of the photosensitive composition layer (positions corresponding to the openings of the mask). By carrying out an alkali development treatment after exposure, the unexposed regions of the photosensitive composition layer are removed, thereby forming a pattern. The method for producing a laminate preferably includes a peeling step of peeling off the mask used in the exposure step between the exposure step and the development treatment.

[0034] When the photosensitive composition layer is a negative photosensitive layer, the light source for pattern exposure can be appropriately selected and used as long as it can irradiate light at least in a wavelength range capable of curing the photosensitive composition layer (e.g., 365 nm and 405 nm). In particular, the dominant wavelength of the exposure light for pattern exposure is preferably 365 nm, where dominant wavelength means the wavelength with the highest intensity.

[0035] 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 to 200 mJ / cm 2 is preferred, and 10 to 200 mJ / cm 2 is more preferred. Examples of light sources, exposure doses, and exposure methods include those described in paragraphs

[0146] to

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

[0036] [Development process] The development step is a step in which the exposed photosensitive composition layer is developed with an alkaline developer to form a pattern. When the photosensitive composition layer is a negative photosensitive layer, the unexposed areas of the photosensitive composition layer are removed by development using an alkaline developer, and a pattern in which the openings of the mask are convex is formed.

[0037] The alkaline developer is preferably an alkaline aqueous solution. Examples of alkaline compounds (compounds that exhibit alkalinity when dissolved in water) contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0038] The development method may be, for example, a known development method, specifically, puddle development, shower development, spin development, and dip development. The developing method is preferably the developing method described in paragraph

[0195] of WO 2015 / 093271.

[0039] [Post-exposure process and post-bake process] The method for producing a laminate of the present invention may further include a step of exposing the pattern obtained by the development step (hereinafter also referred to as a "post-exposure step") and / or a step of heating (hereinafter also referred to as a "post-bake step"). When the method for producing a laminate includes both a post-exposure step and a post-bake step, it is preferable to carry out the post-bake step after carrying out the post-exposure step. The exposure dose in the post-exposure process is 100 to 5000 mJ / cm 2 is preferred, and 200 to 3000 mJ / cm 2 is more preferred. In the post-baking step, the post-baking temperature is preferably 80 to 250°C, more preferably 90 to 160°C. In the post-baking step, the post-baking time is preferably from 1 to 180 minutes, more preferably from 10 to 60 minutes.

[0040] The position and size of the pattern formed on the substrate obtained by the method for producing the laminate are not particularly limited. Among these, a thin line 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 particularly preferably 5 μm or less. The lower limit is preferably 1 μm or more, more preferably 3 μm or more.

[0041] [Applications of laminates] The laminate produced by the laminate production method of the present invention can be applied to various devices. Examples of devices equipped with the laminate include input devices, preferably touch panels, more preferably capacitance touch panels. The input devices can be applied to display devices such as organic EL (organic electroluminescence) display devices and liquid crystal display devices.

[0042] [Circuit wiring manufacturing method] The method for manufacturing circuit wiring of the present invention includes, when a conductive substrate is used as the substrate, an etching step of etching the conductive layer in areas of a laminate having a pattern manufactured by the above-mentioned method for manufacturing a laminate where no pattern is arranged.

[0043] Each step of the circuit wiring manufacturing method of the present invention will be described in detail below. Note that the following description of the constituent elements may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

[0044] [Etching process] The etching step is a step of etching the conductive layer in the areas where no pattern is arranged. Specifically, in the etching step, the conductive layer is etched using, as an etching resist, the pattern obtained from the photosensitive composition layer in the development step in the above-described method for producing a laminate. The substrate has the same meaning as the substrate in the above-mentioned method for producing a laminate, and the preferred embodiments are also the same.

[0045] The etching method may be, for example, a known etching method. Specific examples include the method described in paragraphs

[0209] to

[0210] of JP 2017-120435 A, the method described in paragraphs

[0048] to

[0054] of JP 2010-152155 A, wet etching in which the substrate is immersed in an etching solution, and dry etching such as plasma etching.

[0046] The etching solution used in the wet etching can be selected appropriately from acidic and alkaline etching solutions depending on the target to be etched. Examples of the acidic etching solution include an acidic aqueous solution containing one or more acidic compounds, and an acidic mixed aqueous solution 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 exhibits acidity when dissolved in water) 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 mixed aqueous solutions of an alkaline compound and a salt (such as potassium permanganate). The alkaline compound (a compound that exhibits alkalinity when dissolved in water) contained in the alkaline aqueous solution is preferably at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide).

[0047] [Removal process] The method for producing circuit wiring of the present invention may include a removal step of removing the remaining pattern. The removal step is preferably carried out after the etching step described above. The remaining pattern can be removed by, for example, chemical treatment, and preferably by using a remover. The temperature of the removal liquid is preferably 30 to 80°C, more preferably 50 to 80°C. One preferred embodiment of the removal method is, for example, a method in which a substrate having a pattern to be removed is immersed in a stirring removal liquid at a liquid temperature of 50 to 80° C. for 1 to 30 minutes. Examples of methods for removing the remaining pattern include a method using a remover by a known method such as a spray method, a shower method, or a puddle method.

[0048] Examples of the removal liquid include a removal liquid 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 a mixed solution thereof. Alkaline inorganic compounds include, for example, 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.

[0049] [Other processes] The method for manufacturing circuit wiring may include other steps in addition to the steps described above. Other steps include, for example, the step of reducing the visible light reflectance described in paragraph

[0172] of WO 2019 / 022089 and the step of forming a new conductive layer on the surface of the insulating film described in paragraph

[0172] of WO 2019 / 022089.

[0050] <Step of reducing visible light reflectance> The 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 plurality of conductive layers of the substrate. An example of a treatment for reducing the visible light reflectance is oxidation treatment. When the substrate has a conductive layer containing copper, the visible light reflectance of the conductive layer can be reduced by oxidizing the copper to copper oxide and blackening the conductive layer. Examples of treatments for reducing visible light reflectance include those described in paragraphs

[0017] to

[0025] of JP 2014-150118 A, and paragraphs

[0041] ,

[0042] ,

[0048] , and

[0058] of JP 2013-206315 A, the contents of which are incorporated herein by reference.

[0051] <Step of forming an insulating film, step of forming a new conductive layer on the surface of the insulating film> The method for manufacturing the circuit wiring may include a step of forming an insulating film on the surface of the circuit wiring, and a step of forming a new conductive layer on the surface of the insulating film. By the above steps, a first electrode pattern and an insulated second electrode pattern can be formed. Examples of the step of forming the insulating film include a known method for forming a permanent film. Alternatively, an insulating film having a desired pattern may be formed by photolithography using an insulating photosensitive composition. In the step of forming a new conductive layer on the surface of the insulating film, for example, a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive composition having conductivity.

[0052] In a preferred method for producing circuit wiring, a substrate having a plurality of conductive layers on both surfaces of the substrate is used, and circuit wiring is formed sequentially or simultaneously on the conductive layers formed on both surfaces of the substrate. With the above configuration, a circuit wiring for a touch panel can be formed in which a first conductive pattern is formed on the surface of one substrate and a second conductive pattern is formed on the surface of the other substrate. It is also preferable to form the circuit wiring for a touch panel having the above configuration from both sides of the substrate by roll-to-roll.

[0053] [Circuit wiring applications] The circuit wiring manufactured by the circuit wiring manufacturing method can be applied to various devices. Examples of devices equipped with the circuit wiring include input devices, preferably touch panels, and more preferably capacitance touch panels. The input devices can be applied to display devices such as organic electroluminescence (EL) display devices and liquid crystal display devices.

[0054] [Transfer film] The transfer film of the present invention has a temporary support, an intermediate layer, and a photosensitive composition layer in this order, and is subjected to a development step in which the film is developed using an alkaline developer after an exposure treatment to form a pattern, and the difference between the contact angle X obtained by measurement X and the contact angle Y obtained by measurement Y is 20 degrees or less. The contact angle X, contact angle Y, and the difference between the contact angles X and Y in the transfer film are respectively synonymous with the contact angle X, contact angle Y, and the difference between the contact angles X and Y in the above-mentioned method for producing a laminate, and the preferred ranges are also the same.

[0055] The transfer film may have other layers in addition to the photosensitive composition layer and the intermediate layer. Examples of the other layer include a thermoplastic resin layer, which will be described later. The transfer film may also have a protective film, which will be described later, on the photosensitive composition layer.

[0056] The transfer film may have any of the following configurations, but is not limited thereto. (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-mentioned configurations, the photosensitive composition layer is preferably a negative photosensitive composition layer, and also preferably a colored resin layer.

[0057] In order to prevent the generation of bubbles during the lamination step, the maximum width of the undulations 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 undulation of the transfer film is a 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, horizontal stage with the surface of the temporary support facing the stage. After placement, a 10 cm square area in the center of the test sample is scanned with a laser microscope (e.g., Keyence VK-9700SP) to obtain a 3D surface image. The minimum concave height is subtracted from the maximum convex height observed in the obtained 3D surface image. This procedure is performed on 10 test samples, and the arithmetic average value is taken as the maximum waviness width of the transfer film.

[0058] To obtain better adhesion, the transmittance of the photosensitive composition layer at a wavelength of 365 nm is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more. There is no upper limit, but it is preferably 99.9% or less.

[0059] An example of an embodiment of the transfer film will now be described. The transfer film 10 shown in FIG. 1 has a temporary support 11, a composition layer 17 including an intermediate layer 13 and a photosensitive composition layer 15, and a protective film 19, in this order. Although the transfer film 10 shown in FIG. 1 has a protective film 19 disposed thereon, the protective film 19 does not necessarily have to be disposed. In FIG. 1, each layer except for the protective film 19 that can be disposed 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 layers, and it is preferable that the thermoplastic resin layer is disposed between the temporary support 11 and the intermediate layer 13 .

[0060] The following describes in detail each component and each ingredient of the transfer film of the present invention. Note that the following description of the constituent elements may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

[0061] [Temporary support] The transfer film has a temporary support. The temporary support is a member that supports the photosensitive composition layer, and is ultimately removed by a peeling treatment.

[0062] The temporary support may have a single layer structure or a multilayer structure. The temporary support is preferably a film, more preferably a resin film. In addition, the temporary support is preferably a film that is flexible and does not significantly deform, shrink, or stretch under pressure or under pressure and heat, and is also preferably a film that is free from deformation such as wrinkles and scratches. Examples of the film include polyethylene terephthalate film (for example, biaxially stretched polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film, with polyethylene terephthalate film being preferred.

[0063] The temporary support preferably has high transparency so that pattern exposure can be performed through the temporary support. Specifically, the transmittance of the temporary support at a wavelength of 365 nm is preferably 60% or more, more preferably 70% or more. The upper limit is preferably less than 100%. From the viewpoint of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, it is preferable that the haze of the temporary support is small. Specifically, the haze of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less. The lower limit is preferably 0% or more.

[0064] From the viewpoint of pattern formation during pattern exposure through the temporary support and the transparency of the temporary support, it is preferable that the number of fine particles, foreign matter, and defects in the temporary support is small. Specifically, the number of fine particles (for example, fine particles with a diameter of 1 μm), foreign matter, and defects in the temporary support is 50 / 10 mm. 2 Preferably less than 10 pieces / 10mm 2 Less than 3 pieces / 10mm is more preferable. 2 Less than 0 / 10mm is more preferable.2 is particularly preferred.

[0065] The thickness of the temporary support is preferably from 5 to 200 μm, and from the viewpoint of ease of handling and versatility, more preferably from 5 to 150 μm, still more preferably from 5 to 50 μm, and particularly preferably from 5 to 25 μm. The thickness of the temporary support is calculated as the average value of measurements taken at any five points by cross-sectional observation using an SEM (Scanning Electron Microscope).

[0066] From the viewpoint of handling, the temporary support may have a layer containing fine particles (lubricant layer) on one or both sides of the temporary support. The diameter of the fine particles contained in the lubricant layer is preferably 0.05 to 0.8 μm. The thickness of the lubricant layer is preferably 0.05 to 1.0 μm.

[0067] In order to improve the adhesion between the temporary support and the photosensitive composition layer, the surface of the temporary support that comes into contact with the photosensitive composition layer may be subjected to a surface modification treatment. Examples of surface modification treatments include treatments using UV irradiation, corona discharge, plasma, and the like. The exposure dose for UV irradiation is 10 to 2000 mJ / cm 2 is preferred, and 50 to 1000 mJ / cm 2 is more preferred. As long as the exposure amount is within the above range, the lamp output and illuminance are not particularly limited. Examples of light sources for UV irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes (LEDs), all of which emit light in the 150 to 450 nm wavelength band.

[0068] Examples of the temporary support include a biaxially oriented polyethylene terephthalate film having a thickness of 16 μm, a biaxially oriented polyethylene terephthalate film having a thickness of 12 μm, and a biaxially oriented polyethylene terephthalate film having a thickness of 9 μm. Further, examples of temporary supports include those described in paragraphs

[0017] to

[0018] of JP 2014-085643 A, paragraphs

[0019] to

[0026] of JP 2016-027363 A, paragraphs

[0041] to

[0057] of WO 2012 / 081680 A, and paragraphs

[0029] to

[0040] of WO 2018 / 179370 A, the contents of which are incorporated herein by reference. Commercially available temporary supports include, for example, Lumirror 16KS40 and Lumirror 16FB40 (all manufactured by Toray Industries, Inc.), Cosmoshine A4100, Cosmoshine A4300, and Cosmoshine A8300 (all manufactured by Toyobo Co., Ltd.).

[0069] [Photosensitive composition layer] The transfer film of the present invention has a photosensitive composition layer. In display devices (e.g., organic EL display devices and liquid crystal display devices) equipped with a touch panel such as a capacitance input device, conductive layer patterns such as an electrode pattern corresponding to the sensor of the viewing area, and wiring of the peripheral wiring portion and the lead-out wiring portion are provided inside the touch panel. Generally, a method of forming a patterned layer is widely adopted in which a negative photosensitive composition layer (photosensitive layer) is provided on a substrate using a transfer film or the like, and the photosensitive layer is exposed to light through a mask having a desired pattern, and then developed. Therefore, a negative photosensitive composition layer is preferred as the photosensitive composition layer. When the photosensitive composition layer is a negative photosensitive composition layer, the pattern formed corresponds to a cured layer.

[0070] The photosensitive composition layer preferably contains a resin, a polymerizable compound, and a polymerization initiator, as described below. Furthermore, as described below, the photosensitive composition layer preferably contains an alkali-soluble resin (e.g., a resin that is an alkali-soluble resin). That is, the photosensitive composition layer preferably contains a resin containing an alkali-soluble resin, a polymerizable compound, and a polymerization initiator. The photosensitive composition layer preferably contains 10 to 90% by mass of a resin, 5 to 70% by mass of a polymerizable compound, and 0.01 to 20% by mass of a polymerization initiator, based on the total mass of the photosensitive composition layer.

[0071] <Resin> The photosensitive composition layer may contain a resin. The resin is preferably an alkali-soluble resin. As the resin, an alkali-soluble resin in the thermoplastic resin layer described below may be used.

[0072] In order to prevent line width thickening and deterioration of resolution when the focus position is shifted during exposure, the resin preferably contains a structural unit derived from a monomer having an aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group. The content of structural units derived from monomers having an aromatic hydrocarbon group in the resin is preferably 10% by mass or more, more preferably 20% 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, and even more preferably 38% 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 content of structural units derived from monomers having an aromatic hydrocarbon group falls within the above range. The above average value is a mass average value.

[0073] Examples of the monomer having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer), of which a monomer having an aralkyl group or styrene is preferred, and styrene is more preferred. When the aromatic hydrocarbon group-containing monomer in the resin is styrene, the content of structural units derived from styrene is preferably 10 to 80 mass%, more preferably 10 to 60 mass%, still more preferably 20 to 60 mass%, particularly preferably 20 to 50 mass%, and most preferably 20 to 38 mass%, relative to the total mass of the resin. When the photosensitive composition layer contains a plurality of resins, the average content of structural units having an aromatic hydrocarbon group preferably falls within the above range. The average value is a mass average value.

[0074] Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group) and a substituted or unsubstituted benzyl group, with a substituted or unsubstituted benzyl group being preferred.

[0075] An example of a monomer having a phenylalkyl group is phenylethyl (meth)acrylate.

[0076] Examples of the monomer 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 vinylbenzyl chloride and vinylbenzyl alcohol. Of 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 the structural unit derived from benzyl (meth)acrylate is preferably 50 to 95 mass%, more preferably 60 to 90 mass%, even more preferably 70 to 90 mass%, and particularly preferably 75 to 90 mass%, relative to the total mass of the resin.

[0077] The resin containing a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing a monomer having an aromatic hydrocarbon group with at least one type of first monomer described below and / or at least one type of second monomer described below.

[0078] The resin that does not contain a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one type of first monomer described below, and more preferably obtained by copolymerizing at least one type of first monomer with at least one type of second monomer described below.

[0079] The first monomer is a monomer having a carboxy group in the 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 half ester, with (meth)acrylic acid being preferred. The content of the structural unit derived from the first monomer in the resin is preferably 5 to 50 mass% relative to the total mass of the resin, more preferably 10 to 40 mass%, and from the viewpoint of achieving better effects of the present invention, even more preferably 15 to 30 mass%, particularly preferably 15 to 20 mass%. When the content is 5% by mass or more, excellent developability and control of edge fusing properties can be achieved, etc. When the content is 50% by mass or less, high resolution and control of foot shape of the resist pattern, as well as high chemical resistance of the resist pattern can be achieved. Furthermore, when the content is within the above range, the contact angle X and contact angle Y can be adjusted.

[0080] The second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in the 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. Of these, methyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or n-butyl (meth)acrylate is preferred, and methyl (meth)acrylate or ethyl (meth)acrylate is more preferred. The content of the constitutional units derived from the second monomer in the resin is preferably 5 to 80 mass %, more preferably 15 to 60 mass %, and even more preferably 30 to 60 mass %, relative to the total mass of the resin.

[0081] When the resin contains a structural unit derived from a monomer having an aralkyl group and / or a structural unit derived from styrene, it is possible to suppress line width thickening and deterioration in resolution when the focal position is shifted during exposure. The resin is preferably a copolymer containing a structural unit derived from methacrylic acid, a structural unit derived from benzyl methacrylate, and a structural unit derived from styrene; a copolymer containing a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, a structural unit derived from benzyl methacrylate, and a structural unit derived from styrene; or a copolymer containing a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from styrene. One preferred embodiment of the resin includes 20 to 60 mass% of structural units derived from a monomer having an aromatic hydrocarbon group, 10 to 40 mass% of structural units derived from a first monomer, and 15 to 60 mass% of structural units derived from a second monomer. Another preferred embodiment of the resin includes 70 to 90 mass % of structural units derived from a monomer having an aromatic hydrocarbon group and 10 to 25 mass % of structural units derived from the first monomer.

[0082] The resin may have a linear structure, a branched structure, or an alicyclic structure in the side chain. By using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain, it is possible to introduce a branched structure or an alicyclic structure into the side chain of the resin. The group having an alicyclic structure may be either monocyclic or polycyclic. Examples of monomers containing a group having a branched structure in the 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. Of these, isopropyl (meth)acrylate, isobutyl (meth)acrylate, or tert-butyl methacrylate is preferred, and isopropyl methacrylate or tert-butyl methacrylate is more preferred. Examples of the monomer containing a group having an alicyclic structure in the side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group, and also include a (meth)acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. Specifically, (meth)acrylic acid (bicyclo[2.2.1]heptyl-2) (meth)acrylate, (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, fenchyl (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, fenchyl (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecane (meth)acrylate is preferred, and cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate is more preferred.

[0083] The glass transition temperature (Tg) of the resin is preferably from 30 to 150°C, more preferably from 100 to 150°C, and even more preferably from more than 110°C to 130°C or less.

[0084] The I / O value of the resin is preferably from 0.30 to 0.90, more preferably from 0.45 to 0.70, and even more preferably from 0.50 to 0.70. The I / O value is a parameter that indicates the hydrophilicity / lipophilicity of a resin. For information on I / O values, please refer to "Organic Conceptual Diagram" (by Yoshio Koda, Sankyo Publishing, 1984). The closer the I / O value of a resin is to 0 (zero), the less polar the resin is (the more lipophilic the resin is), and the higher the I / O value of a resin is, the more polar the resin is (the more hydrophilic the resin is). The I / O value was calculated by calculating I (hydrophilicity) and O (lipophilicity) based on the chemical structure of the resin.

[0085] In one preferred embodiment of the acid value of the resin, from the viewpoint of achieving better effects of the present invention, the acid value is preferably 10 to 200 mgKOH / g, more preferably 30 to 150 mgKOH / g, even more preferably 50 to 150 mgKOH / g, and particularly preferably 90 to 130 mgKOH / g. The acid value (mgKOH / g) is the mass (mg) of potassium hydroxide required to neutralize 1 g of a sample. The acid value can be determined, for example, according to the method described in JIS K0070:1992. The acid value of the resin can be adjusted by the type of structural unit contained in the resin and / or the content of structural units containing an acid group.

[0086] The weight average molecular weight of the resin is preferably from 5,000 to 500,000, more preferably from 10,000 to 100,000, still more preferably from 20,000 to 50,000, and particularly preferably from 20,000 to 40,000. When the weight-average molecular weight is 500,000 or less, resolution and developability can be improved. Furthermore, when the weight-average molecular weight is 5,000 or more, the properties of the development aggregates and the properties of the unexposed film, such as the edge fusing property and cut-chip property of the transfer film, can be controlled. Edge fusing property refers to the degree to which the photosensitive composition layer easily protrudes from the edge of the roll when the transfer film is wound into a roll. Cut-chip property refers to the degree to which chips fly off when the unexposed film is cut with a cutter. If these chips adhere to the top surface of the transfer film, they can be transferred to a mask in a subsequent exposure process, causing defective products. The dispersity of the resin is preferably from 1.0 to 6.0, more preferably from 1.0 to 5.0, still more preferably from 1.0 to 4.0, and particularly preferably from 1.0 to 3.0.

[0087] The photosensitive composition layer may contain other resins in addition to the above-mentioned resins. Examples of other resins include 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.

[0088] The resins may be used alone or in combination of two or more. When two or more resins are used, it is preferable to mix two resins containing structural units derived from a monomer having an aromatic hydrocarbon group, or to mix a resin containing structural units derived from a monomer having an aromatic hydrocarbon group with a resin not containing structural units derived from a monomer having an aromatic hydrocarbon group. In the latter case, the content of the resin containing structural units derived from a monomer having an aromatic hydrocarbon group 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.

[0089] The resin content is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, still more preferably 30 to 70% by mass, and particularly preferably 40 to 60% by mass, based on the total mass of the photosensitive composition layer. When the resin content is 90% by mass or less, based on 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, based on the total mass of the photosensitive composition layer, edge fuse resistance can be improved.

[0090] Examples of resin synthesis methods include adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to a solution prepared by diluting one or more of the above-mentioned monomers with a solvent such as acetone, methyl ethyl ketone, or isopropanol, and then heating and stirring the mixture. Synthesis may also be performed by adding a portion of the mixture dropwise to the reaction solution. Alternatively, after the reaction is complete, additional solvent may be added to adjust the concentration to the desired level. In addition to the above, other methods for synthesizing the resin include bulk polymerization, suspension polymerization, and emulsion polymerization.

[0091] <Polymerizable compound> The photosensitive composition layer preferably contains a polymerizable compound having a polymerizable group. In this specification, the term "polymerizable compound" refers to a compound that undergoes polymerization in the presence of a polymerization initiator, which will be described later, and is different from the resin described above.

[0092] The polymerizable group contained in the polymerizable compound is not particularly limited as long as it is a group that participates in a polymerization reaction, and examples thereof include groups having an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group; and groups having a cationically polymerizable group such as an epoxy group and an oxetane group. Of these, the polymerizable group is preferably a group having an ethylenically unsaturated group, and more preferably an acryloyl group or a methacryloyl group.

[0093] As the polymerizable compound, a compound having one or more ethylenically unsaturated groups (ethylenically unsaturated compound) is preferred, and a compound having two or more ethylenically unsaturated groups in one molecule (polyfunctional ethylenically unsaturated compound) is more preferred, in that the photosensitivity of the photosensitive composition layer is superior. In addition, the number of ethylenically unsaturated groups that the ethylenically unsaturated compound has in one molecule is preferably 1 to 6, more preferably 1 to 3, even more preferably 2 or 3, and particularly preferably 3, in terms of better resolution and releasability.

[0094] The content of the bifunctional ethylenically unsaturated compound is preferably 20% by mass or more, more preferably more than 40% by mass, even more preferably 55% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of the polymerizable compounds, from the viewpoint of excellent releasability. The upper limit is not particularly limited, but is preferably 100% by mass or less. In other words, all of the polymerizable compounds contained in the photosensitive composition layer may be bifunctional 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 compounds, from the viewpoint of adjusting the contact angle X and the contact angle Y. 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 of the polymerizable compounds contained in the photosensitive composition layer may be trifunctional ethylenically unsaturated compounds. Moreover, the ethylenically unsaturated compound is preferably a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group.

[0095] (Polymerizable compound B1) The photosensitive composition layer preferably contains a polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups. The polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule, among the above-mentioned polymerizable compounds B.

[0096] Examples of the aromatic ring contained in the polymerizable compound B1 include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, and an anthracene ring; aromatic heterocycles such as a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring, and a pyridine ring; and fused rings thereof, with an aromatic hydrocarbon ring being preferred and a benzene ring being more preferred. The aromatic ring may have a substituent. The polymerizable compound B1 may have only one aromatic ring, or may have two or more aromatic rings.

[0097] The polymerizable compound B1 preferably has a bisphenol structure, since this inhibits swelling of the photosensitive composition layer due to a developer, thereby improving resolution. Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), a bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and a bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), with the bisphenol A structure being preferred.

[0098] Examples of the polymerizable compound B1 having a bisphenol structure include a compound having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. The two polymerizable groups may be bonded to both ends of the bisphenol structure directly or via one or more alkyleneoxy groups. The alkyleneoxy groups added to both ends of the bisphenol structure are preferably ethyleneoxy groups or propyleneoxy groups, more preferably ethyleneoxy groups. The number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14 per molecule. The polymerizable compound B1 having a bisphenol structure is described in paragraphs

[0072] to

[0080] of JP-A-2016-224162, the contents of which are incorporated herein by reference.

[0099] As the polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferred, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferred. Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), and 2,2-bis(4-(methacryloxydodecaethoxy)phenyl)propane. Examples of suitable ethoxylated bisphenol A diacrylate include 2,2-bis(4-(methacryloxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.), and ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0100] The polymerizable compound B1 is also preferably a compound represented by formula (B1).

[0101] [ka]

[0102] 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 of 1 to 39. n1 + n3 is an integer of 2 to 40. n2 and n4 each independently represent an integer of 0 to 29. n2 + n4 is an integer of 0 to 30. The arrangement of the -(AO)- and -(BO)- structural units may be random or in blocks. When in blocks, either -(AO)- or -(BO)- may be on the bisphenyl group side. n1+n2+n3+n4 is preferably 2 to 20, more preferably 2 to 16, and still more preferably 4 to 12. Furthermore, n2+n4 is preferably 0 to 10, more preferably 0 to 4, still more preferably 0 to 2, and particularly preferably 0.

[0103] The polymerizable compound B1 may be used alone or in combination of two or more. The content of the 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, based on the total mass of the photosensitive composition layer, from the viewpoint of better resolution. The upper limit is not particularly limited, but from the viewpoint of transferability and edge fusion (a phenomenon in which the photosensitive composition seeps out from the edge of a transfer member), it is preferably 70% by mass or less, more preferably 60% by mass or less.

[0104] The content of the 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, based on the total mass of the polymerizable compounds, from the viewpoint of superior resolution. The upper limit is not particularly limited, but from the viewpoint of releasability, 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.

[0105] (Other polymerizable compounds) The photosensitive composition layer may contain other polymerizable compounds in addition to the above-mentioned polymerizable compound B1. The other polymerizable compounds are not particularly limited and can be appropriately selected from known polymerizable compounds, such as compounds having one ethylenically unsaturated group per molecule (monofunctional ethylenically unsaturated compounds), bifunctional ethylenically unsaturated compounds without aromatic rings, and trifunctional or higher ethylenically unsaturated compounds.

[0106] 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.

[0107] Examples of the difunctional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate. Examples of alkylene glycol di(meth)acrylates include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate. Examples of polyalkylene glycol di(meth)acrylates include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate. Examples of urethane di(meth)acrylates include propylene oxide-modified urethane di(meth)acrylates and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates. Commercially available products include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0108] Examples of tri- or higher functional ethylenically unsaturated compounds include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide-modified products thereof. Here, "(tri / tetra / penta / hexa)(meth)acrylate" is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate.

[0109] Examples of alkylene oxide-modified trifunctional or higher ethylenically unsaturated compounds include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel-Allnex Corporation, etc.), ethoxylated glycerin triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), ARONIX (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), ARONIX M-520 (manufactured by Toagosei Co., Ltd.), and ARONIX M-510 (manufactured by Toagosei Co., Ltd.).

[0110] The polymerizable compound may also be a polymerizable compound having an acid group (such as a carboxy group). The acid group may form an acid anhydride group. Examples of polymerizable compounds having an acid group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and Aronix (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.). Examples of the polymerizable compound having an acid group include those described in paragraphs

[0025] to

[0030] of JP-A No. 2004-239942.

[0111] The molecular weight (weight average molecular weight when the polymerizable compound (including polymerizable compound B1) has a molecular weight distribution) is preferably from 200 to 3,000, more preferably from 280 to 2,200, and even more preferably from 300 to 2,200.

[0112] The polymerizable compounds may be used alone or in combination of two or more. The content of the polymerizable compound is preferably from 10 to 70% by mass, more preferably from 15 to 70% by mass, and even more preferably from 20 to 70% by mass, based on the total mass of the photosensitive composition layer.

[0113] The mass ratio of the content of the difunctional or higher polymerizable compound to the content of the resin (content of the difunctional or higher polymerizable compound / content of the resin) 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, in order to achieve better effects of the present invention.

[0114] The photosensitive composition layer preferably contains the above-described polymerizable compound B1 and a trifunctional or higher ethylenically unsaturated compound, and more preferably contains the above-described polymerizable compound B1 and two or more trifunctional or higher ethylenically unsaturated compounds. The mass ratio of the mass of the polymerizable compound B1 to the mass of the tri- or higher functional ethylenically unsaturated compound is preferably from 1.0 to 5.0, more preferably from 1.2 to 4.0, and even more preferably from 1.5 to 3.0. The photosensitive composition layer preferably contains the above-mentioned polymerizable compound B1 and a trifunctional ethylenically unsaturated compound.

[0115] <Polymerization initiator> The photosensitive composition layer also preferably contains a polymerization initiator. The polymerization initiator is selected depending on the type of polymerization reaction, and examples thereof include a thermal polymerization initiator and a photopolymerization initiator. The polymerization initiator may be a radical polymerization initiator or a cationic polymerization initiator.

[0116] The photosensitive composition layer preferably contains a photopolymerization initiator. A photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound when exposed to actinic rays such as ultraviolet light, visible light, and X-rays. The photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used. Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferred.

[0117] Examples of the photoradical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α-aminoalkylphenone structure, a photopolymerization initiator having an α-hydroxyalkylphenone structure, a photopolymerization initiator having an acylphosphine oxide structure, and a photopolymerization initiator having an N-phenylglycine structure.

[0118] In addition, from the viewpoints of photosensitivity, visibility of exposed and unexposed areas, and resolution, the photosensitive composition layer preferably contains, as a photoradical polymerization initiator, at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof. Note that the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimers and derivatives thereof may be the same or different. Examples of derivatives of 2,4,5-triarylimidazole dimers 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.

[0119] Examples of the photoradical polymerization initiator include the polymerization initiators described in paragraphs

[0031] to

[0042] of JP-A No. 2011-095716 and paragraphs

[0064] to

[0081] of JP-A No. 2015-014783.

[0120] Examples of the photoradical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (trade name: manufactured by Midori Chemical Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (trade name: manufactured by Midori Chemical Co., Ltd.), 1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), and IRGACURE OXE-04 (manufactured by BASF). OXE-04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins BV), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907, manufactured by IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (trade name: Omnirad 127, manufactured by IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (trade name: Omnirad 369, manufactured by IGM Resins BV), BV), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, IGM Resins BV), 1-hydroxycyclohexyl phenyl ketone (trade name: Omnirad 184, IGM Resins BV), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651, IGM Resins BV), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, IGM Resins BV)(trade name: Omnirad 819, manufactured by IGM Resins BV), oxime ester photoinitiator (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 Chemical Industry Co., Ltd.), 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-benzoyloxime) (trade name: TR-PBG-305, manufactured by Changzhou Qiang Chemical Co., Ltd.), Examples of suitable oxime include 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyloxime) (trade name: TR-PBG-326, Changzhou Strong Electronics New Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, Changzhou Strong Electronics New Materials Co., Ltd.).

[0121] A photocationic polymerization initiator (photoacid generator) is a compound that generates an acid when exposed to actinic rays. A preferred photocationic polymerization initiator is a compound that responds to actinic rays with a wavelength of 300 nm or more (preferably 300 to 450 nm) and generates an acid. Even if a photocationic polymerization initiator is not directly sensitive to actinic rays with a wavelength of 300 nm or more, it can be preferably used in combination with a sensitizer, as long as it responds to actinic rays with a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. The cationic photopolymerization initiator is preferably a cationic photopolymerization initiator that generates an acid with a pKa of 4 or less, more preferably a cationic photopolymerization initiator that generates an acid with a pKa of 3 or less, and particularly preferably a cationic photopolymerization initiator that generates an acid with a pKa of 2 or less. There is no particular restriction on the lower limit of the pKa, but it is preferably -10.0 or more.

[0122] Examples of the photocationic polymerization initiator include an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator. Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts. Examples of the ionic photocationic polymerization initiator include the ionic photocationic polymerization initiators described in paragraphs

[0114] to

[0133] of JP-A No. 2014-085643.

[0123] Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Examples of trichloromethyl-s-triazines, diazomethane compounds, and imide sulfonate compounds include the compounds described in paragraphs

[0083] to

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

[0084] to

[0088] of WO 2018 / 179640 A.

[0124] The polymerization initiator may be used alone 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, more preferably 0.5% by mass or more, based on the total mass of the photosensitive composition layer, and 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.

[0125] <Dye> From the viewpoints of the visibility of exposed and unexposed areas, and the pattern visibility and resolution after development, the photosensitive composition layer preferably contains a dye (also referred to as "dye N") that has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 to 780 nm during color development and whose maximum absorption wavelength changes in response to an acid, a base, or a radical. When dye N is contained, adhesion to adjacent layers (for example, a water-soluble resin layer) is improved, resulting in better resolution, although the detailed mechanism is unknown.

[0126] In this specification, the expression "the maximum absorption wavelength of a dye changes in response to an acid, a base, or a radical" may mean any of an embodiment in which a dye in a colored state is decolorized by an acid, a base, or a radical, an embodiment in which a dye in a decolorized state develops color by an acid, a base, or a radical, and an embodiment in which a dye in a colored state changes to a colored state of another hue. Specifically, dye N may be a compound that changes from a decolorized state to develop a color upon exposure, or a compound that changes from a colored state to decolorize upon exposure. In the above cases, dye N may be a dye whose color-developing or decolorizing state changes when an acid, base, or radical is generated and acts within the photosensitive composition layer upon exposure, or a dye whose color-developing or decolorizing state changes when the state (e.g., pH) within the photosensitive composition layer changes due to an acid, base, or radical. Alternatively, dye N may be a dye whose color-developing or decolorizing state changes upon direct stimulation by an acid, base, or radical, without exposure.

[0127] Among these, from the viewpoint of visibility and resolution of exposed and unexposed areas, dye N is preferably a dye whose maximum absorption wavelength changes in response to an acid or a radical, and more preferably a dye whose maximum absorption wavelength changes in response to a radical. When the photosensitive composition layer is a photosensitive composition layer, the photosensitive composition layer preferably contains, as dye N, both a dye whose maximum absorption wavelength changes in response to radicals and a photoradical polymerization initiator, from the viewpoints of visibility and resolution of exposed and unexposed areas. In addition, from the viewpoint of visibility of exposed and unexposed areas, it is preferable that dye N is a dye that develops color in response to an acid, a base, or a radical.

[0128] The color-developing mechanism of dye N may be, for example, an embodiment in which a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator), or a photobase generator is added to the photosensitive composition layer, and after exposure, a radical-reactive dye, an acid-reactive dye, or a base-reactive dye (e.g., a leuco dye) develops color due to a radical, acid, or base generated from the photoradical polymerization initiator, the photocationic polymerization initiator, or the photobase generator.

[0129] In terms of visibility of exposed and unexposed areas, the maximum absorption wavelength of dye N in the wavelength range of 400 to 780 nm during color development is preferably 550 nm or more, more preferably 550 to 700 nm, and even more preferably 550 to 650 nm. Furthermore, dye N may have only one or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm when it develops color. When dye N has two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm when it develops color, it is sufficient that the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths is 450 nm or longer.

[0130] The maximum absorption wavelength of dye N can be measured by measuring the transmission spectrum of a solution containing dye N (liquid temperature 25°C) in the range of 400 to 780 nm using a spectrophotometer UV3100 (Shimadzu Corporation) in an atmospheric environment and detecting the wavelength at which the light intensity is minimum (maximum absorption wavelength).

[0131] Examples of dyes that develop or lose color upon exposure include leuco compounds. Examples of dyes that are decolorized by exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes. As the dye N, a leuco compound is preferred from the viewpoint of visibility of exposed and unexposed areas.

[0132] Examples of leuco compounds include leuco compounds having a triarylmethane skeleton (triarylmethane-based dyes), leuco compounds having a spiropyran skeleton (spiropyran-based dyes), leuco compounds having a fluoran skeleton (fluoran-based dyes), leuco compounds having a diarylmethane skeleton (diarylmethane-based dyes), leuco compounds having a rhodamine lactam skeleton (rhodamine lactam-based dyes), leuco compounds having an indolylphthalide skeleton (indolylphthalide-based dyes), and leuco compounds having a leucoauramine skeleton (leucoauramine-based dyes). Among these, triarylmethane dyes or fluoran dyes are preferred, and leuco compounds having a triphenylmethane skeleton (triphenylmethane dyes) or fluoran dyes are more preferred.

[0133] From the viewpoint of visibility of 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 a radical generated from a photoradical polymerization initiator or an acid generated from a photocationic polymerization initiator, thereby converting the leuco compound into a ring-closed state and thereby discoloring, or converting the leuco compound into a ring-open state and thereby developing a color. The leuco compound is preferably a compound having a lactone ring, a sultine ring, or a sultone ring, which develops a color upon ring-opening of the lactone ring, the sultine ring, or the sultone ring by a radical or an acid, and more preferably a compound having a lactone ring, which develops a color upon ring-opening of the lactone ring by a radical or an acid.

[0134] Examples of the dye N include dyes and leuco compounds. Examples of dyes include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, quinaldine red, rose bengal, metanil yellow, thymolsulfophthalein, xylenol blue, methyl orange, paramethyl red, Congo red, benzopurpurin 4B, α-naphthyl red, Nile blue 2B, Nile blue A, methyl violet, malachite green, parafuchsin, Victoria Pure Blue naphthalene sulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Industries Co., Ltd.), Oil Pink #312 (manufactured by Orient Chemical Industries Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Industries Co., Ltd.), and Oil Scarlet #308 (manufactured by Orient Chemical Industries Co., Ltd.). Examples of suitable anti-inflammatory agents include erythritol erythritol, ...

[0135] Examples of leuco compounds include p,p',p''-hexamethyltriaminotriphenylmethane (leuco crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl leuco methylene blue, 2-(N-phenyl-N-methylamino)-6-(Np-tolyl-N-ethyl)aminofluoran, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluoran, 3,6-dimethoxyfluoran, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluoran, 3-(N-cyclohexyl-N-methylamino)- 6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-xylidinofluoran, 3-(N,N-diethylamino)-6-methyl-7-chlorofluoran, 3-(N,N-diethylamino)-6-methoxy-7-aminofluoran, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluoran, 3-(N,N-diethylamino)-7-chlorofluoran, 3-(N,N-di 3-(N,N-Diethylamino)-7-benzylaminofluoran, 3-(N,N-Diethylamino)-7,8-benzofluoran, 3-(N,N-Dibutylamino)-6-methyl-7-anilinofluoran, 3-(N,N-Dibutylamino)-6-methyl-7-xylidinofluoran, 3-Piperidino-6-methyl-7-anilinofluoran, 3-Pyrrolidino-6-methyl-7-anilinofluoran, 3,3-Bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-Bis(1-n-butyl-2 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-zaphthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthen-3-one.

[0136] Dye N is preferably a dye whose maximum absorption wavelength changes in response to radicals, and more preferably a dye that develops color in response to radicals, in view of excellent visibility of exposed and unexposed areas, and excellent pattern visibility and resolution after development. As dye N, leuco crystal violet, crystal violet lactone, brilliant green or Victoria Pure Blue-naphthalene sulfonate is preferred.

[0137] The dye N may be used alone or in combination of two or more. The content of dye N is preferably 0.1 mass % or more, more preferably 0.1 to 10 mass %, even more preferably 0.1 to 5 mass %, and particularly preferably 0.1 to 1 mass %, relative to the total mass of the photosensitive composition layer, from the viewpoint of excellent visibility of exposed and unexposed areas, and pattern visibility and resolution after development.

[0138] The content of dye N means the content of dye when all of dye N contained in the total mass of the photosensitive composition layer is in a color-developing state. A method for quantifying the content of dye N will be described below using a dye that develops color by radicals as an example. A solution of 0.001 g of dye N and a solution of 0.01 g of dye N were dissolved in 100 mL of methyl ethyl ketone. A photoradical polymerization initiator (Irgacure OXE01, manufactured by BASF Japan) was added to each solution, and radicals were generated by irradiating them with light of 365 nm wavelength, causing all of the dye N to develop color. The absorbance of each solution was then measured at 25°C using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) under atmospheric conditions, and a calibration curve was created. Next, the absorbance of the solution in which all the dyes have developed color is measured in the same manner 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 resulting solution containing the photosensitive composition layer, the content of dye N contained in the photosensitive composition layer is calculated based on a calibration curve. The photosensitive composition layer 3 g is the same as the total solid content 3 g in the photosensitive resin composition.

[0139] <Thermal crosslinkable compound> The photosensitive composition layer may contain a thermally crosslinkable compound from the viewpoints of the strength of the resulting cured film and the adhesiveness of the resulting uncured film. In this specification, a thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is not considered to be a polymerizable compound but is considered to be a thermally crosslinkable compound. Examples of the thermally crosslinkable compound include methylol compounds and blocked isocyanate compounds. Among these, blocked isocyanate compounds are preferred from the viewpoints of the strength of the resulting cured film and the adhesiveness of the resulting uncured film. Since the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when a resin and / or a polymerizable compound or the like has at least one of a hydroxy group and a carboxy group, the hydrophilicity of the formed film tends to decrease, and the functionality tends to be enhanced when the film obtained by curing the photosensitive composition layer is used as a protective film. The blocked isocyanate compound means a compound having a structure in which the isocyanate group of an isocyanate is protected (so-called masked) with a blocking agent.

[0140] The dissociation temperature of the blocked isocyanate compound is preferably 100 to 160°C, more preferably 130 to 150°C. The dissociation temperature of a blocked isocyanate means "the temperature of the endothermic peak accompanying the deprotection reaction of the blocked isocyanate when measured by DSC (Differential Scanning Calorimetry) analysis using a differential scanning calorimeter." As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be suitably used, although the differential scanning calorimeter is not limited to this.

[0141] Examples of blocking agents having a dissociation temperature of 100 to 160°C include active methylene compounds (malonic acid diesters (e.g., dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)), and oxime compounds (compounds having a structure represented by -C(=N-OH)- in the molecule, such as formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime). Among them, as the blocking agent having a dissociation temperature of 100 to 160° C., at least one selected from oxime compounds is preferred from the viewpoint of storage stability, for example.

[0142] The blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the film and improving the adhesive strength to the transfer target. A blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by protecting hexamethylene diisocyanate by isocyanuration. Among these, as a blocked isocyanate compound having an isocyanurate structure, a compound having an oxime structure in which an oxime compound is used as a blocking agent is preferred, because the dissociation temperature can be more easily adjusted to a preferred range and development residues can be reduced compared to a compound not having an oxime structure.

[0143] The blocked isocyanate compound may have a polymerizable group. The polymerizable group is not particularly limited, and any known polymerizable group can be used, with a radical polymerizable group being preferred. Examples of the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloxy group, a (meth)acrylamide group and a styryl group, and groups having an epoxy group such as a glycidyl group. Of these, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloxy group, and even more preferably an acryloxy group.

[0144] Examples of blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, and the like (all manufactured by Showa Denko K.K.), and the blocked Duranate series (e.g., Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, and the like, manufactured by Asahi Kasei Chemicals Corporation). Examples of the blocked isocyanate compound include compounds having the following structure:

[0145] [ka]

[0146] The thermally crosslinkable compounds may be used alone or in combination of two or more. When the photosensitive composition layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1 to 50 mass %, more preferably 5 to 30 mass %, based on the total mass of the photosensitive composition layer.

[0147] <Pigments> The photosensitive composition layer may be a colored resin layer containing a pigment. In order to protect the liquid crystal display window of recent electronic devices, a cover glass having a black frame-shaped light-shielding layer formed on the periphery of the back surface of a transparent glass substrate or the like is sometimes attached. A colored resin layer can be used to form such a light-shielding layer. The pigment may be appropriately selected according to the desired hue, and may be selected from black pigments, white pigments, and pigments of chromatic colors other than black and white. In particular, when a black pattern is to be formed, a black pigment is preferably selected as the pigment.

[0148] (black pigment) As the black pigment, any known black pigment (organic pigment, inorganic pigment, etc.) can be appropriately selected within a range that does not impair the effects of the present invention. Among these, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, or graphite is preferred as the black pigment from the viewpoint of optical density, and carbon black is more preferred. As the carbon black, carbon black at least a part of the surface of which is coated with a resin is preferred from the viewpoint of surface resistance.

[0149] The particle size (number average particle size) of the black pigment is preferably from 0.001 to 0.1 μm, more preferably from 0.01 to 0.08 μm, from the viewpoint of dispersion stability. The particle size refers to the diameter of a circle of the same area as the pigment particle, calculated from the area of ​​the pigment particle in a photograph taken with an electron microscope. The number average particle size is the average value obtained by calculating the particle size of any 100 particles and averaging the particle sizes of the 100 particles.

[0150] Examples of the white pigment include inorganic pigments and the white pigments described in paragraphs

[0015] and

[0114] of JP-A No. 2005-007765. As the inorganic pigment, titanium oxide, zinc oxide, lithopone, precipitated calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate is preferred, titanium oxide or zinc oxide is more preferred, titanium oxide is even more preferred, rutile or anatase titanium oxide is particularly preferred, and rutile titanium oxide is most preferred. The surface of titanium oxide may be subjected to silica treatment, alumina treatment, titania treatment, zirconia treatment, or organic treatment, or may be subjected to two or more of these treatments, which suppresses the catalytic activity of titanium oxide and improves heat resistance and light fading resistance. In order to reduce the thickness of the photosensitive composition layer after heating, it is preferable to perform at least one of alumina treatment and zirconia treatment on the surface of the titanium oxide, and it is more preferable to perform both alumina treatment and zirconia treatment.

[0151] Furthermore, when the photosensitive composition layer is a colored resin layer, it is also preferable that the photosensitive composition layer contains a chromatic pigment other than a black pigment or a white pigment from the viewpoint of transferability. When a chromatic pigment is contained, the particle size of the chromatic pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, from the viewpoint of better dispersibility. The lower limit is preferably 10 nm or more. Examples of 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 Supra (CI Pigment Red 81), and Monastral Fast Blue (CI Pigment Blue 15). , Monolight Fast 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.

[0152] The pigments may be used alone or in combination of two or more. When the photosensitive composition layer contains a pigment, the content of the pigment is preferably more than 3 mass% and not more than 40 mass%, more preferably more than 3 mass% and not more than 35 mass%, even more preferably more than 5 mass% and not more than 35 mass%, and particularly preferably 10 to 35 mass%, relative to the total mass of the photosensitive composition layer.

[0153] When the photosensitive composition layer contains pigments other than black pigments (white pigments and chromatic pigments), the content of the pigments other than black pigments is preferably 30 mass % or less, more preferably 1 to 20 mass %, and even more preferably 3 to 15 mass %, relative to the total mass of the black pigments.

[0154] When the photosensitive composition layer contains a black pigment, the black pigment (preferably carbon black) is preferably introduced into the photosensitive composition in the form of a pigment dispersion. The dispersion may be prepared by premixing a black pigment and a pigment dispersant, adding the resulting mixture to an organic solvent (or vehicle), and dispersing the mixture using a disperser. The pigment dispersant may be selected depending on the pigment and solvent; for example, a commercially available dispersant may be used. The vehicle refers to the medium in which the pigment is dispersed when a pigment dispersion is prepared. It is liquid and includes a binder component that maintains the black pigment in a dispersed state and a solvent component (organic solvent) that dissolves and dilutes the binder component.

[0155] Examples of the dispersing machine include known dispersing machines such as a kneader, a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill. Alternatively, fine pulverization may be carried out by utilizing frictional force through mechanical grinding. For details of dispersers and fine pulverization, see, for example, "Encyclopedia of Pigments" (Kunizo Asakura, 1st Edition, Asakura Shoten, 2000, pp. 438 and 310).

[0156] <Other additives> The photosensitive composition layer may contain known additives (other additives) in addition to the above components, if necessary. Other additives include, for example, radical polymerization inhibitors, benzotriazoles, carboxybenzotriazoles, sensitizers, surfactants, plasticizers, heterocyclic compounds (triazoles, etc.), pyridines (isonicotinamide, etc.), and purine bases (adenine, etc.). Other additives include metal oxide particles, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic suspending agents, as well as those described in paragraphs

[0165] to

[0184] of JP2014-085643A, the contents of which are incorporated herein by reference. The other additives may be used alone or in combination of two or more.

[0157] (radical polymerization inhibitor) Examples of the radical polymerization inhibitor include the thermal polymerization inhibitors described in paragraph

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

[0158] (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.

[0159] (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 the carboxybenzotriazoles is CBT-1 (trade name, manufactured by Johoku Chemical Industry Co., Ltd.).

[0160] The total content of the radical polymerization inhibitor, benzotriazoles, and carboxybenzotriazoles is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass, based on the total mass of the photosensitive composition layer. When the content is 0.01% by mass or more, the storage stability of the photosensitive composition layer is improved. On the other hand, when the content is 3% by mass or less, the sensitivity is maintained and the decolorization of the dye is suppressed better.

[0161] (sensitizer) Examples of the sensitizer 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.

[0162] When the photosensitive composition layer contains a sensitizer, the content of the sensitizer is preferably 0.01 to 5 mass %, more preferably 0.05 to 1 mass %, relative to the total mass of the photosensitive composition layer, from the viewpoints of improving sensitivity to the light source and improving the curing rate by balancing the polymerization rate and chain transfer.

[0163] (surfactant) Examples of the surfactant include those described in paragraph

[0017] of Japanese Patent No. 4502784 and paragraphs

[0060] to

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

[0164] The surfactant is preferably a nonionic surfactant, a fluorine-based surfactant, or a silicone-based surfactant. 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); Fluorad 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); Futergent 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 Co., Ltd.).

[0165] Further, as the fluorine-based surfactant, an acrylic compound having a molecular structure with a functional group containing a fluorine atom, in which the functional group containing the fluorine atom is cleaved when heat is applied, causing the fluorine atom to volatilize, is also preferred. Examples of such fluorine-based surfactants include the Megafac DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016) and The Nikkei Business Daily (February 23, 2016)). As the 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. Furthermore, a block polymer can also be used as the fluorine-based surfactant. Furthermore, as the fluorine-based surfactant, a fluorine-containing polymer compound containing 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) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups) is also preferred. In addition, as the fluorine-based surfactant, for example, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can be used, and examples thereof include Megafac RS-101, RS-102, RS-718K and RS-72-K (all manufactured by DIC Corporation).

[0166] As the fluorine-based surfactant, from the viewpoint of improving environmental compatibility, surfactants derived from alternative materials to compounds having a linear perfluoroalkyl group having seven or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), are preferred.

[0167] 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 (registered trademark) 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); and Solsperse 20000 (all manufactured by Lubrizol Japan Corporation); NCW-101, NCW-1001 and NCW-1002 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.); Paionin D-1105, D-6112, D-6112-W and D-6315 (all manufactured by Takemoto Oil & Fat Co., Ltd.); Olfine E1010, Surfynol 104, 400 and 440 (all manufactured by Nissin Chemical Industry Co., Ltd.).

[0168] Examples of silicone surfactants include linear polymers consisting of siloxane bonds, and modified siloxane polymers in which organic groups have been introduced into the side chains and / or terminals.

[0169] Specific examples of silicone surfactants include EXP.S-309-2, EXP.S-315, EXP.S-503-2, and EXP.S-505-2 (all manufactured by DIC Corporation), DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.); X-22-4952, X-22-4272, X-22-6266, and 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-6 001 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, 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 Co., Ltd.) Performance Materials); BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378 and BYK323 (all manufactured by BYK-Chemie).

[0170] When the photosensitive composition layer contains a surfactant, the content of the surfactant is preferably 0.01 to 3.0 mass %, more preferably 0.01 to 1.0 mass %, and even more preferably 0.05 to 0.8 mass %, relative to the total mass of the photosensitive composition layer.

[0171] Examples of the plasticizer and heterocyclic compound include the compounds described in paragraphs

[0097] to

[0103] and paragraphs

[0111] to

[0118] of WO 2018 / 179640.

[0172] <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.

[0173] (metal impurities and halide ions) Examples of metal impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, and ions thereof, as well as halide ions. Among these, sodium ions, potassium ions, and halide ions are easily mixed in, so it is preferable to set the contents to the following ranges. Metal impurities are compounds that are different from the particles (eg, metal oxides).

[0174] 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. Although there is no particular lower limit, it is preferably 1 ppb by mass or more, more preferably 0.1 ppm by mass or more, relative to the total mass of the photosensitive composition layer.

[0175] Methods for adjusting the content of impurities include, for example, selecting raw materials for the photosensitive composition layer that have a low content of impurities, preventing impurities from being mixed in when forming the photosensitive composition layer, and removing impurities by washing. The content of impurities can be determined by known methods such as ICP emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0176] (Residual organic solvents) Examples of the remaining organic solvent include benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane. The content of the residual organic solvent 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. Although there is no particular lower limit, it is preferably 10 ppb by mass or more, and more preferably 100 ppb by mass or more. The content of the residual organic solvent can be determined by the same method as for the metal impurities, and can be quantified by a known method such as gas chromatography analysis.

[0177] (residual monomer) The photosensitive composition layer may contain residual monomers of the structural units of the resins described above. From the viewpoint of patterning ability and reliability, the content of residual monomers is preferably 5000 ppm by mass or less, more preferably 2000 ppm by mass or less, and even more preferably 500 ppm by mass or less, relative to the total mass of the resin. Although there is no particular lower limit, it is preferably 1 ppm by mass or more, more preferably 10 ppm by mass or more, relative to the total mass of the resin. From the viewpoints of patterning ability and reliability, the residual monomer content of each structural unit of the alkali-soluble resin is preferably 3,000 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. Although there is no particular lower limit, it is preferably 0.1 ppm by mass or more, more preferably 1 ppm by mass or more, relative to the total mass of the photosensitive composition layer.

[0178] The amount of residual monomers in the synthesis of an alkali-soluble resin by a polymer reaction is also preferably within the above range. For example, when the alkali-soluble resin is synthesized by reacting glycidyl acrylate with a carboxylic acid side chain, the content of glycidyl acrylate is preferably within the above range. The amount of residual monomer can be measured by known methods such as liquid chromatography and gas chromatography.

[0179] The content of water in the photosensitive composition layer is preferably from 0.01 to 1.0% by mass, more preferably from 0.05 to 0.5% by mass, from the viewpoint of improving reliability and lamination properties.

[0180] [Characteristics of the Photosensitive Composition Layer] The thickness (film thickness) of the photosensitive composition layer is often 0.1 to 300 μm, preferably 0.2 to 100 μm, more preferably 0.5 to 50 μm, still more preferably 0.5 to 30 μm, and particularly preferably 1 to 20 μm, which can improve the developability of the photosensitive composition layer and the resolution.

[0181] The content of double bonds in the photosensitive composition layer is preferably from 0.8 to 3.0 mmol / g, more preferably from 1.0 to 3.0 mmol / g, and even more preferably from 1.2 to 2.0 mmol / g.

[0182] The acid value of the photosensitive composition layer is preferably 10 to 150 mgKOH / g, more preferably 40 to 100 mgKOH / g, even more preferably 50 to 100 mgKOH / g, particularly preferably 50 to 90 mgKOH / g, and most preferably 60 to 90 mgKOH / g from the viewpoint of more excellent suppression of development residues. The acid value can be measured, for example, by the above-mentioned method for measuring the acid value of a resin, or by a method for calculating the acid value from the content of a resin whose acid value is known.

[0183] [Middle class] The transfer film of the present invention has an intermediate layer. Examples of the intermediate layer include a water-soluble resin layer and an oxygen-blocking layer having an oxygen-blocking function, which is described as a "separation layer" in JP-A No. 5-072724. The intermediate layer is preferably an oxygen blocking layer, since it improves sensitivity during exposure, reduces the time load on the exposure machine, and improves productivity. The oxygen barrier layer can be appropriately selected from known layers described in the above publications. Among these, an oxygen-blocking layer that exhibits low oxygen permeability and disperses or dissolves in water or an alkaline aqueous solution (a 1% by mass aqueous solution of sodium carbonate at 22° C.) is preferred. Hereinafter, each component that may be contained in the water-soluble resin layer (intermediate layer) will be described.

[0184] <Water-soluble resin> The intermediate layer preferably contains a water-soluble resin. Examples of water-soluble resins include polyvinyl alcohol resins, polyvinylpyrrolidone resins, cellulose resins, polyether resins, gelatin, and polyamide resins.

[0185] Examples of the cellulose-based resin include water-soluble cellulose derivatives. Examples of water-soluble cellulose derivatives include hydroxyethyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, methyl cellulose, and ethyl cellulose.

[0186] Examples of polyether resins include polyethylene glycol, polypropylene glycol, and alkylene oxide adducts thereof, and vinyl ether resins. Examples of polyamide resins include acrylamide resins, vinylamide resins, and allylamide resins. Among these, the water-soluble resin is preferably a water-soluble cellulose derivative or a polyamide resin.

[0187] Further, examples of the water-soluble resin include copolymers of (meth)acrylic acid and vinyl compounds. As the copolymer of (meth)acrylic acid and vinyl compounds, a copolymer of (meth)acrylic acid and allyl (meth)acrylate is preferred, and a copolymer of methacrylic acid and allyl methacrylate is more preferred. When the water-soluble resin is a copolymer of (meth)acrylic acid and vinyl compounds, the composition ratio (mol%) of each is preferably 90 / 10 to 20 / 80, and more preferably 80 / 20 to 30 / 70.

[0188] 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 dispersity (Mw / Mn) of the water-soluble resin is preferably 1-10, and more preferably 1-5.

[0189] The water-soluble resins may be used alone or in combination of two or more. The content of the water-soluble resin is preferably 50% by mass or more, and more preferably 70% by mass or more, based on the total mass of the intermediate layer, from the viewpoint of achieving better effects of the present invention and / or better oxygen blocking 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.

[0190] <Other ingredients> The intermediate layer may contain other components in addition to the above resins. The molecular weight of the other component 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.

[0191] As the other component, polyhydric alcohols, alkylene oxide adducts of polyhydric alcohols, phenol derivatives or amide compounds are preferred, and polyhydric alcohols or phenol derivatives are more preferred.

[0192] Examples of polyhydric alcohols include glycerin, diglycerin, and diethylene glycol. The polyhydric alcohol preferably contains 2 to 10 hydroxyl groups. Examples of alkylene oxide adducts of polyhydric alcohols include compounds in which ethylene oxide, propylene oxide, etc. are added to the above-mentioned polyhydric alcohols. The average number of adducts is preferably 1 to 100, more preferably 2 to 50, and even more preferably 2 to 20. Phenol derivatives include, for example, bisphenol A and bisphenol S. An example of the amide compound is N-methylpyrrolidone.

[0193] The intermediate layer preferably contains at least one selected from the group consisting of polyhydric alcohols, oxide adducts of polyhydric alcohols, phenol derivatives, water-soluble cellulose derivatives, polyether resins, and polyamide resins.

[0194] The thickness of the intermediate layer is preferably 3.0 μm or less, more preferably 2.0 μm or less, and the lower limit is preferably 1.0 μm or more.

[0195] The other components may be used alone or in combination of two or more. The content of other components is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, relative to the total mass of the intermediate layer. The upper limit is preferably less than 30% by mass, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0196] [Thermoplastic resin layer] The transfer film of the present invention may have a thermoplastic resin layer. The thermoplastic resin layer is usually disposed between the temporary support and the photosensitive composition layer. By providing the transfer film with the thermoplastic resin layer, the conformability to the substrate during the lamination process between the transfer film and the substrate is improved, and the inclusion of air bubbles between the substrate and the transfer film can be suppressed. As a result, the adhesion between the thermoplastic resin layer and an adjacent layer (e.g., temporary support) can be ensured. Furthermore, examples of the thermoplastic resin layer include those described in paragraphs

[0189] to

[0193] of JP-A-2014-085643, the contents of which are incorporated herein by reference.

[0197] The thickness of the thermoplastic resin layer is preferably 1 μm or more, more preferably 2 μm or more, from the viewpoint of adhesion to adjacent layers, and 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.

[0198] <Thermoplastic resin> The thermoplastic resin layer preferably contains a thermoplastic resin. The thermoplastic resin is preferably an alkali-soluble resin. 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.

[0199] The alkali-soluble resin is preferably an acrylic resin from the viewpoints of developability and adhesion to adjacent layers. Here, acrylic resin means a resin having at least one type of structural unit selected from the group consisting of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid esters, and structural units derived from (meth)acrylic acid amides. In the acrylic resin, the total content of the structural units derived from (meth)acrylic acid, the structural units derived from (meth)acrylic acid ester, and the structural units derived from (meth)acrylic acid amide is preferably 50% by mass or more relative to the total mass of the acrylic resin, and 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 the structural units derived from (meth)acrylic acid and the structural units derived from (meth)acrylic acid ester is preferably 30 to 100 mass %, more preferably 50 to 100 mass %, relative to the total mass of the acrylic resin.

[0200] The alkali-soluble resin is preferably a polymer having an acid group. Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group, with a carboxy group being preferred. The acid value of the alkali-soluble resin is preferably 60 mgKOH / g or more from the viewpoint of developability, and the upper limit is preferably 300 mgKOH / g or less, more preferably 250 mgKOH / g or less, still more preferably 200 mgKOH / g or less, and particularly preferably 150 mgKOH / g or less. Among these, the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more, and more preferably a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more.

[0201] The carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited, and can be appropriately selected from known resins. Examples include alkali-soluble resins which are carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or more among the polymers described in paragraph

[0025] of JP 2011-095716 A, carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or more among the polymers described in paragraphs

[0033] to

[0052] of JP 2010-237589 A, and carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or more among the resins described in paragraphs

[0053] to

[0068] of JP 2016-224162 A. The copolymerization ratio of the structural unit having a carboxy group in the carboxy group-containing acrylic resin is preferably 5 to 50 mass %, more preferably 10 to 40 mass %, and even more preferably 12 to 30 mass %, relative to the total mass of the acrylic resin. As the alkali-soluble resin, an acrylic resin having a structural unit derived from (meth)acrylic acid is particularly preferred from the viewpoints of developability and adhesion to adjacent layers.

[0202] The alkali-soluble resin may have a reactive group. The reactive group may be any group capable of addition polymerization, and examples thereof include ethylenically unsaturated groups; polycondensable groups such as hydroxy groups and carboxy groups; and polyaddition reactive groups such as epoxy groups and (blocked) isocyanate groups.

[0203] The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably from 10,000 to 100,000, and even more preferably from 20,000 to 50,000.

[0204] The alkali-soluble resins may be used alone or in combination of two or more. From the viewpoints of developability and adhesion to adjacent layers, the content of the 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.

[0205] <Dye> The thermoplastic resin layer preferably contains a dye (hereinafter 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 more and whose maximum absorption wavelength changes in response to an acid, a base, or a radical. Preferred embodiments of dye B are the same as the preferred embodiments of dye N described above, except for the points described below.

[0206] As dye B, from the viewpoints of visibility of exposed and unexposed areas and resolution, dyes whose maximum absorption wavelength changes in response to an acid or radical are preferred, and dyes whose maximum absorption wavelength changes in response to an acid are more preferred. From the viewpoint of the visibility and resolution of exposed and unexposed areas, the thermoplastic resin layer preferably contains both a dye whose maximum absorption wavelength changes in response to an acid as dye B and a compound that generates an acid when exposed to light, as described below.

[0207] The dye B may be used alone or in combination of two or more. From the viewpoint of visibility of exposed and unexposed areas, the content of dye B is preferably 0.2 mass% or more, more preferably 0.2 to 6.0 mass%, even more preferably 0.2 to 5.0 mass%, and particularly preferably 0.25 to 3.0 mass%, relative to the total mass of the thermoplastic resin layer.

[0208] Here, the content of dye B means the content of dye when all of the dye B contained in the thermoplastic resin layer is in a color-developing state. A method for quantifying the content of dye B will be described below using a dye that develops color by radicals as an example. A solution of 0.001 g of dye B and a solution of 0.01 g of dye B were prepared in 100 mL of methyl ethyl ketone. A photoradical polymerization initiator (Irgacure OXE01, manufactured by BASF Japan) was added to each of the resulting solutions, and radicals were generated by irradiating them with light of 365 nm wavelength, causing all of the dye B to develop color. The absorbance of each solution was then measured at 25°C using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) under atmospheric conditions, and a calibration curve was created. Next, the absorbance of the solution in which all the dyes have developed is measured in the same manner 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 resulting solution containing the thermoplastic resin layer, the amount of dye B contained in the thermoplastic resin layer is calculated based on a calibration curve. The thermoplastic resin layer 3g is the same as the 3g of solid content of the composition.

[0209] <Compounds that generate acids, bases, or radicals when exposed to light> The thermoplastic resin layer may contain a compound that generates an acid, a base or a radical when exposed to light (hereinafter, also simply referred to as "compound C"). Compound C is preferably a compound that generates an acid, a base or a radical when exposed to actinic rays such as ultraviolet light and visible light. Examples of the compound C include known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators).

[0210] (Photoacid generator) The thermoplastic resin layer may contain a photoacid generator from the viewpoint of resolution. Examples of the photoacid generator include the cationic photopolymerization initiators that can be contained in the photosensitive composition layer described above, and preferred embodiments are also the same except for the points described below.

[0211] From the viewpoints of sensitivity and resolution, the photoacid generator preferably contains at least one compound selected from the group consisting of an onium salt compound and an oxime sulfonate compound, and from the viewpoints of sensitivity, resolution, and adhesion, it is more preferable that the photoacid generator contains an oxime sulfonate compound. Furthermore, as the photoacid generator, a photoacid generator having the following structure is also preferred.

[0212] [ka]

[0213] (Photoradical polymerization initiator) The thermoplastic resin layer may contain a photoradical polymerization initiator. Examples of the photoradical polymerization initiator include the photoradical polymerization initiators that can be contained in the photosensitive composition layer described above, and preferred embodiments are also the same.

[0214] (Photobase Generator) The thermoplastic resin composition may contain a photobase generator. Examples of the photobase generator include known photobase generators. Specifically, 2-nitrobenzyl cyclohexyl carbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)-1-benzyl-1-dimethylamine methylaminopropane, 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.

[0215] The compound C may be used alone or in combination of two or more. The content of compound C is preferably 0.1 to 10 mass %, more preferably 0.5 to 5 mass %, based on the total mass of the thermoplastic resin layer, from the viewpoint of visibility and resolution of exposed and unexposed areas.

[0216] <Plasticizer> The thermoplastic resin layer preferably contains a plasticizer in terms of resolution, adhesion to adjacent layers, and developability. The plasticizer preferably has a smaller molecular weight (weight average molecular weight when it is an oligomer or polymer and has 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, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, more preferably a polyalkylene glycol compound, and the alkyleneoxy group contained in the plasticizer more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.

[0217] From the viewpoints of resolution and storage stability, the plasticizer preferably contains a (meth)acrylate compound. From the viewpoints 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 the (meth)acrylate compound used as the plasticizer include the (meth)acrylate compounds described above as the polymerizable compound that can be contained in the photosensitive composition layer. In the transfer film, when the thermoplastic resin layer and the photosensitive composition layer are laminated in direct contact with each other, it is preferable that both the thermoplastic resin layer and the photosensitive composition layer contain the same (meth)acrylate compound, because the thermoplastic resin layer and the photosensitive composition layer each contain the same (meth)acrylate compound, which suppresses component diffusion between the layers and improves storage stability.

[0218] When the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, it is preferable that the (meth)acrylate compound does not polymerize even in the exposed area after exposure, in terms of adhesion between the thermoplastic resin layer and an 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 in terms of the resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability. Furthermore, as the (meth)acrylate compound used as a plasticizer, a (meth)acrylate compound having an acid group or a urethane (meth)acrylate compound is also preferred.

[0219] The plasticizers may be used alone or in combination of two or more. The content of the plasticizer 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 viewpoints of the resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability.

[0220] <Sensitizer> The thermoplastic resin layer may contain a sensitizer. The sensitizer is not particularly limited, but examples thereof include the sensitizers that can be contained in the photosensitive composition layer described above.

[0221] The sensitizers may be used alone or in combination of two or more. The content of the sensitizer is preferably 0.01 to 5 mass %, more preferably 0.05 to 1 mass %, based on the total mass of the thermoplastic resin layer, from the viewpoints of improving sensitivity to the light source and visibility of exposed and unexposed areas.

[0222] <Other additives> The thermoplastic resin layer may contain other additives in addition to the above components, if necessary. Examples of other additives include the other additives that can be contained in the photosensitive composition layer described above.

[0223] <Impurities> The thermoplastic resin layer may contain impurities. Examples of the impurities include the impurities that can be contained in the photosensitive composition layer described above.

[0224] [Other parts] The transfer film of the present invention may include other members in addition to the above-mentioned members. The other members include, for example, a protective film.

[0225] (protective film) As the protective film, a resin film having heat resistance and solvent resistance can be used, and examples thereof include polyolefin films such as polypropylene film and polyethylene film, polyester films such as polyethylene terephthalate film, polycarbonate film, and polystyrene film. The protective film may be a resin film made of the same material as the temporary support. Among these, the protective film is preferably a polyolefin film, more preferably a polypropylene film or a polyethylene film, and even more preferably a polyethylene film.

[0226] The thickness of the protective film is preferably from 1 to 100 μm, more preferably from 5 to 50 μm, even more preferably from 5 to 40 μm, and particularly preferably from 15 to 30 μm. The thickness of the protective film is preferably 1 μm or more in terms of excellent mechanical strength, and is preferably 100 μm or less in terms of relatively low cost.

[0227] The number of fisheyes with a diameter of 80 μm or more contained in the protective film is 5 / m 2 It is preferable that: "Fisheyes" refer to foreign matter, undissolved matter, oxidized degradation products, etc. that are trapped in the film when the material is thermally melted and then kneaded, extruded, biaxially stretched, cast, or other methods are used to produce the film.

[0228] The number of particles with a diameter of 3 μm or more contained in the protective film is 30 / mm 2 Preferably less than 10 pieces / mm 2 Less than 5 pieces / mm is more preferable. 2 The lower limit is 0 pieces / mm 2 Within these ranges, defects caused by irregularities due to particles contained in the protective film being transferred to the photosensitive composition layer or the conductive layer can be suppressed.

[0229] In order to provide good winding properties, 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 protective film on 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, 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.

[0230] [Transfer film manufacturing method] The method for producing the transfer film is not particularly limited, and known methods can be used. Examples of methods for manufacturing the transfer film 10 include a method including the steps of applying a water-soluble resin composition to the surface of the temporary support 11 to form a coating film, and then drying this coating film to form the 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 the photosensitive composition layer 15. Furthermore, before the step of forming the intermediate layer 13, a step of applying a thermoplastic resin composition to the surface of the temporary support 11 to form a coating film, and then drying this coating film to form a thermoplastic resin layer may be included.

[0231] The transfer film 10 is produced by pressing a protective film 19 onto the photosensitive composition layer 15 of the laminate produced by the above-mentioned production method. The method for producing a transfer film preferably includes a step of providing a protective film 19 so as to contact the surface of the photosensitive composition layer 15 opposite to the side having the temporary support 11, thereby producing a transfer film 10 comprising the temporary support 11, the intermediate layer 13, the photosensitive composition layer 15, and the protective film 19. Alternatively, the method for producing a transfer film may include a step of providing a protective film 19 so as to contact the surface of the photosensitive composition layer 15 opposite to the side having the temporary support 11, thereby producing a transfer film comprising the temporary support 11, the thermoplastic resin layer, the intermediate layer 13, the photosensitive composition layer 15, and the protective film 19. After producing the transfer film 10 by the above-described production 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 as is to the step of laminating the film to a substrate in a roll-to-roll system, which will be described later.

[0232] Alternatively, the transfer film 10 may be produced by forming the photosensitive composition layer 15 and the intermediate layer 13 on the protective film 19 , and then forming a thermoplastic resin layer on the surface of the intermediate layer 13 .

[0233] [Photosensitive composition and method for forming a photosensitive composition layer] It is preferably formed by a coating method using a photosensitive composition containing the components constituting the photosensitive composition layer described above (for example, a resin, a polymerizable compound, a polymerization initiator, etc.) and a solvent. Specifically, a preferred method for producing the transfer film is to apply a photosensitive composition to the intermediate layer to form a coating film, and then dry the coating film at a predetermined temperature to form the photosensitive composition layer. Note that the amount of remaining solvent is adjusted by drying the coating film.

[0234] The photosensitive composition preferably contains the various components forming the photosensitive composition layer described above and a solvent. Note that, 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, and known solvents can be used. Specific examples include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol, ethanol, etc.), ketone solvents (acetone, 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.

[0235] The solvent preferably contains at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. Among these, a mixed solvent containing at least one solvent selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one solvent selected from the group consisting of ketone solvents and cyclic ether solvents is more preferred, and a mixed solvent containing at least three solvents, namely at least one solvent 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.

[0236] Examples of alkylene glycol ether solvents include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers (e.g., propylene glycol monomethyl ether acetate, etc.), propylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers, and dipropylene glycol dialkyl ethers. 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 the solvent include the solvents described in paragraphs

[0092] to

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

[0014] of Japanese Patent Application Laid-Open No. 2018-177889, the contents of which are incorporated herein by reference. The solvents may be used alone or in combination of two or more. The content of the solvent 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, relative to 100 parts by mass of the total solid content of the composition.

[0237] Examples of methods for applying the photosensitive composition include printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (slit coating).

[0238] As a method for drying the coating film of the photosensitive composition, heat drying and reduced pressure drying are preferred. The drying temperature is preferably 90° C. or higher, more preferably 100° C. or higher, and even more preferably 110° C. or higher. The upper limit is preferably 130° C. or lower, 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, and the upper limit is preferably 600 seconds or less, more preferably 450 seconds or less, and even more preferably 300 seconds or less.

[0239] Furthermore, a transfer film may be produced by laminating a protective film onto the photosensitive composition layer. The protective film may be attached to the photosensitive composition layer by any known method. Examples of a device for laminating the protective film to the photosensitive composition layer include known laminators such as a vacuum laminator and an auto-cut laminator. The laminator is preferably equipped with any heatable roller such as a rubber roller and is capable of applying pressure and heat.

[0240] [Water-soluble resin composition and method for forming intermediate layer (water-soluble resin layer)] The water-soluble resin composition preferably contains the various components forming the intermediate layer (water-soluble resin layer) described above and a solvent. Note that in the water-soluble resin composition, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the 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 alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, with alcohols having 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred. The solvents may be used alone or in combination of two or more. The content of the solvent 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, relative to 100 parts by mass of the total solid content of the composition.

[0241] The method for forming the water-soluble resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, and inkjet coating).

[0242] [Composition for forming thermoplastic resin layer and method for forming thermoplastic resin layer] The method for forming the thermoplastic resin layer on the temporary support is not particularly limited, and any known method can be used. For example, the thermoplastic resin layer can be formed by applying a composition for forming a thermoplastic resin layer on the temporary support and drying it as necessary. The thermoplastic resin layer-forming composition preferably contains the various components for forming the thermoplastic resin layer described above and a solvent. Note that, in the thermoplastic resin layer-forming composition, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the thermoplastic resin layer described above. The solvent is not particularly limited as long as it can dissolve or disperse the components other than the solvent, and any known solvent can be used. Examples of the solvent include the same solvents contained in the photosensitive composition described below, and preferred embodiments are also the same. The content of the solvent is preferably from 50 to 1900 parts by mass, more preferably from 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.

[0243] 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, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.). [Example]

[0244] The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be changed 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. Note that "parts" and "%" are by mass unless otherwise specified. In the following examples, the weight-average molecular weight of the resin is the weight-average molecular weight (Mw) calculated in terms of polystyrene by gel permeation chromatography (GPC). The acid value is the theoretical acid value. The I / O value was measured by the method described above.

[0245] 〔resin〕 <Synthesis of Resin A1> A three-neck flask was charged with propylene glycol monomethyl ether acetate (PGMEA, 67.0 parts by mass) and heated to 90°C under a nitrogen atmosphere. A solution containing MAA (20.0 parts by mass), St (32.0 parts by mass), MMA (48.0 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, 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, the solution in the flask was stirred at 90°C ± 2°C for 1 hour, and then diluted with PGMEA (100.0 parts by mass) to obtain Resin A1 (solids concentration 30.0% by mass).

[0246] <Synthesis of Resin A2> PGMEA (67.0 parts by mass) was placed in a three-neck flask and heated to 90°C under a nitrogen atmosphere. A solution containing MAA (15.0 parts by mass), St (34.0 parts by mass), MMA (31.0 parts by mass), EMA (20.0 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, 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, the solution in the flask was stirred at 90°C ± 2°C for 1 hour, and then diluted with PGMEA (100.0 parts by mass) to obtain Resin A2 (solids concentration 30.0% by mass).

[0247] <Synthesis of Resin A3> PGMEA (67.0 parts by mass) was placed in a three-neck flask and heated to 90°C under a nitrogen atmosphere. A solution containing MAA (25.0 parts by mass), St (30.0 parts by mass), MMA (45.0 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, 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, the solution in the flask was stirred at 90°C ± 2°C for 1 hour, and then diluted with PGMEA (100.0 parts by mass) to obtain Resin A3 (solids concentration 30.0% by mass).

[0248] <Synthesis of Resin A4> PGMEA (67.0 parts by mass) was placed in a three-neck flask and heated to 90°C under a nitrogen atmosphere. A solution containing MAA (13.0 parts by mass), St (36.0 parts by mass), MMA (31.0 parts by mass), EMA (20.0 parts by mass), V-601 (2.5 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, 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, the solution in the flask was stirred at 90°C ± 2°C for 1 hour, and then diluted with PGMEA (100.0 parts by mass) to obtain Resin A4 (solids concentration 30.0% by mass).

[0249] <Synthesis of Resin A5> PGMEA (67.0 parts by mass) was placed in a three-neck flask and heated to 90°C under a nitrogen atmosphere. A solution containing MAA (20.0 parts by mass), St (20.0 parts by mass), MMA (20.0 parts by mass), EMA (40.0 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, 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, the solution in the flask was stirred at 90°C ± 2°C for 1 hour, and then diluted with PGMEA (100.0 parts by mass) to obtain Resin A5 (solids concentration 30.0% by mass).

[0250] <Synthesis of Resin A6> PGMEA (67.0 parts by mass) was placed in a three-neck flask and heated to 90°C under a nitrogen atmosphere. A solution containing MAA (25.0 parts by mass), St (25.0 parts by mass), MMA (50.0 parts by mass), 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 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 then diluted with PGMEA (100.0 parts by mass) to obtain Resin A6 (solids concentration 30.0% by mass).

[0251] <Synthesis of Resin A7> PGMEA (67.0 parts by mass) was placed in a three-neck flask and heated to 90°C under a nitrogen atmosphere. A solution containing MAA (10.0 parts by mass), St (40.0 parts by mass), MMA (50.0 parts by mass), V-601 (2.5 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 then diluted with PGMEA (100.0 parts by mass) to obtain Resin A7 (solids concentration 30.0% by mass).

[0252] Resins A1 to A7 are shown in Table 1 below. In Table 1, the abbreviations for the monomers that form each structural unit (% by mass) are shown. Resins A1 to A7 are alkali-soluble resins.

[0253] [Table 1]

[0254] In Table 1, the following symbols are used: The symbols used in the synthesis of the above resins are as follows: MAA: methacrylic acid (Fujifilm Wako Pure Chemical Industries, Ltd.) St: Styrene (Fujifilm Wako Pure Chemical Industries, Ltd.) MMA: Methyl methacrylate (Fujifilm Wako Pure Chemical Industries, Ltd.) EMA: Ethyl methacrylate (Fujifilm Wako Pure Chemical Industries, Ltd.)

[0255] [Photosensitive composition] Photosensitive compositions having the components and formulations shown in Table 2 below were prepared. In Table 2, the numerical values ​​in the component columns indicate the content (parts by mass) of each component, with the amount of each resin in the "Resin" column indicating the amount of resin solution (solid concentration 30% by mass).

[0256] [Table 2]

[0257] <Polymerizable compound> Ethoxylated Bisphenol A Dimethacrylate Ethoxylated (3) trimethylolpropane triacrylate 4-n-octylphenoxypentaethylene glycol monopropylene glycol acrylate Ethylene oxide propylene oxide modified urethane dimethacrylate

[0258] <Photopolymerization initiator> 2-(o-chlorophenyl)-4,5-diphenylimidazole

[0259] <Sensitizer> 4,4-Bis(diethylamino)benzophenone

[0260] <Color former> Leucocrystal Violet

[0261] <Solvent> acetone toluene methanol

[0262] [Composition for forming intermediate layer] Composition 1 for forming an intermediate layer 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): Fujifilm, polyvinylpyrrolidone Metrolose 60SH03 (1.00% by mass): water-soluble cellulose derivative manufactured by Shin-Etsu Chemical Co., Ltd. F444 (0.08% by mass): DIC Corporation, surfactant

[0263] [Transfer film] Each transfer film was prepared, each composed of a temporary support, an intermediate layer, and a photosensitive composition layer, so as to have the configuration shown in Table 3. Specifically, the configuration is as follows. First, the intermediate layer forming composition 1 for forming the above-mentioned intermediate layer was applied onto a temporary support (a 16 μm thick polyethylene terephthalate film (Lumirror 16KS40, manufactured by Toray Industries, Inc.)) using a bar coater so that the thickness after drying would be 1.0 μm, and the coating was dried at 90°C in an oven to form an intermediate layer. Furthermore, a photosensitive composition for forming a photosensitive composition layer shown in Table 3 was applied onto the intermediate layer using a bar coater to a thickness after drying shown in Table 3, and then dried at 80°C in an oven to form a negative photosensitive composition layer. A 16 μm thick polyethylene terephthalate film (16KS40, manufactured by Toray Industries, Inc.) was pressure-bonded onto the obtained negative photosensitive composition layer to prepare transfer films for Examples and Comparative Examples.

[0264] [Measurement and Evaluation] <Contact angle X and contact angle Y> The contact angle X and the contact angle Y were measured by the method described above.

[0265] <Pattern shape (flared bottom shape)> 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 formed by Ni plating (thickness 100 nm) on glass (lamination conditions: substrate temperature 80°C, rubber roller temperature 110°C, linear pressure 3 N / cm, conveying speed 2 m / min) to obtain a laminate. Next, the temporary support was peeled off from the obtained laminate, and a photomask having a line (μm) / space (μm) pattern of 1 / 1 was adhered to the surface of the intermediate layer side of the obtained laminate. The photosensitive composition layer was exposed to light using a high-pressure mercury lamp exposure machine (MAP-1200L, manufactured by Dai-Nippon Kaken Co., Ltd., dominant wavelength: 365 nm). 2 The pattern was then exposed to light at 1000 W. Thereafter, a pattern was formed by shower development for 30 seconds using an aqueous sodium carbonate solution at a liquid temperature of 25°C. The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope, and the length of the part (the flared part in Figure 1) on the side of each pattern that protruded from the upper surface of the pattern (the surface opposite the substrate) was taken as the skirt length. The longest skirt length was used to evaluate the pattern shape according to the following evaluation criteria. A: The tail length is 0.3 μm or less B: The tail length is more than 0.3 μm and less than 0.5 μm C: The tail length is more than 0.5 μm and less than 0.7 μm D: The tail length is more than 0.7 μm

[0266] <Resolution> The protective film of the transfer film prepared above was peeled off, and the exposed surface of the photosensitive composition layer was laminated onto a conductive substrate made of glass plated with Ni (thickness 100 nm) (lamination conditions: substrate temperature 80°C, rubber roller temperature 110°C, linear pressure 3 N / cm, conveying speed 2 m / min) to obtain a laminate. Next, the temporary support was peeled off from the obtained laminate, and a photomask having a line (μm) / space (μm) pattern of 1 / 1 was adhered to the surface of the intermediate layer side of the obtained laminate. The photosensitive composition layer was exposed to light using a high-pressure mercury lamp exposure machine (MAP-1200L, manufactured by Dai-Nippon Kaken Co., Ltd., dominant wavelength: 365 nm). 2Then, a pattern was formed by shower development for 30 seconds using an aqueous sodium carbonate solution at a liquid temperature of 25°C. The minimum line width of the obtained pattern was taken as the resolution (µm).

[0267] <Development residue suppression property> A pattern was formed in the same manner as in the above <Resolution>, and the resulting line / space pattern was observed by a scanning electron microscope to measure the thickness of residues in the space portions and also by visual observation, and the suppression of development residues was evaluated according to the following criteria. A: The thickness of the residue in the space is 50 nm or less, and no residue is visible to the naked eye. B: The thickness of the residue in the space area is 50 nm or less, and the residue can be seen visually. C: Residue thickness in the space area is more than 50 nm

[0268] Table 3 shows the evaluation results. In Table 3, each description indicates the following. The column "M / B" indicates the mass ratio of the content of the difunctional or higher polymerizable compound to the content of the resin (content of the difunctional or higher polymerizable compound / content of the resin). The column "YX" indicates the value (YX) obtained by subtracting the contact angle X from the contact angle Y. "I / O value" and "Tg" indicate the respective values ​​of the resin contained in the photosensitive composition layer. "M / B", "double bond content" and "acid value" indicate the respective values ​​of the photosensitive composition layer.

[0269] [Table 3]

[0270] From the results in Table 3, it was confirmed that the method for producing a laminate of the present invention provides an excellent pattern shape. It was confirmed that the effects of the present invention were more excellent when the content of double bonds in the photosensitive composition layer was 1.0 to 3.0 mmol / g (comparison between Examples 1 and 2 and Example 5). It was confirmed that the effects of the present invention are more excellent when the acid value of the photosensitive composition layer is 50 to 100 mgKOH / g (comparison between Examples 1 to 4 and Examples 6 and 9), and that the effects of the present invention are even more excellent when the acid value of the photosensitive composition layer is 50 to 90 mgKOH / g (comparison between Examples 1 to 2 and Example 4).Furthermore, it was confirmed that the suppression of development residues is more excellent when the acid value of the photosensitive composition layer is 60 to 90 mgKOH / g (comparison between Example 1 and Example 2, etc.). It was confirmed that the effects of the present invention were more excellent when the mass ratio of the content of the difunctional or higher polymerizable compound to the content of the resin was 0.60 to 1.00 (comparison between Examples 1 and 2 and Example 3). It was confirmed that the effects of the present invention are more excellent when the Tg of the resin is more than 110° C. and not more than 130° C. (Comparison between Examples 1 and 2 and Example 7). [Explanation of symbols]

[0271] 1 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 lamination step of bringing a surface of a transfer film having a temporary support, an intermediate layer, and a photosensitive composition layer in this order opposite to the intermediate layer side of the photosensitive composition layer into contact with a substrate, and laminating 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-exposing the photosensitive composition layer; a developing step of developing the exposed photosensitive composition layer with an alkaline developer to form a pattern, the difference between the contact angle X obtained by measurement X and the contact angle Y obtained by measurement Y is 20 degrees or less; The contact angle X is 50 degrees or more, The thickness of the intermediate layer is 1.0 μm or more, The method for producing a laminate, wherein the intermediate layer contains a water-soluble resin. Measurement X: The surface of the transfer film opposite to the intermediate layer side of the photosensitive composition layer is brought into contact with the substrate, the transfer film and the substrate are bonded together, the temporary support is peeled off from the obtained laminate between the temporary support and the intermediate layer, and the photosensitive composition layer is exposed entirely from the exposed intermediate layer side under the same exposure conditions as in the exposure step, and then brought into contact with the alkaline developer used in the development step, and the water contact angle of the exposed surface of the cured layer is measured, which is defined as contact angle X. Measurement Y: The surface of the transfer film opposite to the intermediate layer side of the photosensitive composition layer is brought into contact with the substrate, and 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, and the photosensitive composition layer is exposed entirely from the exposed intermediate layer side under the same exposure conditions as in the exposure step. Thereafter, the photosensitive composition layer is brought into contact with water, and the water contact angle of the exposed surface of the cured layer is measured, which is defined as contact angle Y.

2. The method for producing a laminate according to claim 1, wherein the contact angle X is 50 to 80 degrees.

3. The method for producing a laminate according to claim 1 or 2, wherein the contact angle Y is more than 70 degrees and not more than 90 degrees.

4. The 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 contains a resin, The method for producing a laminate according to any one of claims 1 to 4, wherein the resin has an I / O value of 0.50 to 0.

70.

6. The method for producing a laminate according to any one of claims 1 to 5, wherein the photosensitive composition layer has an acid value of 50 to 100 mgKOH / g.

7. the photosensitive composition layer contains a difunctional or higher functional polymerizable compound and a resin, The method for producing a laminate according to any one of claims 1 to 6, wherein a mass ratio of a content of the di- or higher functional polymerizable compound to a content of the resin is 0.60 to 1.

00.

8. The method for producing a laminate according to any one of claims 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, water-soluble cellulose derivatives, polyether-based resins, and polyamide-based resins.

9. The method for producing a laminate according to any one of claims 1 to 8, wherein the photosensitive composition layer has a thickness of 1 to 20 µm.

10. The method for producing a laminate according to any one of claims 1 to 9, wherein the intermediate layer has a thickness of 3.0 µm or less.

11. The method for producing a laminate according to any one of claims 1 to 10, wherein the exposure step is a step of bringing the exposed intermediate layer into contact with a mask and performing pattern exposure.

12. a lamination step of bringing a surface of a transfer film having a temporary support, an intermediate layer, and a photosensitive composition layer in this order opposite to the intermediate layer side of the photosensitive composition layer into contact with a substrate having a conductive layer, and laminating 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-exposing the photosensitive composition layer; a developing step of developing the exposed photosensitive composition layer with an alkaline developer to form a pattern; an etching step of etching the conductive layer in an area where the pattern is not arranged, the difference between the contact angle X obtained by measurement X and the contact angle Y obtained by measurement Y is 20 degrees or less; The contact angle X is 50 degrees or more, The thickness of the intermediate layer is 1.0 μm or more, The method for manufacturing circuit wiring, wherein the intermediate layer contains a water-soluble resin. Measurement X: The surface of the transfer film opposite to the intermediate layer side of the photosensitive composition layer is brought into contact with the substrate, the transfer film and the substrate are bonded together, the temporary support is peeled off from the obtained laminate between the temporary support and the intermediate layer, and the photosensitive composition layer is exposed entirely from the exposed intermediate layer side under the same exposure conditions as in the exposure step, and then brought into contact with the alkaline developer used in the development step, and the water contact angle of the exposed surface of the cured layer is measured, which is defined as contact angle X. Measurement Y: The surface of the transfer film opposite to the intermediate layer side of the photosensitive composition layer is brought into contact with the substrate, and 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, and the photosensitive composition layer is exposed entirely from the exposed intermediate layer side under the same exposure conditions as in the exposure step. Thereafter, the photosensitive composition layer is brought into contact with water, and the water contact angle of the exposed surface of the cured layer is measured, which is defined as contact angle Y.

13. a temporary support, an intermediate layer, and a photosensitive composition layer in this order; A transfer film that is subjected to a development step in which the film is developed using an alkaline developer to form a pattern after the exposure treatment, the difference between the contact angle X obtained by measurement X and the contact angle Y obtained by measurement Y is 20 degrees or less; The contact angle X is 50 degrees or more, The thickness of the intermediate layer is 1.0 μm or more, The transfer film, wherein the intermediate layer contains a water-soluble resin. Measurement X: The surface of the transfer film opposite to the intermediate layer side of the photosensitive composition layer is brought into contact with the substrate, the transfer film and the substrate are bonded together, the temporary support is peeled off from the obtained laminate between the temporary support and the intermediate layer, and the photosensitive composition layer is exposed entirely from the exposed intermediate layer side under the same exposure conditions as in the exposure treatment, and then brought into contact with the alkaline developer used in the developing step, and the water contact angle of the exposed surface of the cured layer is measured, which is defined as contact angle X. Measurement Y: The surface of the transfer film opposite to the intermediate layer side of the photosensitive composition layer is brought into contact with the substrate, and 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, and the photosensitive composition layer is exposed entirely from the exposed intermediate layer side under the same exposure conditions as in the exposure treatment. Thereafter, the photosensitive composition layer is brought into contact with water, and the water contact angle of the exposed surface of the cured layer is measured, which is defined as contact angle Y.

14. The transfer film according to claim 13, wherein the contact angle X is 50 to 80 degrees.

15. The transfer film according to claim 13 or 14, wherein the contact angle Y is greater than 70 degrees and equal to or less than 90 degrees.

16. The transfer film according to any one of claims 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 claims 13 to 16, wherein the resin has an I / O value of 0.5 to 0.

7.

18. The transfer film according to any one of claims 13 to 17, wherein the photosensitive composition layer has an acid value of 50 to 100 mgKOH / g.

19. the photosensitive composition layer contains a difunctional or higher functional polymerizable compound and a resin, The transfer film according to any one of claims 13 to 18, wherein the mass ratio of the content of the difunctional or higher functional polymerizable compound to the content of the resin is 0.60 to 1.

00.

20. The transfer film according to any one of claims 13 to 19, wherein the intermediate layer comprises at least one selected from the group consisting of polyhydric alcohols, oxide adducts of polyhydric alcohols, phenol derivatives, water-soluble cellulose derivatives, polyether-based resins, and polyamide-based resins.

21. The transfer film according to any one of claims 13 to 20, wherein the photosensitive composition layer has a thickness of 1 to 20 µm.

22. The transfer film according to any one of claims 13 to 21, wherein the thickness of the intermediate layer is 3.0 µm or less.

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