TW202234179A - Method for producing a conductive pattern, and method for manufacturing an electronic device - Google Patents

Abstract

A method for producing a conductive pattern according to the present disclosure comprises a formation step 1, a formation step 2, a light exposure step, a removal step 1 and a removal step 2. In the formation step 1, a conducive layer that contains a metal nanomaterial and a resin is formed on a part or the entirety of the surface of a supporting body. In the formation step 2, a photosensitive resin layer is formed on the conductive layer. In the light exposure step, the photosensitive resin layer is subjected to light exposure. In the removal step 1, a resin pattern is formed by removing unnecessary portions from the light-exposed photosensitive resin layer. In the removal step 2, a conductive pattern is obtained by removing the conductive layer in portions where the resin pattern is not formed. A method for producing an electronic device according to the present disclosure is provided with a conductive pattern which is obtained by the above-described method for producing a conductive pattern.

Description

Manufacturing method of conductive pattern and manufacturing method of electronic component

The present invention relates to a method of manufacturing a conductive pattern and a method of manufacturing an electronic component.

In a display device (organic electroluminescence (EL) display device, liquid crystal display device, etc.) including a touch panel such as an electrostatic capacitance type input device, electrodes corresponding to a sensor of a visual recognition portion are provided inside the touch panel. Conductive patterns such as patterns, peripheral wiring portions, and wirings of lead-out wiring portions. Usually, the layer of the photosensitive resin composition provided on an arbitrary substrate using a photosensitive transfer material is separated from the photosensitive transfer material due to the small number of steps for obtaining the desired pattern shape when forming the patterned layer. Exposure through a mask having a desired pattern followed by development is widely used.

Printed conductive patterns have been widely used in various fields as various sensors such as pressure sensors and biosensors, printed substrates, solar cells, capacitors, electromagnetic shields, touch panels, and antennas. .

As a conventional method for forming a high-resolution pattern, the one described in Patent Document 1 is known. In Patent Document 1, a method for forming a high-resolution pattern is described, which includes: a step of attaching a dry film photoresist to a substrate ( S1 ); exposing and developing the above dry film photoresist to form a desired The step (S2) of pattern casting of the pattern-shaped concave portion; the step (S3) of filling the above-mentioned pattern-shaped concave portion with ink containing functional materials; and the step (S4) of drying the above-mentioned ink, which is characterized in that the above-mentioned dry film is The thickness (μm) of the photoresist is 100×β/α or more [wherein, α is the volume fraction (volume %) of the functional material in the ink, and β is the thickness (μm) of the high-resolution pattern. ]. As a method of forming a conductive pattern, those described in Non-Patent Document 1 or Patent Document 2 are known. Non-Patent Document 1 and Patent Document 2 describe a method of directly drawing a pattern by attaching ink containing a fine metal to a substrate by ink jetting. The resolution of the thin line pattern obtained by this method is generally several tens of μm to several hundreds of μm.

Patent Document 1: Japanese Patent Laid-Open No. 2007-296509 Patent Document 2: Japanese Patent Laid-Open No. 2009-37880

Non-Patent Document 1: Development of High-Performance Silver Nanoparticle Ink for Printing Integrated Circuits, Daisuke Kumaki, Journal of the Printing Society of Japan, 53, 4, pp.24-27 (2016)

A problem to be solved by one embodiment of the present invention is to provide a method for producing a conductive pattern having excellent resolution. The problem to be solved by another embodiment of this invention is to provide the manufacturing method of the electronic element provided with the conductive pattern obtained by the manufacturing method of the said conductive pattern.

Mechanisms for solving the above-mentioned problems include the following aspects. <1> A method of manufacturing a conductive pattern, comprising: forming a conductive layer comprising a metal nanomaterial and a resin on a part or the entire surface of a support body; forming step 1; forming a photosensitive resin layer on the conductive layer Step 2; an exposure step of exposing the photosensitive resin layer to light; a removal step 1 of removing unnecessary parts from the exposed photosensitive resin layer and forming a resin pattern; and removing the above-mentioned resin pattern in the part where the resin pattern is not formed Step 2 of removing the conductive layer and obtaining the conductive pattern. <2> The method for producing a conductive pattern according to <1>, wherein The aforementioned metal nanomaterials include silver nanomaterials. <3> The method for producing a conductive pattern according to <1> or <2>, wherein The aforementioned metal nanomaterials are particles having an average primary particle diameter of 1 nm to 200 nm. <4> The method for producing a conductive pattern according to any one of <1> to <3>, wherein The said photosensitive resin layer contains an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator. <5> The method for producing a conductive pattern according to any one of <1> to <3>, wherein The said photosensitive resin layer contains a polymer which has a structural unit which has an acid group protected by an acid-decomposable group, and a photoacid generator. <6> The method for producing a conductive pattern according to any one of <1> to <3>, wherein The said photosensitive resin layer contains the resin provided with the structural unit which has a phenolic hydroxyl group, and a quinonediazide compound. <7> The method for producing a conductive pattern according to any one of <1> to <6>, wherein The said photosensitive resin layer contains the compound which has an unshared electron pair. <8> The method for producing a conductive pattern according to <7>, wherein The compound having the above-mentioned unshared electron pair is a heterocyclic compound. <9> The method for producing a conductive pattern according to any one of <1> to <8>, wherein The said formation process 2 is the process of forming the said photosensitive resin layer by making a photosensitive transfer material contact and transfer on the said conductive layer. <10> The method for producing a conductive pattern according to any one of <1> to <9>, wherein The above-mentioned forming step 2 is a step of forming an intermediate layer and a photosensitive resin layer on the above-mentioned conductive layer. <11> The method for producing a conductive pattern according to any one of <1> to <10>, wherein The exposure in the above-mentioned exposure step is performed by contact exposure. <12> The method for producing a conductive pattern according to any one of <1> to <10>, wherein The exposure in the above-mentioned exposure step is performed by direct drawing exposure. <13> The method for producing a conductive pattern according to any one of <1> to <10>, wherein The exposure in the above-mentioned exposure step is performed by projection exposure. <14> The method for producing a conductive pattern according to any one of <1> to <13>, wherein The above-mentioned unnecessary part removal in the above-mentioned removal step 1 is performed by a developer. <15> The method for producing a conductive pattern according to any one of <1> to <14>, wherein The removal of the conductive layer in the removal step 2 is performed by wet etching. <16> The method for producing a conductive pattern according to any one of <1> to <14>, wherein The removal of the conductive layer in the removal step 2 is performed by dry etching. <17> The manufacturing method of an electronic component provided with the conductive pattern obtained by the manufacturing method of the conductive pattern in any one of <1>-<16>. [Inventive effect]

According to one embodiment of the present invention, it is possible to provide a method for producing a conductive pattern with excellent resolution. According to another aspect of this invention, the manufacturing method of the electronic element provided with the conductive pattern obtained by the manufacturing method of the said conductive pattern can be provided.

Hereinafter, the content of the present invention will be described. In addition, although it demonstrates referring drawings, a code|symbol may be abbreviate|omitted. In this specification, the numerical range represented using "-" shows the range which includes the numerical value described before and after "-" as a lower limit and an upper limit. In this specification, "(meth)acrylic acid" means both or either of acrylic acid and methacrylic acid, and "(meth)acrylate" means both or either of acrylate and methacrylate, The "(meth)acryloyl group" represents both or any one of an acryl group and a methacryloyl group. Furthermore, in the present invention, when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified, the amount of each component in the composition represents the amount of the corresponding plurality of substances present in the composition. total. In this specification, the term "step" includes not only an independent step, but also in the case where it cannot be clearly distinguished from other steps, as long as the intended function of the step is exerted, it is also included in the term. In the notation of groups (atomic groups) in the present specification, the notation that is not substituted and unsubstituted includes a group without a substituent and a group with a substituent. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups), but also substituted alkyl groups (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure by light but also drawing by particle beams such as electron beams and ion beams. As the light used for exposure, the bright-line spectrum of a mercury lamp, and activating light rays (active energy rays) such as extreme ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams are usually mentioned. The chemical structural formula in this specification may be described as a simplified structural formula in which a hydrogen atom is omitted. In the present invention, "mass %" and "weight %" have the same meaning, and "mass part" and "weight part" have the same meaning. In the present invention, a combination of two or more preferred aspects is a more preferred aspect. Unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present invention are determined by using a gel permeation chromatography (GPC) analyzer, THF (tetrahydrofuran) as a solvent, and using differential Refractometer was used for detection, and polystyrene was used as a standard material to convert the molecular weight. The columns used in the GPC analysis device are TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all are product names manufactured by TOSOH CORPORATION). In this specification, the "total solid content" means the total mass of the components excluding the solvent from all the components of the composition. As described above, the "solid content" refers to a component from which the solvent is removed, and may be solid or liquid, for example, at 25°C.

(Manufacturing method of conductive pattern) The manufacturing method of the conductive pattern of the present invention includes: forming step 1 of forming a conductive layer comprising metal nanomaterials and resin on a part or the entire surface of the support body; forming step 2 of forming a photosensitive resin layer on the conductive layer; An exposure step of exposing the photosensitive resin layer to light; a removal step 1 of removing unnecessary parts from the exposed photosensitive resin layer and forming a resin pattern; and removing the conductive layer in the part where the resin pattern is not formed, and Step 2 of removing the conductive pattern is obtained.

Conventionally, when a conductive pattern is formed by an ink containing a metal nanomaterial and a resin, sufficient resolution has not been obtained in the formation of a conductive pattern by printing such as an ink jet method. In the method for producing a conductive pattern of the present invention, a conductive layer comprising a metal nanomaterial and a resin is used, a resin pattern is formed on the conductive layer, and the conductive pattern is obtained by removing the conductive layer in a portion where the resin pattern is not formed. . Thereby, even the conductive layer including the metal nanomaterial and the resin can form a high-resolution conductive pattern.

Hereinafter, the manufacturing method of the conductive pattern of this invention is demonstrated in detail.

<Formation step 1> The manufacturing method of the conductive pattern of the present invention includes the forming step 1 of forming a conductive layer comprising a metal nanomaterial and a resin on a part or the entire surface of the support. As the material of the metal nanomaterial contained in the conductive layer, copper, silver, zinc, iron, chromium, molybdenum, nickel, aluminum, gold, platinum, palladium, alloys of two or more of these, and ITO (Indium Tin Oxide: tin indium oxide), IZO (Indium Zinc Oxide: indium zinc oxide), conductive silicon dioxide, etc. Among them, as the material of the metal nanomaterials, copper, silver, nickel, aluminum, gold, platinum, palladium or alloys thereof are preferred from the viewpoints of resistance value, cost, sintering temperature, etc. The alloy is more preferable, and in particular, silver or an alloy of silver is more preferable, and silver is particularly preferable from the viewpoint of sintering temperature and oxidation inhibition. That is, it is particularly preferable that the metal nanomaterials are silver nanomaterials. The shape of the metal nanomaterial is not particularly limited as long as it is a known shape. As the metal nanomaterial, metal nanoparticle or metal nanowire is preferable, and metal nanoparticle is more preferable.

As metal nanoparticles, spherical particles, flat-shaped particles, or irregular-shaped particles may be used. The flattened particles include plate-shaped particles (eg, polygonal columnar particles, cylindrical particles, elliptical particles), ellipsoid-shaped particles, spindle-shaped particles, and the like. From the viewpoints of stability and melting temperature, the average primary particle size of the metal nanoparticles is preferably 0.1 nm to 500 nm, more preferably 1 nm to 200 nm, and particularly preferably 1 nm to 100 nm. The average primary particle size of the metal nanoparticles in the present invention can be obtained by taking a scanning electron microscope (SEM image) of 100 particles with a scanning electron microscope (for example, S-3700N, manufactured by Hitachi High-Technologies Corporation). ), and the particle diameter was measured using an image processing measuring device (LUZEX AP; manufactured by NIRECO CORPORATION) to obtain an arithmetic mean value. That is, the particle size referred to in the present invention represents the diameter of the metal nanoparticle when the projected shape of the metal nanoparticle is a circle. The diameter of time is represented.

As the above-mentioned metal nanoparticles, flat silver particles are preferably used, flat silver particles are more preferably used, and polygonal columnar silver particles or cylindrical silver particles are further preferably used.

From the viewpoint of electrical conductivity, it is preferable that the above-mentioned metal nanoparticles contain a metal that is more expensive than silver, and it is more preferable to contain flat particles at least partially coated with gold. Here, "a metal more expensive than silver" means "a metal having a standard electrode potential higher than that of silver". The ratio of the metal more expensive than silver to silver in the above-mentioned metal nanoparticles is preferably 0.01 atomic % to 5 atomic %, more preferably 0.1 atomic % to 2 atomic %, and further preferably 0.2 atomic % to 0.5 atomic %. good. In addition, the content of a metal more expensive than silver can be measured by, for example, dissolving a sample with an acid or the like, and then performing a high-frequency Inductively Coupled Plasma (ICP) spectrophotometric analysis.

The size (long axis length) of the flat particles is not particularly limited, and can be appropriately selected according to the purpose. The average equivalent circle diameter of the flat particles is preferably 10 nm to 500 nm, more preferably 20 nm to 300 nm, and even more preferably 50 nm to 200 nm.

The thickness T of the flat particles is preferably 20 nm or less, more preferably 2 nm to 15 nm, and particularly preferably 4 nm to 12 nm. The particle thickness T can be measured by an atomic force microscope (Atomic Force Microscope: AFM) or a transmission electron microscope (TEM).

As a method of measuring the average particle thickness by AFM, for example, a particle dispersion liquid containing flat particles is dropped on a glass substrate, and the method of drying and measuring the thickness of one particle is mentioned. As a method of measuring the average particle thickness by TEM, for example, a particle dispersion liquid containing flat particles is dropped on a silicon substrate, and after drying, a coating treatment by carbon vapor deposition and metal vapor deposition is performed. Focused ion beam (Focused Ion Beam: FIB) processing to produce cross-section slices, and a method of measuring the thickness of particles by observing the cross-section with a TEM (hereinafter, also referred to as FIB-TEM.) and the like.

As for the metal nanomaterial in the said conductive layer, only 1 type may be used, and 2 or more types may be used together. The content of the metal nanomaterial is preferably 10% by mass to 95% by mass, and preferably 30% by mass to 80% by mass, relative to the total mass of the conductive layer, from the viewpoints of the metal coating film formability and dispersion stability during sintering for better.

As the resin contained in the above-mentioned conductive layer, it is preferable to contain a binder polymer from the viewpoint of durability. Examples of the binder polymer include polyvinyl acetal resin, polyvinyl alcohol resin, polyvinyl butyral resin, polyacrylate resin, polyfluoroacrylate resin, polymethyl methacrylate resin, and polycarbonate. Ester resins, polyvinyl chloride resins, polyester resins, polyurethane resins, polyester resins, polyoxazoline resins, natural polymers (eg, gelatin or cellulose, etc.), methyl cellulose, ethyl Cellulose, hydroxypropyl cellulose and its derivatives, etc. Wherein, the binder polymer preferably comprises polyvinyl alcohol resin, polyvinyl butyral resin, polyvinyl chloride resin, polyester resin, polyurethane resin, ethyl cellulose or hydroxypropyl cellulose, It is more preferable to contain polyester resin, polyurethane resin or hydroxypropyl cellulose. Only one type of binder polymer may be used, or two or more types may be used in combination.

The resin in the said conductive layer may use only 1 type, and may use 2 or more types together. The content of the resin contained in the conductive layer is preferably 1% by mass to 90% by mass, preferably 10% by mass to 80% by mass, based on the total mass of the conductive layer, from the viewpoints of the metal film formability and conductivity during sintering. The mass % is more preferable, and 20 mass % to 70 mass % is particularly preferable.

The above-mentioned conductive layer may further contain other additives. As another additive, well-known additives, such as surfactant, are mentioned. As the surfactant, Rapisol A-90 (manufactured by NOF CORPORATION, solid content concentration 1%), Naro Acty CL-95 (manufactured by Sanyo Chemical Industries, Ltd., solid content concentration 1%), etc. are mentioned.

The thickness of the above-mentioned conductive layer is not limited. From the viewpoint of conductivity and film formability, the average thickness of the conductive layer is preferably 0.001 μm to 1,000 μm, more preferably 0.005 μm to 15 μm, and particularly preferably 0.01 μm to 10 μm. The average thickness of the conductive layer and the support in the present invention is the average value of the thicknesses at 10 locations measured by observing a cross section in a direction perpendicular to the in-plane direction using a scanning electron microscope (SEM).

Although it does not specifically limit as a formation method of the said conductive layer, It is preferable to form by apply|coating a conductive ink. The method of applying the conductive ink is not particularly limited, and examples thereof include an ink jet method, a spray method, a roll coating method, a bar coating method, a curtain coating method, and a die coating method (ie, a slit coating method), and the like. . The conductive ink used in the present invention may be a curable conductive ink. The curable conductive ink may be, for example, a thermosetting type, a photocurable type, or a thermosetting type and a photocurable type conductive ink. The aforementioned conductive ink includes a metal nanomaterial and a resin, and may further include at least any one of a solvent and the aforementioned other additives. As the solvent contained in the above-mentioned conductive ink, water and an organic solvent can be used. As the organic solvent, hydrocarbons such as toluene, dodecane, tetradecane, cyclododecene, n-heptane, and n-undecane; and alcohols such as ethanol and isopropanol are preferred. As a method for forming the above-mentioned conductive layer, after the conductive ink is applied, steps such as drying and calcination of the coated product of the conductive ink may be included as necessary.

The above-mentioned conductive layer is preferably formed in a shape larger than the shape of the desired conductive pattern.

As a support body used for the manufacturing method of the conductive pattern of this invention, a well-known support body should just be used, and a resin film, a board|substrate, etc. are mentioned. Among them, as a support, a substrate is preferable. The substrate may have any layer other than the conductive layer as desired. As a board|substrate, a resin substrate, a glass substrate, and a semiconductor substrate are mentioned, for example. As a preferable aspect of a board|substrate, the thing described in the paragraph 0140 of International Publication No. WO 2018/155193, for example, is incorporated in this specification.

As a base material which comprises a board|substrate, glass, silicon, and a thin film are mentioned, for example. It is preferable that the base material which comprises a board|substrate is transparent. Examples of the transparent glass substrate include tempered glass typified by Corning Incorporated's Gorilla Glass. Moreover, as a transparent glass base material, the material used in Unexamined-Japanese-Patent No. 2010-86684, Unexamined-Japanese-Patent No. 2010-152809, and Unexamined-Japanese-Patent No. 2010-257492 can be used.

When a film substrate is used as the substrate, it is preferable to use a film substrate with low optical distortion and/or high transparency. As such a film substrate, for example, polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymers can be mentioned.

When a substrate is produced by a roll-to-roll method, a film substrate is preferable as the substrate. Moreover, when manufacturing the circuit wiring for touch panels by a roll-to-roll method, it is preferable that a base material is a sheet-like resin composition.

The said support body may have the said conductive layer of 1 layer independently, and may have 2 or more layers. When the support has two or more conductive layers, it is preferable that the support has conductive layers with different materials. The said support body may have the said conductive layer on one surface, and may have it respectively on both surfaces.

As a board|substrate, it may further have the board|substrate of routing wiring. The above-mentioned substrate can be preferably used as a substrate for a touch panel. As the material of the detour wiring, metal is preferable. Examples of metals used as materials for routing wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and alloys composed of two or more of these metal elements. As the material of the detour wiring, copper, molybdenum, aluminum, or titanium are preferable, and copper is particularly preferable.

<Formation step 2> The manufacturing method of the electroconductive pattern of this invention includes the formation step 2 of forming the photosensitive resin layer on the said electroconductive layer. There is no restriction|limiting in particular as a method of forming the photosensitive resin layer on the said conductive layer, A well-known resist formation method can be used. Among them, the above-mentioned forming step 2 is preferably a step of forming the above-mentioned photosensitive resin layer by contacting and transferring a photosensitive transfer material on the above-mentioned conductive layer. The above-mentioned forming step 2 is preferably a step of forming an intermediate layer and a photosensitive resin layer on the above-mentioned conductive layer, and it is more preferred that the above-mentioned intermediate layer is a water-soluble resin layer and a thermoplastic resin layer. As a method of transferring a photosensitive resin layer onto the conductive layer using a photosensitive transfer material, the conductive layer is brought into contact with the photosensitive resin layer in the photosensitive transfer material, and the photosensitive transfer material and the conductive layer are brought into contact with each other. Lamination is preferred. In the above aspect, the adhesiveness between the photosensitive resin layer and the support in the photosensitive transfer material is improved. Therefore, the patterned photosensitive resin layer after exposure and development can be preferably used as an etching resist in etching the conductive layer. In addition, the preferable aspect of the photosensitive transfer material used for the manufacturing method of the electroconductive pattern of this invention is summarized and described later.

There is no restriction|limiting in particular as a method of press-bonding a board|substrate and a photosensitive transfer material, A well-known transfer method and a lamination method can be used. For the dummy support in the photosensitive transfer material, the outermost layer on the side having the photosensitive resin layer and the conductive layer are overlapped, and pressure and heating are performed using a mechanism such as a roller to perform the transfer of the photosensitive transfer material to the conductive layer. Fitting is better. A known laminator such as a laminator, a vacuum laminator, and an automatic cutting laminator which can further improve productivity can be used for lamination. The lamination temperature is not particularly limited, for example, it is preferably 70°C to 130°C.

The method for producing the conductive pattern of the present invention is preferably carried out by a roll-to-roll method. Hereinafter, the roll-to-roll method will be described. The roll-to-roll method is a method including using a support capable of winding and unwinding as a support, and having the above-mentioned support or the above-mentioned support before any steps included in the method for producing a conductive pattern of the present invention The step of unwinding the support of the conductive layer and the like (also referred to as "unwinding step".); and after any of the steps, the step of winding the support having the above-mentioned conductive layer and the like (also referred to as "winding up". step"), at least one of the steps (preferably all steps or all steps except the heating step) is carried out while conveying the support having the above-mentioned support or the above-mentioned conductive layer. The unwinding method in the unwinding step and the winding method in the coiling step are not particularly limited, and a known method may be used in the manufacturing method to which the roll-to-roll method is applied.

In the case where the photosensitive transfer material has a protective film, it is preferable that the manufacturing method of the conductive pattern of the present invention includes a protective film peeling step of peeling the protective film from the photosensitive transfer material before the above-mentioned forming step 2. The method of peeling off the cover film is not limited, and a known method can be applied.

In the case of using the above-mentioned photosensitive transfer material, the method for producing a conductive pattern of the present invention includes peeling off the dummy support between the above-mentioned forming step 2 and the exposure step, or between the exposure step and the removing step 1. steps are better. The peeling method of the dummy support is not particularly limited, and the same mechanism as the cover film peeling mechanism described in paragraphs 0161 to 0162 of Japanese Patent Application Laid-Open No. 2010-072589 can be used.

<Exposure step> The manufacturing method of the conductive pattern of this invention includes the exposure process of exposing the said photosensitive resin layer. The exposure in the exposure step is a pattern-like exposure treatment (also referred to as "pattern exposure".) That is, an exposure treatment of a form in which an exposed portion and a non-exposed portion are present. The positional relationship between the exposed area and the unexposed area in pattern exposure is not particularly limited, and can be appropriately adjusted.

The detailed arrangement and specific size of the pattern in the pattern exposure are not particularly limited. At least a part of the pattern (preferably the electrode pattern of the touch panel and/or the part where the wiring is taken out) preferably includes a thin line with a width of 20 μm or less, in order to improve the input of the circuit wiring with the circuit wiring manufactured by the circuit wiring manufacturing method The display quality of the display device (such as a touch panel) of the device, and the area occupied by the extraction wiring is reduced, and it is better to include thin lines with a width of less than 10 μm. From the viewpoint of further exerting the effects of the present invention, the obtained resin pattern preferably has a resin pattern with a line width of 20 μm or less, more preferably has a resin pattern with a line width of 10 μm or less, and has a resin pattern with a line width of 8 μm or less The pattern is more preferable, and it is especially preferable to have a resin pattern with a line width of 5 μm or less.

The light source used for exposure can be appropriately selected and used as long as it irradiates light of a wavelength capable of exposing the photosensitive resin layer (for example, 365 nm or 405 nm). Specifically, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode) can be mentioned. The exposure amount is preferably 5mJ/cm ² to 200mJ/cm ² , and more preferably 10mJ/cm ² to 100mJ/cm ² . Preferable aspects of the light source, exposure amount, and exposure method used for exposure include, for example, the aspects described in paragraphs 0146 to 0147 of International Publication No. WO 2018/155193, and these contents are incorporated into this specification middle.

In the case of using a photosensitive transfer material, in the exposure step, pattern exposure may be performed after the dummy support is peeled off from the transfer layer, or the dummy support may be passed through the dummy support before peeling off the transfer layer. Pattern exposure was performed, and then the dummy support was peeled off from the transfer layer. Before exposure, when the dummy support is peeled off from the transfer layer, exposure can be performed with the mask in contact with the transfer layer, or the mask can be exposed without being in contact with the transfer layer and close to the transfer layer. When exposing the dummy support without peeling it off from the transfer layer, the exposure may be performed without bringing the mask into contact with the dummy support, or the mask may not come into contact with the dummy support and approach the dummy support. Exposure. In order to prevent contamination of the mask caused by the contact between the composition layer and the mask and to avoid influence on exposure caused by foreign matter adhering to the mask, it is preferable to perform pattern exposure without peeling off the dummy support. In addition, in the case of contact exposure, a contact exposure method can be used as an exposure method. In the case of the non-contact exposure method, as the exposure method, direct exposure (direct drawing exposure) using a proximity exposure method, a lens-based or mirror-based projection exposure (projection exposure) method, an exposure laser, or the like can be appropriately selected and used. Way. In the case of projection exposure of a lens system and a mirror system, an exposure machine having an appropriate number of lens openings (NA) can be used according to the required resolution and depth of focus. In the case of the direct exposure method, drawing may be performed directly on the photosensitive resin composition layer, or reduction projection exposure may be performed on the photosensitive resin composition layer through a lens. Exposure may be performed not only under the atmosphere, but also under reduced pressure or vacuum. Exposure can be performed via a liquid such as water between the light source and the transfer layer. From the viewpoint of resolution, it is preferable to perform the exposure in the exposure step by contacting the above-mentioned transfer layer with a mask and performing contact exposure. From the viewpoint of being able to reduce the influence of the mask and the photosensitive resin layer, it is preferable to perform the exposure in the exposure step by direct drawing exposure or projection exposure.

<Removal step 1> The method for producing a conductive pattern of the present invention includes a removal step 1 of removing unnecessary parts from the exposed photosensitive resin layer to form a resin pattern. It is preferable to carry out the removal of the above-mentioned unnecessary part in the removal step 1 by a developer. The developer is not particularly limited as long as it can remove the non-image portion (unnecessary portion) of the photosensitive resin layer. For example, a known developer such as the developer described in Japanese Patent Laid-Open No. 5-72724 can be used. . As the developing solution, an aqueous alkaline solution containing a compound having pKa=7 to 13 at a concentration of 0.05 mol/L to 5 mol/L (liter) is preferable. The developer may contain a water-soluble organic solvent and/or a surfactant. Examples of basic compounds that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, tetramethylammonium hydroxide, and tetraethyl hydroxide. ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and choline (2-hydroxyethyltrimethylammonium hydroxide). As an alkali developer, the developer described in the paragraph 0194 of International Publication No. 2015/093271 is also preferable. As a development method preferably used, for example, the development method described in the paragraph 0195 of International Publication No. 2015/093271 can be mentioned.

It does not specifically limit as a developing method, Any of spin-on immersion development, shower development, shower and spin development, and immersion development may be used. The spray development refers to a development process in which a developing solution is sprayed on the exposed photosensitive resin layer by a shower to remove the non-exposed portion. After the developing step, it is preferable to remove the developing residue while spraying the cleaning agent by spraying and wiping with a brush. The liquid temperature of the developing solution is not particularly limited, but is preferably 20°C to 40°C.

<Removal step 2> The manufacturing method of the conductive pattern of the present invention includes a removal step 2 of removing the above-mentioned conductive layer in the portion where the above-mentioned resin pattern is not formed and obtaining a conductive pattern. In the etching step, the conductive layer is etched using the resin pattern formed of the photosensitive resin layer as an etching resist. As a method of the etching treatment, a known method can be applied, for example, the method described in paragraphs 0209 to 0210 of JP 2017-120435 A and the methods described in paragraphs 0048 to 0054 of JP 2010-152155 A The method described above, the wet etching method immersed in the etching solution, and the dry etching method such as plasma etching. From the viewpoint of productivity, the removal of the above-mentioned conductive layer in the removal step 2 is preferably performed by wet etching. From the standpoint of analyticity, the removal of the conductive layer in the removal step 2 is preferably performed by dry etching.

Regarding the etching solution used in the wet etching, an acidic or alkaline etching solution may be appropriately selected according to the etching target. Examples of the acidic etching solution include an aqueous solution of an acidic component alone selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, an acidic component, and iron(II) chloride, iron chloride A mixed aqueous solution of a salt selected from the group consisting of (III), iron (II) nitrate, iron (III) nitrate, iron (II) sulfate, iron (III) sulfate, ammonium fluoride and potassium permanganate. The acidic component may be a combination of a plurality of acidic components. Examples of the alkaline etching solution include aqueous solutions containing only alkaline components and alkaline components selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (tetramethylammonium hydroxide, etc.) Aqueous mixed solution with salt (potassium permanganate, etc.). The basic component may be a combination of a plurality of basic components. In order to control the etching rate or the shape of the material to be etched, an organic solvent and a surfactant may be used in combination.

<Removal step 3> In the manufacturing method of the conductive pattern of the present invention, it is preferable to perform the step of removing the residual resin pattern (removal step 3 ) after the removal step 2 . Although there is no restriction|limiting in particular as a method of removing the residual resin pattern, The method of removing by chemical treatment is mentioned, The method of removing using a removal liquid is preferable. As a removal method of the photosensitive resin layer, the method of immersing the support which has the resin pattern which remained in the removal liquid in a stirring process for 1 minute - 30 minutes is mentioned. The liquid temperature of the removal liquid in the stirring process is preferably 30°C to 80°C, more preferably 40°C to 80°C.

As the removal liquid, for example, a removal liquid obtained by dissolving an inorganic basic component or an organic basic component in water, dimethylsulfite, N-methylpyrrolidone, or a mixed solution thereof can be mentioned. As an inorganic alkaline component, sodium hydroxide and potassium hydroxide are mentioned, for example. As an organic basic component, a primary amine compound, a secondary amine compound, a tertiary amine compound, and a quaternary ammonium salt compound are mentioned. Moreover, it can remove by well-known methods, such as a spray method, a spray method, and a spin-dipping method, using a removal liquid.

<Other steps> The manufacturing method of the conductive pattern of this invention may contain arbitrary steps (other steps) other than the above-mentioned steps. For example, the following steps can be exemplified, but are not limited to these steps. Moreover, as an exposure process, a developing process, and other processes applicable to the manufacturing method of a circuit wiring, the process described in the 0035-0051 paragraphs of Unexamined-Japanese-Patent No. 2006-23696 can be mentioned. Further, as other steps, for example, the step of reducing the visible light reflectance described in paragraph 0172 of International Publication No. WO 2019/022089, and the formation on the insulating film described in paragraph 0172 of International Publication No. 2019/022089 can be mentioned. Steps of a new conductive layer, etc., but these steps are not limited.

-Steps to reduce the reflectance of visible light- The manufacturing method of the conductive pattern of the present invention may include the step of performing a process of reducing the visible light reflectance of a part or the whole of the conductive layer. An oxidation treatment is mentioned as a treatment for lowering the visible light reflectance. When the base material has a conductive layer containing copper, copper is oxidized to form copper oxide, and the conductive layer is blackened, whereby the visible light reflectance of the conductive layer can be reduced. The treatment for reducing the reflectance of visible light is described in paragraphs 0017 to 0025 of Japanese Patent Laid-Open No. 2014-150118, and paragraphs 0041, 0042, 0048, and 0058 of Japanese Patent Laid-Open No. 2013-206315, and these The contents described in the official gazette are incorporated into this manual.

<The step of forming an insulating film, the step of forming a new conductive layer on the surface of the insulating film> The manufacturing method of the conductive pattern of the present invention preferably includes the step of forming an insulating film on the surface of the conductive pattern and the step of forming a new conductive layer on the surface of the insulating film. Through the above steps, the second electrode pattern insulated from the first electrode pattern can be formed. It does not specifically limit as a process of forming an insulating film, The method of forming a well-known permanent film is mentioned. In addition, an insulating film of a desired pattern can be formed by photolithography using a photosensitive material having insulating properties. The step of forming a new conductive layer on the insulating film is not particularly limited. For example, a new conductive layer of a desired pattern can be formed by photolithography using a photosensitive material having conductivity.

In the manufacturing method of the conductive pattern of the present invention, a support having a plurality of conductive layers on both surfaces of the support is used, and the conductive layers formed on the two surfaces of the support are preferably formed sequentially or simultaneously. With this structure, the circuit wiring for a touch panel in which the first conductive pattern is formed on one surface of the base material and the second conductive pattern is formed on the other surface can be formed. Moreover, it is also preferable to form the circuit wiring for touch panels of such a structure from both surfaces of a base material by roll-to-roll.

＜Use＞ The conductive pattern manufactured by the manufacturing method of the conductive pattern of the present invention can be applied to various devices. As a device provided with the said conductive pattern, an input device etc. are mentioned, for example, a touch panel is preferable, and an electrostatic capacitance type touch panel is more preferable. In addition, the above-described input device can be applied to display devices such as organic electroluminescence display devices and liquid crystal display devices. The conductive pattern produced by the method for producing the conductive pattern of the present invention can be preferably applied to a flexible display device, especially a flexible touch panel.

<Photosensitive transfer material> Preferably, the photosensitive transfer material used in the manufacturing method of the conductive pattern of the present invention has a dummy support and a transfer layer including a photosensitive resin layer, and has a dummy support and a transfer layer including the photosensitive resin layer in this order. Printing layer and protective film are better. The photosensitive transfer material used in the present invention may have other layers between the dummy support and the photosensitive resin layer, between the photosensitive resin layer and the protective film, or the like. Furthermore, it is preferable that the photosensitive transfer material used by this invention further has a thermoplastic resin layer and a water-soluble resin layer between a dummy support body and a photosensitive resin layer. Furthermore, it is preferable that the said transfer layer further contains a thermoplastic resin layer and a water-soluble resin layer. From the viewpoint of further exerting the effects of the present invention, the photosensitive transfer material used in the present invention is preferably a roll-shaped photosensitive transfer material.

Hereinafter, an example of the aspect of the photosensitive transfer material used by this invention is shown, but it is not limited to this. (1) "Pseudo support/photosensitive resin layer/refractive index adjustment layer/protective film" (2) "Pseudo support/photosensitive resin layer/protective film" (3) "Pseudo support/water-soluble resin layer/photosensitive resin layer/protective film" (4) "Pseudo support/thermoplastic resin layer/water-soluble resin layer/photosensitive resin layer/protective film" In addition, in each of the above-mentioned structures, the photosensitive resin layer may be a positive-type photosensitive resin layer or a negative-type photosensitive resin layer, but a negative-type photosensitive resin layer is preferable. It is also preferable that the photosensitive resin layer is a colored resin layer. Among them, as the structure of the photosensitive transfer material, for example, the structures of (2) to (4) above are preferable.

In the photosensitive transfer material, in the case where the photosensitive resin layer further has a structure on the side opposite to the temporary support side, it is arranged on the side opposite to the temporary support side of the photosensitive resin layer. The total thickness of the other layers is preferably 0.1% to 30%, more preferably 0.1% to 20%, with respect to the layer thickness of the photosensitive resin layer.

Hereinafter, an example of a specific embodiment is given and the photosensitive transfer material used by this invention is demonstrated.

Hereinafter, an example of the photosensitive transfer material will be described. The photosensitive transfer material 20 shown in FIG. 1 includes a dummy support 11 , a transfer layer 12 including a thermoplastic resin layer 13 , a water-soluble resin layer 15 and a photosensitive resin layer 17 , and a protective film 19 in this order. The photosensitive transfer material 20 shown in FIG. 1 is a form in which the thermoplastic resin layer 13 and the water-soluble resin layer 15 are arranged, but the photosensitive transfer material of the present invention may not have the thermoplastic resin layer 13 and the water-soluble resin layer 15 arranged. . Hereinafter, each requirement constituting the photosensitive transfer material will be described.

[pseudo support] Preferably, the photosensitive transfer material used in the present invention has a dummy support. The dummy support system supports the layered body including the photosensitive resin layer or the photosensitive resin layer, and the support body which can be peeled off.

From the viewpoint that exposure of the photosensitive resin layer through the temporary support can be performed when pattern exposure of the photosensitive resin layer is performed, it is preferable that the temporary support has light transmittance. In addition, in this specification, "it has light transmittance" means that the transmittance of the light of the wavelength used for pattern exposure is 50% or more. From the viewpoint of improving the exposure sensitivity of the photosensitive resin layer, the transmittance of light with a wavelength (preferably a wavelength of 365 nm) used for pattern exposure of the temporary support is preferably 60% or more, more preferably 70% or more . In addition, the transmittance of the layer included in the transfer film is the ratio of the intensity of the light emitted through the layer to the intensity of the incident light when light is incident in a direction perpendicular to the main surface of the layer (thickness direction). , and measured using MCPD Series manufactured by Otsuka Electronics Co., Ltd.

As a material which comprises a dummy support body, a glass substrate, a resin film, and paper are mentioned, for example, From a viewpoint of intensity|strength, flexibility, and light transmittance, a resin film is preferable. As a resin film, a polyethylene terephthalate (PET: polyethylene terephthalate) film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film are mentioned. Among them, as the resin film, a PET film is preferable, and a biaxially stretched PET film is more preferable.

The thickness (layer thickness) of the dummy support is not particularly limited, and is not particularly limited in terms of strength as a support, flexibility required for bonding with the circuit wiring substrate, and light transmittance required for the first exposure step. Considering the point of view, as long as you choose according to the material. The thickness of the dummy support is preferably 5 to 100 μm, more preferably 10 to 50 μm, further preferably 10 to 20 μm, and particularly preferably 10 to 16 μm from the viewpoint of ease of handling and versatility. The thickness of the dummy support is preferably 50 μm or less, more preferably 25 μm or less, still more preferably 20 μm or less, and particularly preferably 16 μm or less, from the viewpoints of defect suppression, resolution, and linearity of the resin pattern.

In addition, it is preferable that there are no deformations such as wrinkles, scratches, defects, and the like in the film used as a dummy support. From the viewpoints of pattern formability during pattern exposure through the dummy support and transparency of the dummy support, the number of particles, foreign substances, defects, precipitates, and the like contained in the dummy support is preferably small. The number of particles, foreign objects, and defects with a diameter of 1 μm or more is preferably 50 pieces/10mm ² or less, more preferably 10 pieces/10mm ² or less, further preferably 3 pieces/10mm ² or less, and 0 pieces/10mm ² Excellent.

From the viewpoints of defect suppression properties, analytical properties of the resin pattern, and transparency of the dummy support, it is preferable that the haze of the dummy support is small. Specifically, the haze value of the dummy support is preferably 2% or less, more preferably 1.5% or less, further preferably less than 1.0%, and particularly preferably 0.5% or less. The haze value in the present invention uses a haze meter (NDH-2000, manufactured by NIPPON DENSHOKU INDUSTRIES Co., Ltd.), and is measured according to the method of JIS K 7105:1981.

From the viewpoint of imparting handleability to the surface of the dummy support, a layer (lubricant layer) containing fine particles may be provided. The lubricant layer may be provided on one side of the dummy support, or may be provided on both sides. The diameter of the particles contained in the lubricant layer is preferably, for example, 0.05 μm to 0.8 μm. The thickness of the lubricant layer is preferably 0.05 μm to 1.0 μm, for example.

The arithmetic mean roughness Ra of the surface on the opposite side to the photosensitive resin layer side in the dummy support is larger than that in the dummy support from the viewpoints of transportability, defect suppression property of the resin pattern, and analytical performance. The arithmetic mean roughness Ra of the surface on the side of the resin layer is preferable. The arithmetic mean roughness Ra of the surface on the opposite side to the photosensitive resin layer side in the dummy support is preferably 100 nm or less, and is preferably 50 nm from the viewpoints of transportability, defect suppression performance of the resin pattern, and analytical performance. The following is more preferable, 20 nm or less is further preferable, and 10 nm or less is particularly preferable. The arithmetic mean roughness Ra of the surface on the side of the photosensitive resin layer in the dummy support is preferably 100 nm or less, and preferably 50 nm or less, from the viewpoints of the peelability of the dummy support, the defect suppression property of the resin pattern, and the analytical performance. More preferably, 20 nm or less is further preferred, and 10 nm or less is particularly preferred. From the viewpoints of transportability, defect suppression properties of the resin pattern, and analytical properties, "the arithmetic mean roughness Ra of the surface on the opposite side to the photosensitive resin layer side in the dummy support" - "in the dummy support" The subtraction value of the arithmetic mean roughness Ra" of the surface on the side of the photosensitive resin layer is preferably 0 nm to 10 nm, and more preferably 0 nm to 5 nm.

The arithmetic mean roughness Ra of the surface of the dummy support or the protective film in the present invention is measured by the following method. Using a three-dimensional optical profiler (New View7300, manufactured by Zygo Corporation), the surface of the cover film was measured under the following conditions, thereby obtaining the surface profile of the optical film. As measurement and analysis software, Microscope Application of MetroPro ver8.3.2 was used. Next, use the above analysis software to display the Surface Map screen, and obtain the histogram data on the Surface Map screen. The arithmetic mean roughness is calculated according to the obtained histogram data to obtain the Ra value of the surface of the cover film. When bonding a dummy support or a protective film to a photosensitive resin layer or the like, the dummy support or the protective film is peeled off from the photosensitive resin layer, and the Ra value of the peeled-off surface may be measured.

The peeling force of the dummy support, specifically, from the viewpoint of the peeling-suppression property of the dummy support caused by the adjoining of the vertically stacked laminated body and the laminated body when the wound layered body is conveyed again by the roll-to-roll method, is: The peeling force between the dummy support and the photosensitive resin layer or thermoplastic resin layer is preferably 0.5 mN/mm or more, more preferably 0.5 mN/mm to 2.0 mN/mm.

The peeling force of the dummy support in the present invention was measured in the following manner. A PET substrate with a copper layer was prepared by providing a copper layer with a thickness of 200 nm on a polyethylene terephthalate (PET) film with a thickness of 100 μm by a sputtering method. The protective film was peeled off from the produced photosensitive transfer material, and the film was laminated to the tape with the above-mentioned copper under the lamination conditions of a lamination roll temperature of 100° C., a linear pressure of 0.6 MPa, and a linear speed (lamination speed) of 1.0 m/min. layer of PET substrate. Next, after affixing a tape (PRINTACK manufactured by Nitto Denko Corporation) to the surface of the dummy support, the laminate having at least the dummy support and the photosensitive resin layer was cut into a 70mm×10mm size on the PET substrate with the copper layer to produce sample. The PET substrate side of the above-mentioned sample was fixed on the sample stage. Using a tensile-compression tester (manufactured by IMADA-SS Corporation, SV-55), the tape was stretched in a direction of 180 degrees at a speed of 5.5 mm/sec, between the photosensitive resin layer or thermoplastic resin layer and the dummy support. The peeling was performed, and the force required for peeling (peeling force) was measured.

Preferable aspects of the dummy support are described in, for example, paragraphs 0017 to 0018 of Japanese Patent Application Laid-Open No. 2014-85643, paragraphs 0019 to 0026 of Japanese Patent Application Laid-Open No. 2016-27363, and paragraphs 0041 to 0041 of WO2012/081680A1 It is described in paragraph 0057, paragraphs 0029 to 0040 of WO2018/179370A1, and paragraphs 0012 to 0032 of Japanese Patent Application Laid-Open No. 2019-101405, and the contents of these publications are incorporated into this specification.

[Photosensitive resin layer] The photosensitive transfer material used in the present invention has a photosensitive resin layer. The photosensitive resin layer may be a positive-type photosensitive resin layer or a negative-type photosensitive resin layer, and a negative-type photosensitive resin layer is preferable. The negative photosensitive resin layer preferably contains an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator, and based on the total mass of the photosensitive resin layer, contains 10% by mass to 90% by mass of an alkali-soluble resin, vinyl More preferably, the unsaturated compound is 5% by mass to 70% by mass and the photopolymerization initiator is 0.01% by mass to 20% by mass. There is no restriction|limiting as a positive type photosensitive resin layer, A well-known positive type photosensitive resin layer can be utilized. It is preferable that the positive photosensitive resin layer contains an acid-decomposable resin, that is, a polymer having a structural unit having an acid group protected by an acid-decomposable group, and a photoacid generator. It is preferable that the positive photosensitive resin layer contains a resin having a structural unit having a phenolic hydroxyl group and a quinonediazide compound. The positive-type photosensitive resin layer is more preferably a chemically amplified positive-type photosensitive resin layer containing a polymer having a structural unit having an acid group protected by an acid-decomposable group and a photoacid generator. Hereinafter, each component will be described in order. In addition, when it is abbreviated as "photosensitive resin layer", it means both a positive type photosensitive resin layer and a negative type photosensitive resin layer.

＜＜Polymerizable compound＞＞ It is preferable that the negative photosensitive resin layer contains a polymerizable compound. In addition, in this specification, a "polymerizable compound" is a compound polymerized by the action of a polymerization initiator described later, and means a compound different from the above-mentioned polymer A.

The polymerizable group of the polymerizable compound is not particularly limited as long as it is a group related to a polymerization reaction, and examples thereof include vinyl, acryl, methacryloyl, styryl, and cis Groups having ethylenically unsaturated groups such as butenediimide groups; and groups having cationic polymerizable groups such as epoxy groups and oxetanyl groups. As the polymerizable group, a group having an ethylenically unsaturated group is preferred, and an acryl group or a methacryl group is more preferred. The polymerizable compound preferably contains an ethylenically unsaturated compound, and more preferably contains a (meth)acrylate compound.

From the viewpoints of analytical properties and pattern-forming properties, it is preferable that the photosensitive resin layer contains a bifunctional or more polymerizable compound (polyfunctional polymerizable compound), and it is more preferable to contain a trifunctional or more functional polymerizable compound. Here, the bifunctional or more polymerizable compound means a compound having two or more polymerizable groups in one molecule. From the viewpoint of being excellent in analytical properties and releasability, the number of polymerizable groups contained in one molecule of the polymerizable compound is preferably 6 or less.

The negative photosensitive resin layer preferably contains a bifunctional or trifunctional ethylenically unsaturated compound, and contains a bifunctional ethylenically unsaturated compound from the viewpoint of more excellent balance of photosensitivity, resolution, and peelability of the photosensitive resin layer. Compounds are even better. From the viewpoint of being excellent in releasability, the lower limit of the content of the bifunctional or trifunctional ethylenically unsaturated compound with respect to the total content of the ethylenically unsaturated compound in the negative photosensitive resin layer is preferably 60% by mass or more, more than 70 mass % is more preferable, and 90 mass % or more is more preferable. The upper limit in particular of the said content is not restrict|limited, It can be 100 mass %. That is, all the ethylenically unsaturated compounds contained in the negative photosensitive resin layer may be bifunctional ethylenically unsaturated compounds.

From the viewpoints of analytical properties and pattern formability, the negative photosensitive resin layer preferably contains a polymerizable compound having a polyalkylene oxide structure, and more preferably contains a polymerizable compound having a polyethylene oxide structure. As a polymerizable compound which has a polyalkylene oxide structure, polyalkylene glycol di(meth)acrylate etc. mentioned later are mentioned preferably.

-ethylenically unsaturated compound B1- It is preferable that the negative photosensitive resin layer contains an aromatic ring and an ethylenically unsaturated compound B1 having two ethylenically unsaturated groups. The ethylenically unsaturated compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule among the above-mentioned ethylenically unsaturated compounds.

From the viewpoint of being more excellent in resolution, in the negative photosensitive resin layer, the lower limit of the mass ratio of the content of the ethylenically unsaturated compound B1 to the total content of the ethylenically unsaturated compounds is preferably 40% by mass or more. 50 mass % or more is more preferable, 55 mass % or more is further preferable, and 60 mass % or more is particularly preferable. The upper limit of the above-mentioned mass ratio is not particularly limited, but from the viewpoint of releasability, 99 mass % or less is preferable, 95 mass % or less is more preferable, 90 mass % or less is further preferable, and 85 mass % or less is particularly preferable. .

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, and aromatics such as a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring, and a pyridine ring In the case of heterocyclic rings and these condensed rings, aromatic hydrocarbon rings are preferred, and benzene rings are more preferred. In addition, the above-mentioned aromatic ring may have a substituent. The polymerizable compound B1 may have only one aromatic ring, or may have two or more aromatic rings.

It is preferable that the ethylenically unsaturated compound B1 has a bisphenol structure from a viewpoint of improving the analytical property by suppressing swelling of the negative photosensitive resin layer by a developer. Examples of the bisphenol structure include bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), bisphenol F (2,2-bis(4-hydroxyphenyl)propane) derived The bisphenol F structure of hydroxyphenyl)methane) and the bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), and the bisphenol A structure are preferred.

As the polymerizable compound B1 having a bisphenol structure, for example, one having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure can be mentioned. compound. Both ends of the bisphenol structure may be directly bonded to the two polymerizable groups, or may be bonded via one or more alkaneoxy groups. As the alkaneoxy group added to both ends of the bisphenol structure, an ethoxy group or a propoxy group is preferable, and an ethoxy group is more preferable. The number of alkaneoxy 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 Japanese Patent Application Laid-Open No. 2016-224162, and the contents described in this publication are incorporated into the present specification.

As the polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferable, and 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane is better. Examples of 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloyloxydiethyl) oxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxyethoxypropoxy)phenyl)propane, 2 , 2-bis(4-(methacryloyloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methyl) Propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxydeca) Pentaethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxydiethoxy)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.) .

As the ethylenically unsaturated compound B1, a compound represented by the following formula (Bis) can be used.

[Chemical formula 1]

In formula (I), R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , n ₁ and n ₃ are each independently an integer of 1 to 39, And n ₁ +n ₃ is an integer from 2 to 40, n ₂ and n ₄ are each independently an integer from 0 to 29, and n ₂ +n ₄ is an integer from 0 to 30, -(AO)- and -(BO )- The arrangement of the repeating units can be random or capped. And, in the case of capping, both -(AO)- and -(BO)- can be on the biphenyl side. In one aspect, n ₁ +n ₂ +n ₃ +n ₄ is preferably an integer of 2-20, more preferably an integer of 2-16, and even more preferably an integer of 4-12. n ₂ +n ₄ is preferably an integer of 0 to 10, more preferably an integer of 0 to 4, further preferably an integer of 0 to 2, and particularly preferably 0.

The ethylenically unsaturated compound B1 may be used individually by 1 type, and may use 2 or more types together. The lower limit of the content of the ethylenically unsaturated compound B1 in the negative-type photosensitive resin layer is preferably 10% by mass or more with respect to the total mass of the negative-type photosensitive resin layer, and is preferably 20% by mass from the viewpoint of being more excellent in resolution. The above is better. The upper limit of the content of the ethylenically unsaturated compound B1 is not particularly limited, but from the viewpoints of transferability and edge fusion (the phenomenon in which the components in the negative photosensitive resin layer bleed out from the edge of the photosensitive transfer material), 70 It is preferably not more than 60% by mass, and more preferably not more than 60% by mass.

The negative photosensitive resin layer may contain ethylenically unsaturated compounds other than the above-mentioned ethylenically unsaturated compound B1. The ethylenically unsaturated compounds other than the ethylenically unsaturated compound B1 are not particularly limited, and can be appropriately selected from known compounds. Examples of ethylenically unsaturated compounds other than the ethylenically unsaturated compound B1 include compounds having one ethylenically unsaturated group in one molecule (hereinafter, also referred to as "monofunctional ethylenically unsaturated compounds"). .), bifunctional ethylenically unsaturated compounds without aromatic rings and ethylenically unsaturated compounds with trifunctional or more functions.

Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene Glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate and phenoxy(meth)ethyl acrylate.

Examples of bifunctional ethylenically unsaturated compounds not having an aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane ester 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 diacrylate Methanol 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 new Pentylene glycol di(meth)acrylate. Examples of polyalkylene glycol di(meth)acrylates include polyethylene glycol di(meth)acrylates, dipropylene glycol diacrylates, tripropylene glycol diacrylates, and polypropylene glycol di(meth)acrylates. )Acrylate. Examples of urethane di(meth)acrylates include propylene oxide-modified urethane di(meth)acrylates, and ethylene oxide and propylene oxide-modified amino groups. Formate di(meth)acrylate. As a commercial item of urethane di(meth)acrylate, for example, 8UX-015A (manufactured by TAISEI FINE CHEMICAL CO,. LTD.), UA-32P (Shin Nakamura Chemical Industry Co., LTD.), . manufactured) and UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., LTD.).

Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipeotaerythritol (tri/tetra/penta/hexa) (meth)acrylate, neotaerythritol (tri/tetra) (methyl) Acrylates, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid triacrylate (Meth)acrylates, glycerol tri(meth)acrylates, and modified alkylene oxides thereof. Here, "(tri/tetra/penta/hexa)(meth)acrylate" means tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate and hexa(meth)acrylate ) concept of acrylate, "(tri/tetra)(meth)acrylate" is a concept including tri(meth)acrylate and tetra(meth)acrylate. In one aspect, it is also preferable that the negative photosensitive resin layer contains the above-mentioned polymerizable compound B1 and a trifunctional or more ethylenically unsaturated compound, and includes the above-mentioned polymerizable compound B1 and two or more kinds of trifunctional or more functional ethylenically unsaturated compounds. Saturated compounds are more preferred. In this case, the mass ratio of the ethylenically unsaturated compound B1 to the trifunctional or more functional ethylenically unsaturated compound is (total mass of the ethylenically unsaturated compound B1): (total mass of the trifunctional or more functional ethylenically unsaturated compound )=1:1～5:1 is preferable, 1.2:1～4:1 is more preferable, and 1.5:1～3:1 is further preferable. Moreover, in one aspect, it is preferable that the negative photosensitive resin layer contains the above-mentioned polymerizable compound B1 and two or more kinds of trifunctional ethylenically unsaturated compounds.

As an alkylene oxide modified product of a trifunctional or more than trifunctional ethylenically unsaturated compound, a caprolactone modified (meth)acrylate compound (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd.) can be mentioned. , A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide modified (meth)acrylate compound (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., Shin-Nakamura ATM-35E and A-9300 manufactured by Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by DAI-CELL-ALLNEX LTD., etc.), ethoxylated glycerol triacrylate (Shin-Nakamura Chemical Co. ., Ltd. A-GLY-9E etc.), ARONIX (registered trademark) TO-2349 (TOAGOSEI CO., LTD.), ARONIX M-520 (TOAGOSEI CO., LTD.) and ARONIX M-510 (manufactured by TOAGOSEI CO., LTD.).

As the ethylenically unsaturated compounds other than the ethylenically unsaturated compound B1, the ethylenically unsaturated compounds having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942 can be used.

From the viewpoint of resolution and linearity, the value of the ratio (Mm/Mb) of the content Mm of the ethylenically unsaturated compound in the negative photosensitive resin layer to the content Mb of the alkali-soluble resin is preferably 1.0 or less, and is preferably 0.9 The following is more preferable, and 0.5 or more and 0.9 or less are particularly preferable. From the viewpoint of curability and analytical properties, it is preferable that the ethylenically unsaturated compound in the negative photosensitive resin layer contains a (meth)acrylic compound. Furthermore, the ethylenically unsaturated compound in the negative photosensitive resin layer contains a (meth)acrylic compound from the viewpoints of curability, resolution, and linearity, and the content of the acrylic compound is relative to the content of the acrylic compound in the negative photosensitive resin layer. It is more preferable that the total mass of the said (meth)acrylic compound contained is 60 mass % or less.

The molecular weight (weight average molecular weight (Mw) in the case of distribution) of the ethylenically unsaturated compound including the ethylenically unsaturated compound B1 is preferably 200 to 3,000, more preferably 280 to 2,200, and furthermore 300 to 2,200 better.

An ethylenically unsaturated compound may be used individually by 1 type, and may use 2 or more types together. The content of the ethylenically unsaturated compound in the negative photosensitive resin layer is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass relative to the total mass of the negative photosensitive resin layer, and 20% by mass. Mass % - 50 mass % are more preferable.

＜＜Photopolymerization initiator＞＞ It is preferable that the negative photosensitive resin layer contains a photopolymerization initiator. The photopolymerization initiator is a compound that receives activating light rays such as ultraviolet rays, visible rays, and X rays to initiate the polymerization of the polymerizable compound. It does not specifically limit as a photopolymerization initiator, A well-known photopolymerization initiator can be used. As a photopolymerization initiator, a photoradical polymerization initiator and a photocationic polymerization initiator are mentioned, for example. Among them, it is preferable that the photopolymerization initiator is a photoradical polymerization initiator from the viewpoints of analytical properties and pattern forming properties.

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

As the photoradical polymerization initiator, for example, the polymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-95716 and paragraphs 0064-0081 of JP-A-2015-14783 can be used.

As a photoradical polymerization initiator, for example, dimethylaminobenzoic acid ethyl ester (DBE, CAS No. 10287-53-3), benzoin methyl ether, methoxyphenyl (p,p'-diethyl benzoate) can be mentioned. methoxybenzyl ester), TAZ-110 (product name: manufactured by Midori Kagaku Co., Ltd.), benzophenone, TAZ-111 (product name: manufactured by Midori Kagaku Co., Ltd.), IrgacureOXE01, OXE02, OXE03, OXE04 (manufactured by BASF Corporation), Omnirad651 and 369 (product name: manufactured by IGM Resins B.V.) and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl- 1,2'-Bisimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

As a commercial item of a photoradical polymerization initiator, for example, 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzyl oxime ) (product name: IRGACURE (registered trademark) OXE-01, manufactured by BASF Corporation), 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]ethyl Ketone-1-(O-acetoxime) (product name: IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), 2-(dimethylamino)-2-[(4 -Methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (product name: Omnirad 379EG, manufactured by IGM Resins B.V.), 2-methyl-1- (4-Methylthiophenyl)-2-morpholinopropan-1-one (product name: Omnirad 907, manufactured by IGM Resins B.V.), 2-hydroxy-1-{4-[4-(2-hydroxy-2 -Methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (product name: Omnirad 127, manufactured by IGM Resins B.V.), 2-benzyl-2-dimethylamino-1 -(4-Morpholinephenyl)butanone-1 (product name: Omnirad 369, manufactured by IGM Resins B.V.), 2-hydroxy-2-methyl-1-phenylpropan-1-one (product name: Omnirad 1173 , manufactured by IGM Resins B.V.), 1-hydroxycyclohexyl phenyl ketone (product name: Omnirad 184, manufactured by IGM Resins B.V.), 2,2-dimethoxy-1,2-diphenylethan-1-one ( Product name: Omnirad 651, manufactured by IGM Resins B.V.), 2,4,6-trimethylbenzyl-diphenylphosphine oxide (product name: Omnirad TPO H, manufactured by IGM Resins B.V.), bis(2,4 ,6-Trimethylbenzyl)phenylphosphine oxide (product name: Omnirad 819, manufactured by IGM Resins B.V.), oxime ester-based photopolymerization initiator (product name: Lunar 6, manufactured by DKSH Management Ltd.) , 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole bis polymer) (product name: B-CIM, manufactured by Hampford Research Inc.) and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (product name: BCTB, Tokyo Chemical Industry Co., Ltd.) (product name: BCTB, Tokyo Chemical Manufactured by Industry Co., Ltd.).

The photocationic polymerization initiator (photoacid generator) is a compound that receives activating light to generate an acid. As the photocationic polymerization initiator, a compound that generates an acid in response to activating light having a wavelength of 300 nm or more, preferably a wavelength of 300 to 450 nm, is preferable. The chemical structure of the photocationic polymerization initiator is not limited. Regarding the photocationic polymerization initiator that does not directly sense activating light with a wavelength of 300 nm or more, if it is a compound that generates an acid by using a sensitizer to sense activating light with a wavelength of 300 nm or more, it is also preferable to combine with a sensitizer. used. As the photocationic polymerization initiator, a photocationic polymerization initiator that generates an acid having a pKa of 4 or less is preferable, a photocationic polymerization initiator that generates an acid having a pKa of 3 or less is more preferable, and a photocationic polymerization initiator that generates an acid having a pKa of 2 or less is more preferable. Acid photocationic polymerization initiators are particularly preferred. The lower limit of pKa is not particularly limited, but, for example, -10.0 or more is preferable.

As a photocationic polymerization initiator, an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator are mentioned. Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryl iodonium salts and triaryl perionium salts, and quaternary ammonium salts. As the ionic photocationic polymerization initiator, the ionic photocationic polymerization initiators described in paragraphs 0114 to 0133 of JP-A No. 2014-85643 can be used.

Examples of the nonionic photocationic polymerization initiator include trichloromethyl-symmetric tris, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. The compounds described in paragraphs 0083 to 0088 of JP-A No. 2011-221494 can be used as trichloromethyl-symmetric tris, diazomethane compounds, and imide sulfonate compounds. As the oxime sulfonate compound, the compounds described in paragraphs 0084 to 0088 of International Publication No. 2018/179640 can be used.

The negative photosensitive resin layer may contain one type of photopolymerization initiator alone, or two or more types may be contained. The lower limit of the content of the photopolymerization initiator in the negative photosensitive resin layer is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and 1.0 relative to the total mass of the photosensitive resin layer. It is more preferable that it is more than mass %. The upper limit of the content of the photopolymerization initiator is not particularly limited, but is preferably 10% by mass or less, and more preferably 5% by mass or less with respect to the total mass of the photosensitive resin layer.

＜＜Alkali-soluble resin＞＞ It is preferable that the negative photosensitive resin layer contains an alkali-soluble resin. In addition, in this specification, "alkali solubility" means that the solubility of sodium carbonate in 100 g of 1 mass % aqueous solution at liquid temperature 22 degreeC is 0.1 g or more. Although it does not specifically limit as an alkali-soluble resin, For example, the well-known alkali-soluble resin used for an etching resist is mentioned preferably. Preferably, the alkali-soluble resin is a binder polymer. As the alkali-soluble resin, an alkali-soluble resin having an acid group is preferable. Among them, as the alkali-soluble resin, the polymer A described later is preferable.

-Polymer A- As the alkali-soluble resin, it is preferable to contain the polymer A. The upper limit of the acid value of the polymer A is preferably 220 mgKOH/g or less, more preferably less than 200 mgKOH/g, and less than 190 mgKOH/g, from the viewpoint of suppressing the swelling of the photosensitive resin layer by the developer and further improving the resolution. g is further preferred. The lower limit of the acid value of the polymer A is not particularly limited, but from the viewpoint of more excellent developability, it is preferably 60 mgKOH/g or more, more preferably 120 mgKOH/g or more, further preferably 150 mgKOH/g or more, and 170 mgKOH/g. g and above are particularly preferred.

In addition, the acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample. In this specification, the unit of an acid value is described as mgKOH/g. The acid value can be calculated from, for example, the average content of acid groups in the compound. The acid value of the polymer A should just be adjusted according to the kind of the structural unit which comprises the polymer A, and the content of the structural unit containing an acid group.

The weight average molecular weight of the polymer A is preferably 5,000 to 500,000. The upper limit of the weight average molecular weight of the polymer A is preferably 500,000 or less from the viewpoint of improving resolution and developability. The weight average molecular weight of the polymer A is more preferably 100,000 or less, more preferably 60,000 or less, and particularly preferably 50,000 or less. On the other hand, the lower limit of the weight average molecular weight of the polymer A is preferably 5,000 or more from the viewpoint of controlling the properties of the developed aggregates and the properties of the unexposed film such as edge melting properties and wafer dicing properties. The weight average molecular weight of the polymer A is more preferably 10,000 or more, more preferably 20,000 or more, and particularly preferably 30,000 or more. The edge meltability refers to the degree to which the photosensitive resin layer easily overflows from the end surface of the roll when the photosensitive transfer material is wound up in a roll shape. The chipability refers to the degree to which wafers are easily scattered when the unexposed film is cut with a dicing blade. If the wafer adheres to the upper surface of the photosensitive resin layer, etc., it will be transferred to a mask in a subsequent exposure step and the like, and it will be a cause of defective products. The degree of dispersion of the polymer A is preferably 1.0-6.0, more preferably 1.0-5.0, still more preferably 1.0-4.0, and still more preferably 1.0-3.0. In the present invention, the molecular weight is a value measured using gel permeation chromatography. The degree of dispersion is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight).

In the negative photosensitive resin layer, it is preferable that the polymer A contains a monomer component having an aromatic hydrocarbon group from the viewpoint of suppressing the increase in line width and the deterioration of the resolution when the focus position shifts during exposure. Moreover, as such an aromatic hydrocarbon group, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted aralkyl group are mentioned, for example. The lower limit of the content ratio of the monomer component having an aromatic hydrocarbon group in the polymer A is based on the total mass of all the monomer components, preferably 20% by mass or more, more preferably 30% by mass or more, and 40% by mass or more. More preferably, 45 mass % or more is particularly preferable, and 50 mass % or more is most preferable. The upper limit of the content ratio of the monomer component is not particularly limited, but is preferably 95% by mass or less, and more preferably 85% by mass or less. Moreover, the content ratio of the monomer component which has an aromatic hydrocarbon group when several types of polymer A are contained was calculated|required as a weight average value.

Examples of the monomer having the above-mentioned aromatic hydrocarbon group include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (eg, methylstyrene, vinyltoluene, tert-butoxy). styrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.). Among them, a monomer having an aralkyl group or styrene as the monomer system having the above-mentioned aromatic hydrocarbon group is preferable. In one aspect, when the monomer component having an aromatic hydrocarbon group in the polymer A is styrene, the content ratio of the styrene monomer component is based on the total mass of all the monomer components, and ranges from 20% by mass to 50% by mass. The mass % is preferable, 25 mass % to 45 mass % is more preferable, 30 mass % to 40 mass % is further preferable, and 30 mass % to 35 mass % is particularly preferable.

Examples of the aralkyl group include substituted or unsubstituted phenylalkyl groups (excluding benzyl groups), substituted or unsubstituted benzyl groups, and the like, and substituted or unsubstituted benzyl groups are preferred.

As a monomer which has a phenylalkyl group, phenethyl (meth)acrylate etc. are mentioned.

Examples of the monomer having a benzyl group include benzyl (meth)acrylates having benzyl groups, such as benzyl (meth)acrylate and benzyl chloride (meth)acrylate; vinylbenzyl chloride, vinylbenzene Vinyl monomers with benzyl groups such as methanol. Among them, benzyl (meth)acrylate is preferable as the monomer having a benzyl group. In one aspect, when the monomer component having an aromatic hydrocarbon group in the polymer A is benzyl (meth)acrylate, the content ratio of the benzyl (meth)acrylate monomer component is the same as that of all the monomer components. Based on the total mass, 50 to 95% by mass is preferred, 60 to 90% by mass is more preferred, 70 to 90% by mass is further preferred, and 75 to 90% by mass is particularly preferred.

Polymer A containing a monomer component having an aromatic hydrocarbon group is obtained by polymerizing a monomer having an aromatic hydrocarbon group with at least one of the first monomers described later and/or at least one of the second monomers described later It is better to obtain.

The polymer A that does not contain a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the first monomers described later, by polymerizing at least one of the first monomers with the first monomer described later. More preferably, it is obtained by copolymerizing at least one of the two monomers.

The first monomer has a carboxyl 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. Acid half ester, etc. Among these, as the first monomer, (meth)acrylic acid is preferable. The content ratio of the first monomer in the polymer A is based on the total mass of all monomer components, preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and 15% by mass to 30% by mass The mass % is more preferable.

The copolymerization ratio of the first monomer is preferably 10% by mass to 50% by mass based on the total mass of all the monomer components. From the viewpoint of developing good developability, from the viewpoint of controlling edge meltability, etc., it is preferable to set the above-mentioned copolymerization ratio to be 10 mass % or more. The lower limit of the above-mentioned copolymerization ratio is more preferably 15% by mass or more, and even more preferably 20% by mass or more. From the viewpoint of the high resolution and edge shape of the photoresist pattern, and further from the viewpoint of the chemical resistance of the photoresist pattern, the copolymerization ratio is preferably 50 mass % or less. From these viewpoints, the upper limit of the copolymerization ratio is more preferably 35% by mass or less, more preferably 30% by mass or less, and particularly preferably 27% by mass or less.

The second monomer is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and (meth)acrylic acid. n-Butyl, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid (meth)acrylates such as cyclohexyl ester and 2-ethylhexyl (meth)acrylate; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile and the like. Among them, as the second monomer, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and n-butyl (meth)acrylate are preferred, and methyl (meth)acrylate is particularly preferred . The content ratio of the second monomer in the polymer A is based on the total mass of all the monomer components, preferably 5% by mass to 60% by mass, more preferably 15% by mass to 50% by mass, and 20% by mass to 45% by mass The mass % is more preferable.

From the viewpoint of suppressing the increase in line width and the deterioration of resolution when the focus position shifts during exposure, it is preferable that the second monomer contains a monomer having an aralkyl group and/or styrene as a monomer. As the second monomer, for example, a copolymer comprising methacrylic acid, benzyl methacrylate and styrene, a copolymer comprising methacrylic acid, methyl methacrylate, benzyl methacrylate and styrene, etc. good. In one aspect, the polymer A contains 25% to 40% by mass of a monomer component having an aromatic hydrocarbon group, 20% to 35% by mass of the first monomer component, and 30% to 45% by mass of the second monomer component. The mass % of the polymer is preferred. In another aspect, the polymer A is preferably a polymer containing 70% by mass to 90% by mass of the monomer component having an aromatic hydrocarbon group and 10% by mass to 25% by mass of the first monomer component.

The polymer A may have any of a linear structure, a branched structure, and an alicyclic structure in a 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, a branched structure and an alicyclic structure can be introduced into the side chain of the polymer A . The group having an alicyclic structure may be monocyclic or polycyclic. Specific examples of the monomer containing a group having a branched structure in the side chain include, for example, isopropyl (meth)acrylate, isobutyl (meth)acrylate, and second butyl (meth)acrylate. ester, tertiary butyl (meth)acrylate, isoamyl (meth)acrylate, tertiary amyl (meth)acrylate, isoamyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, 3-octyl (meth)acrylate, etc. Among these, isopropyl (meth)acrylate, isobutyl (meth)acrylate or tertiary butyl methacrylate are preferable, and isopropyl methacrylate or tertiary butyl methacrylate is more preferable . 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 examples of the monomer having a carbon number (carbon atom) (number) 5 to 20 (meth)acrylates of alicyclic hydrocarbon groups. More specific examples of the monomer containing a group having an alicyclic structure in the side chain include (meth)acrylic acid (bicyclo[2.2.1]heptyl-2), (meth)acrylic acid- 1-adamantyl ester, (meth)acrylic acid-2-adamantyl ester, (meth)acrylic acid-3-methyl-1-adamantyl ester, (meth)acrylic acid-3,5-dimethyl ester methyl-1-adamantyl ester, (meth)acrylate-3-ethyladamantyl ester, (meth)acrylate-3-methyl-5-ethyl-1-adamantyl ester, (methyl) ) 3,5,8-triethyl-1-adamantyl acrylate, (meth)acrylate-3,5-dimethyl-8-ethyl-1-adamantyl acrylate, (methyl) 2-Methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, (meth)acrylate Octahydro-4,7-mentanoindene-5-yl acrylate, (meth)acrylate octahydro-4,7-menthol-1-ylmethyl ester, (meth)acrylic acid-1- Menthyl ester, (meth)acrylic acid tricyclodecane, (meth)acrylic acid-3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl ester, (meth)acrylic acid- 3,7,7-Trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl ester, (Nor) camphenyl (meth)acrylate, (meth)acrylate isocamphenate, (meth)acrylate base ester, (meth)acrylic acid-2,2,5-trimethylcyclohexyl ester, (meth)acrylic acid cyclohexyl ester, etc. Among these (meth)acrylates, as monomers containing a group having an alicyclic structure in a side chain, cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, isopropyl (meth)acrylate Camphenyl ester, (meth)acrylate-1-adamantyl ester, (meth)acrylate-2-adamantyl ester, (meth)acrylic acid filinium ester, (meth)acrylate 1-menthyl ester or ( Meth) acrylic acid tricyclodecane is preferred, (meth) acrylic acid cyclohexyl, (meth) acrylic acid norbornyl, (meth) acrylic acid isobornyl, (meth) acrylic acid-2-adamantyl Esters or (meth)acrylate tricyclodecane are particularly preferred.

One type of polymer A can be used alone, or two or more types of monomer A can be mixed and used. When two or more kinds of monomers A are mixed and used, two kinds of polymers A containing a monomer component having an aromatic hydrocarbon group are mixed and used, or a polymer A containing a monomer component having an aromatic hydrocarbon group is mixed and used It is preferable to mix and use with the polymer A which does not contain the monomer component which has an aromatic hydrocarbon group. In the latter case, the use ratio of the polymer A containing the monomer having an aromatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, and 80% by mass relative to the total mass of the polymer A. It is more preferably at least 90% by mass, and more preferably at least 90% by mass.

Regarding the synthesis of the polymer A, an appropriate amount of benzyl peroxide, benzoyl peroxide, It is preferable to carry out a radical polymerization initiator, such as azoisobutyronitrile, with heating and stirring. As for the synthesis of the polymer A, the synthesis may be carried out while adding a part of the mixture dropwise to the reaction liquid. After the completion of the reaction for the synthesis of the polymer A, it may be further added to the solvent to adjust the concentration of the solution containing the polymer A to a desired concentration. As a synthesis method, in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization can be used.

The glass transition temperature Tg of the polymer A is preferably 30°C or higher and 135°C or lower. In the photosensitive resin layer, by using the polymer A having a Tg of 135° C. or lower, it is possible to suppress the increase of the line width and the deterioration of the resolution during the shift of the focus position at the time of exposure. From this viewpoint, the upper limit of the Tg of the polymer A is preferably 130°C or lower, more preferably 120°C or lower, and particularly preferably 110°C or lower. From the viewpoint of improving edge melting resistance, it is preferable to use the polymer A having a Tg of 30°C or higher. From this viewpoint, the lower limit of the Tg of the polymer A is more preferably 40°C or higher, more preferably 50°C or higher, particularly preferably 60°C or higher, and most preferably 70°C or higher.

The negative photosensitive resin layer may contain resins other than alkali-soluble resins. Examples of resins other than alkali-soluble resins include acrylic resins, styrene-acrylic copolymers (wherein the styrene content is 40 mass % or less), polyurethane resins, polyvinyl alcohol, polyethylene Formaldehyde, polyamide resin, polyester resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin, polyethyleneimine, Polyallylamine and polyalkylene glycol.

Alkali-soluble resin can be used individually by 1 type, or can also be used in mixture of 2 or more types. The ratio of the alkali-soluble resin to the total mass of the negative photosensitive resin layer is preferably 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, and even more preferably 40% by mass to 60% by mass . From the viewpoint of controlling the development time, the ratio of the alkali-soluble resin to the total mass of the negative photosensitive resin layer is preferably 90% by mass or less. On the other hand, from the viewpoint of improving edge melting resistance, the ratio of the alkali-soluble resin to the total mass of the negative photosensitive resin layer is preferably 10% by mass or more.

＜＜Compounds with unshared electron pairs＞ It is preferable that the said photosensitive resin layer contains the compound which has an unshared electron pair from a viewpoint of adhesiveness with a conductive layer. From the viewpoint of adhesion to the conductive layer, the compound having an unshared electron pair is preferably a compound having at least a nitrogen atom, an oxygen atom or a sulfur atom, and more preferably a heterocyclic compound, a thiol compound and a disulfide compound. Preferably, heterocyclic compounds are further preferred, and nitrogen-containing heterocyclic compounds are particularly preferred.

The heterocyclic ring possessed by the heterocyclic compound may be either a monocyclic ring or a polycyclic heterocyclic ring. A nitrogen atom, an oxygen atom, and a sulfur atom are mentioned as a hetero atom which a heterocyclic compound has. The heterocyclic compound preferably has at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, and more preferably has a nitrogen atom.

Preferable examples of the heterocyclic compound include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazole compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, Benzimidazole compound, benzoxazole compound or pyrimidine compound. Among the above, the heterocyclic compound is selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazole compounds, and rhodanine compounds from the viewpoint of adhesion to the conductive layer. , at least one compound in the group of thiazole compounds, benzimidazole compounds and benzoxazole compounds is preferably selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds At least one compound selected from the group consisting of a compound, a benzothiazole compound, a benzimidazole compound and a benzoxazole compound is more preferably, and at least one compound selected from the group consisting of a triazole compound and a tetrazole compound is More preferably, triazole compounds are particularly preferred.

Hereinafter, preferable specific examples of the heterocyclic compound are shown. The following compounds can be exemplified as the triazole compound and the benzotriazole compound.

[Chemical formula 2]

[Chemical formula 3]

As the tetrazole compound, the following compounds can be exemplified.

[Chemical formula 4]

[Chemical formula 5]

As the thiadiazole compound, the following compounds can be exemplified.

[Chemical formula 6]

The following compounds can be exemplified as the trisium compound.

[Chemical formula 7]

As the rhodanine compound, the following compounds can be exemplified.

[Chemical formula 8]

As the thiazole compound, the following compounds can be exemplified.

[Chemical formula 9]

As a benzothiazole compound, the following compounds can be illustrated.

[Chemical formula 10]

As the benzimidazole compound, the following compounds can be exemplified.

[Chemical formula 11]

[Chemical formula 12]

As the benzoxazole compound, the following compounds can be exemplified.

[Chemical formula 13]

As a thiol compound, an aliphatic thiol compound is mentioned preferably. As the aliphatic thiol compound, a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, a bifunctional or more aliphatic thiol compound) is preferably used. Examples of the polyfunctional aliphatic thiol compound include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutanoyloxy)butane, neopentyltetrakis Alcohol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutanoyloxyethyl)-1,3,5-tris-2,4,6(1H,3H,5H )-trione, trimethylolethane tris(3-mercaptobutyrate), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, trimethylolpropane tris(3-mercaptobutyrate) mercaptopropionate), neotaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipivalerythritol hexa(3-mercaptopropionate), ethyl acetate Glycol dithiopropionate, 1,4-bis(3-mercaptobutanoyloxy)butane, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylene Methyl dithiol, 2,2'-(ethylidene disulfide) diethanethiol, meso-2,3-dimercaptosuccinic acid and bis(mercaptoethyl) ether. Examples of the monofunctional aliphatic thiol compound include 1-octanethiol, 1-dodecanethiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, and 2-ethylhexyl -3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate and stearic acid-3-mercaptopropionate.

Examples of the disulfide compound include 2-(4'-morpholinodithio)benzothiazole, 2,2'-benzimidazole disulfide, bis(2-benzamidephenyl)disulfide Sulfide, 1,1-thiobis(2-naphthol), bis(2,4,5-trichlorophenyl)disulfide, 4,4'-dithiomorpholine, tetraethylthioamine Carboxylic acid disulfide, dibenzyl disulfide, bis(2,4-dinitrobenzene) disulfide, 4,4'-diaminodiphenyl disulfide, diallyl disulfide compound, di-tert-butyl disulfide, bis(6-hydroxy-2-naphthyl) disulfide, dicyclohexyl disulfide, o-isobutyl thiamine disulfide, diphenyl disulfide.

From the viewpoint of adhesiveness with the conductive layer, the molecular weight of the compound having an unshared electron pair is preferably less than 1,000, more preferably 50 to 500, further preferably 50 to 200, and particularly preferably 50 to 115.

The photosensitive resin layer may contain 1 type of compound which has an unshared electron pair independently, and may contain 2 or more types. From the viewpoint of adhesiveness with the conductive layer, the content of the compound having an unshared electron pair is preferably 0.01% by mass to 20% by mass, and more preferably 0.1% by mass to 10% by mass relative to the total mass of the photosensitive resin layer. Preferably, 0.3 mass % to 8 mass % is more preferable, and 0.5 mass % to 5 mass % is particularly preferable.

＜＜Pigment＞＞ From the viewpoint of the visibility of the exposed part and the non-exposed part, the visibility of the pattern after development, and the analytical properties, it is preferable that the photosensitive resin layer contains a dye, and the maximum absorption wavelength in the wavelength range of 400 nm to 780 nm when the photosensitive resin layer is contained is 400 nm to 780 nm. Pigments with a wavelength of 450 nm or more whose maximum absorption wavelength is changed by acids, bases or free radicals (also referred to as "pigment N" for short) are also preferred. When the photosensitive resin layer contains the dye N, the detailed mechanism is not clear, but the adhesiveness with the adjacent layers (for example, the dummy support and the first resin layer) is improved, and the resolution is further excellent.

In this specification, "the maximum absorption wavelength of the dye is changed due to acid, alkali or radical" may refer to the state in which the dye in the color developing state is decolorized by acid, alkali or radical, and the dye in the decolorized state Any one of an aspect in which a color is developed by an acid, an alkali or a radical, and an aspect in which the pigment in the developed state is changed into a colored state of another hue. Specifically, the dye N may be a compound that changes color from a decolorized state by exposure to light, or a compound that decolorizes from a color-developed state by exposure to light. In this case, it may be a dye that generates acid, alkali, or radical in the photosensitive resin layer and acts to change the state of color development or decolorization by exposure, and may be a dye that is exposed to light by acid, alkali, or radical. It is a pigment that changes the state (eg pH) in the resin layer to change the state of color development or decolorization. It may also be a pigment that changes the state of color development or decolorization by directly receiving acid, alkali or radical as a stimulus without exposure.

Among them, from the viewpoints of visibility and resolution of the exposed part and the non-exposed part, the dye N is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and a dye whose maximum absorption wavelength is changed by a radical for better. From the viewpoints of visibility and resolution of the exposed portion and the non-exposed portion, it is relatively preferable for the photosensitive resin layer to contain a dye whose maximum absorption wavelength is changed by radicals as the dye N and to contain a photoradical polymerization initiator. good. From the viewpoint of the visibility of the exposed portion and the non-exposed portion, it is preferable that the coloring matter N is a coloring matter developed by an acid, a base, or a radical.

As an example of the color-developing mechanism of the dye N in the present invention, an aspect in which a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator) or a photosensitive resin layer is added to the photosensitive resin layer can be mentioned. Alkali generators, radical-reactive dyes, acid-reactive dyes or base-reactive dyes after exposure due to radicals, acids or bases generated by photoradical polymerization initiators, photocationic polymerization initiators or photobase generators (e.g. leuco pigments) to develop color.

From the viewpoint of visibility of the exposed part and the non-exposed part, the maximum absorption wavelength of the dye N in the wavelength range of 400 nm to 780 nm during color development of the dye N is preferably 550 nm or more, more preferably 550 nm to 700 nm, and 550 nm to 550 nm 650nm is further preferable.

The maximum absorption wavelength of dye N is in the atmospheric environment, using a spectrophotometer: UV3100 (manufactured by SHIMADZU CORPORATION), measuring the transmission spectrum of a solution containing dye N (liquid temperature 25°C) in the range of 400nm to 780nm, and the above wavelengths The intensity of light in the range becomes the minimum wavelength (maximum absorption wavelength).

As a coloring matter which develops or decolorizes by exposure, a colorless compound is mentioned, for example. Examples of dyes decolorized by exposure include leuco compounds, diarylmethane-based dyes, oxa-based dyes, Kouyamaguchi-based dyes, imino naphthoquinone-based dyes, azomethine-based dyes, and Anthraquinone pigments. As the dye N, a colorless compound is preferable from the viewpoint of the visibility of the exposed part and the non-exposed part.

As the leuco compound, for example, a leuco compound having a triarylmethane skeleton (triarylmethane-based dye), a leuco compound having a spiropyran skeleton (spiropyran-based dye), and a leuco compound having a fluorescent yellow parent skeleton can be mentioned. (Fluorescent yellow parent system pigments), colorless compounds with diarylmethane skeleton (diarylmethane-based pigments), colorless compounds with rhodamine lactamide skeleton (rhodamine lactamide-based pigments), with indole Colorless compounds (indolylphthalide-based pigments) with a phthalolactone skeleton and colorless compounds with a white golden amine skeleton (white golden amine-based pigments). Among them, as the colorless compound, triarylmethane-based pigments or fluorescent yellow parent-based pigments are preferable, and colorless compounds (triphenylmethane-based pigments) or fluorescent yellow parent-based pigments having a triphenylmethane skeleton are more preferable.

As a colorless compound, it is preferable to have a lactone ring, a sultine ring, or a sultone ring from the viewpoint of the visibility of an exposed part and a non-exposed part. Thereby, the lactone ring, sulfinolactone ring or sultone ring possessed by the colorless compound can be reacted with the radical generated by the photoradical polymerization initiator or the acid generated by the photocationic polymerization initiator , the colorless compound is changed into a closed ring state to decolorize or the colorless compound is changed into an open ring state to develop color. As a colorless compound, a compound having a lactone ring, a sultone ring or a sultone ring and developing a color due to the opening of the lactone ring, the sultone ring or the sultone ring by a free radical or an acid is relatively Preferably, a compound having a lactone ring and developing color due to the ring-opening of the lactone ring by a radical or an acid is more preferable.

Examples of the dye N include the following dyes and leuco compounds. Specific examples of the dye in the dye N include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsine, methyl violet 2B, and quinardine red ( quinaldine red), rose bengal, metanil yellow, thymol sulfonphthalein, xylenol blue, methyl orange, p-methyl red, Congo red, benzene Red violet 4B, α-naphthyl red, Nile blue 2B, Nile blue A, methyl violet, malachite green, parafuchsin, Victoria pure blue-naphthalene sulfonate, Victoria pure blue BOH (Hodogaya Chemical Co. ., Ltd.), Oil Blue #603 (Orient Chemical Co., Ltd.), Oil Powder #312 (Orient Chemical Co., Ltd.), Oil Red 5B (Orient Chemical Co., Ltd.) , Oil Scarlet #308 (manufactured by Orient Chemical Co., Ltd.), Oil Red OG (manufactured by Orient Chemical Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Co., Ltd.), Oil Green #502 (Orient Chemical Co., Ltd. Co., Ltd.), SPIRON Red BEH SPECIAL (manufactured by Hodogaya Chemical Co., Ltd.), m-cresol violet, cresyl red, rhodamine B, rhodamine 6G, sulforhodamine B, golden amine, 4 - p-diethylaminophenylimino-naphthoquinone, 2-carboxyanilino-4-p-diethylaminophenylimino-naphthoquinone, 2-carboxystearylamino-4-p-N, N-bis(hydroxyethyl)amino-phenylimino-naphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone and 1 - β-Naphthalene-4-p-diethylaminophenylimino-5-pyrazolone.

Specific examples of the leuco compound in the dye N include p,p',p"-hexamethyltriaminotriphenylmethane (leuco crystal violet), Pergascript Blue SRB (manufactured by Ciba Geigy), crystal violet Lactone, malachite green lactone, benzalkonium colorless methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)amino fluorescent yellow parent , 2-anilino-3-methyl-6-(N-ethyl-p-toluidine) fluorescent yellow parent, 3,6-dimethoxyfluorescent yellow parent, 3-(N,N-diethyl amino)-5-methyl-7-(N,N-dibenzylamino)fluorescein yellow parent, 3-(N-cyclohexyl-N-methylamino)-6-methyl-7 - Anilino fluorescent yellow precursor, 3-(N,N-diethylamino)-6-methyl-7-anilino fluorescent yellow precursor, 3-(N,N-diethylamino)- 6-Methyl-7-Amino Lucifer Yellow Parent, 3-(N,N-Diethylamino)-6-Methyl-7-Chloro Lucifer Yellow Parent, 3-(N,N-Diethylamino) Ethylamino)-6-methoxy-7-amino fluorescent yellow precursor, 3-(N,N-diethylamino)-7-(4-chloroanilino) fluorescent yellow precursor, 3 -(N,N-Diethylamino)-7-chlorofluorescein precursor, 3-(N,N-diethylamino)-7-benzylaminofluorescein precursor, 3-(N ,N-diethylamino)-7,8-benzofluorescein yellow parent, 3-(N,N-dibutylamino)-6-methyl-7-anilino fluorescent yellow parent, 3 -(N,N-Dibutylamino)-6-methyl-7-sulfanyl fluorescein precursor, 3-piperidinyl-6-methyl-7-anilino fluorescein precursor, 3- Pyrrolidyl-6-methyl-7-anilino fluorescent yellow parent, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis( 1-n-Butyl-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-phthalolactone, 3-(4-diethyl) aminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide and 3',6'-bis(diphenylamino)spiroisobenzofuran- 1(3H),9'-[9H]koushin-3-one.

From the viewpoints of the visibility of the exposed part and the non-exposed part, the visibility of the pattern after development, and the analytical properties, the dye N is preferably a dye whose maximum absorption wavelength is changed by radicals, and a dye that develops color by radicals for better. As the pigment N, leuco crystal violet, crystal violet lactone, brilliant green or Victoria pure blue-naphthalene sulfonate is preferable.

A coloring matter may be used individually by 1 type, and may use 2 or more types. From the viewpoint of the visibility of the exposed part and the non-exposed part, the visibility of the pattern after development, and the analytical properties, the content of the dye is preferably 0.1 mass % or more with respect to the total mass of the photosensitive resin layer, and 0.1 mass % to 0.1 mass %. 10 mass % is more preferable, 0.1 mass % - 5 mass % are more preferable, and 0.1 mass % - 1 mass % are especially preferable. From the viewpoints of the visibility of the exposed part and the non-exposed part, the visibility of the pattern after development, and the analytical properties, the content of the dye N is preferably 0.1% by mass or more, preferably 0.1% by mass, with respect to the total mass of the photosensitive resin layer. -10 mass % is more preferable, 0.1 mass % - 5 mass % are more preferable, and 0.1 mass % - 1 mass % are especially preferable.

The content of the dye N means the content of the dye when all the dyes N contained in the photosensitive resin layer are brought into a colored state. Hereinafter, a method for quantifying the content of the dye N will be described by taking a dye that develops color by radicals as an example. First, 2 solutions are adjusted. Specifically, a solution in which 0.001 g of a dye was dissolved in 100 mL of methyl ethyl ketone and a solution in which 0.01 g of a dye was dissolved in 100 mL of methyl ethyl ketone were prepared. A photo-radical polymerization initiator Irgacure OXE01 (product name, BASF Japan Ltd.) was added to each of the obtained solutions, and light of 365 nm was irradiated to generate radicals, thereby setting all the dyes in a color-developed state. Then, the absorbance of each solution at a liquid temperature of 25° C. was measured using a spectrophotometer (UV3100, manufactured by SHIMADZU CORPORATION) in an atmospheric atmosphere, and a calibration curve was prepared. Next, except that 3 g of the photosensitive resin layer was dissolved in methyl ethyl ketone instead of the dye, the absorbance of the solution in which all the dyes were developed was measured by the same method as described above. Based on the absorbance of the obtained solution containing the photosensitive resin layer, the content of the pigment contained in the photosensitive resin layer was calculated according to the calibration curve.

＜＜Thermal crosslinkable compound＞＞ From the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film, it is preferable that the photosensitive resin layer contains a thermally crosslinkable compound. In addition, in this specification, the thermally crosslinkable compound which has an ethylenically unsaturated group mentioned later is not regarded as a polymerizable compound, but is regarded as a thermally crosslinkable compound. As a thermally crosslinkable compound, a methylol compound and a blocked isocyanate compound are mentioned. Among them, as a thermally crosslinkable compound, a blocked isocyanate compound is preferable from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. The blocked isocyanate compound reacts with hydroxyl and carboxyl groups. Therefore, for example, when a resin and/or a polymerizable compound or the like has at least one of a hydroxyl group and a carboxyl group, the hydrophilicity of the formed film is lowered, and the film formed by curing the photosensitive resin layer is strengthened for protection. The tendency of the membrane to function. In addition, the blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of the isocyanate is protected (so-called masking) with a blocking agent".

The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100°C to 160°C, more preferably 130°C to 150°C. The dissociation temperature of the blocked isocyanate means "the temperature of the endothermic peak accompanying the deprotection reaction of the blocked isocyanate when analyzed and measured by DSC (Differential scanning calorimetry) 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 preferably used. However, the differential scanning calorimeter is not limited to this.

As a blocking agent whose dissociation temperature is 100 degreeC - 160 degreeC, an active methylene compound and an oxime compound are mentioned. Examples of the active methylene compound include malonate diesters (for example, dimethyl malonate, diethyl malonate, di-n-butyl malonate, and di-2-ethylhexyl malonate) and many more. Examples of the oxime compound include formaldehyde oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, and the like having a structure represented by -C(=N-OH)- in the molecule. compounds, etc. Among these, it is preferable that the end-capping agent having a dissociation temperature of 100°C to 160°C contains an oxime compound, for example, from the viewpoint of storage stability.

For example, it is preferable that the blocked isocyanate compound has an isocyanurate structure from the viewpoints of improving the brittleness of the film, improving the adhesive force with the transfer target body, and the like. The blocked isocyanate compound having an isocyanurate structure is obtained, for example, by isocyanurating and protecting hexamethylene diisocyanate. Among the blocked isocyanate compounds having an isocyanurate structure, a compound having an oxime structure having an oxime compound as a blocking agent is easier to set the dissociation temperature in a preferable range than a compound having no oxime structure, and It is preferable from the viewpoint that it is easy to reduce the development residue.

The blocked isocyanate compound may have a polymerizable group. It does not specifically limit as a polymerizable group, A well-known polymerizable group can be used, and a radical polymerizable group is preferable. The polymerizable group includes an ethylenically unsaturated group such as a (meth)acryloyloxy group, a (meth)acrylamido group, and a styryl group, and a group having an epoxy group such as a glycidyl group. Among them, as the polymerizable group, an ethylenically unsaturated group is preferable, a (meth)acryloyloxy group is more preferable, and an acryloxy group is further preferable.

As the blocked isocyanate compound, a commercial item can be used. Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, and Karenz (registered trademark) MOI-BP (the above are manufactured by SHOWA DENKO K.K.) , End-capped DURANATE series (for example, DURANATE (registered trademark) TPA-B80E, DURANATE (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation.). As the blocked isocyanate compound, compounds having the following structures can also be used.

[Chemical formula 14]

A thermally crosslinkable compound may be used individually by 1 type, and may use 2 or more types. When the photosensitive resin layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1% by mass to 50% by mass, and preferably 5% by mass to 30% by mass relative to the total mass of the photosensitive resin layer. for better.

<<Polymer having a structural unit having an acid group protected by an acid-decomposable group>> The positive-type photosensitive resin layer includes a polymer (hereinafter, sometimes referred to as "polymer X") having a structural unit (hereinafter, sometimes referred to as "structural unit A") having an acid group protected by an acid-decomposable group .) is preferred. The positive photosensitive resin layer may contain one type of polymer X alone, or two or more types of polymer X may be contained.

In the polymer X, the acid group protected by the acid-decomposable group is converted into an acid group through a deprotection reaction by the action of an acidic substance (eg, acid) based on the catalytic amount generated by exposure. An acid group is generated in the polymer X, and the solubility of the positive-type photosensitive resin layer to a developer increases.

As the polymer X, an addition polymerization type polymer is preferable, and a polymer having a structural unit derived from (meth)acrylic acid or its ester is more preferable.

-Constituent unit having an acid group protected by an acid-decomposable group- It is preferable that the polymer X has a structural unit having an acid group having an acid-decomposable group (that is, the structural unit A). Since the polymer X has the structural unit A, the sensitivity of the positive-type photosensitive resin layer is improved.

The acid group is not limited, and a known acid group can be used. The acid group is preferably a carboxyl group or a phenolic hydroxyl group.

Examples of the acid-decomposable group include a group relatively easily decomposed by an acid and a group relatively difficult to decompose by an acid. Examples of groups that are relatively easily decomposed by an acid include acetal-type protecting groups (for example, 1-alkoxyalkyl groups, tetrahydropyranyl groups, and tetrahydrofuranyl groups). As a group which is relatively hard to decompose by an acid, a tertiary alkyl group (for example, 3rd butyl group) and a tertiary alkoxycarbonyl group (for example, 3rd butoxycarbonyl group) are mentioned, for example. Among the above, the acid-decomposable group is preferably an acetal-type protecting group.

The molecular weight of the acid-decomposable group is preferably 300 or less from the viewpoint of suppressing variation in the line width of the resin pattern.

From the viewpoints of sensitivity and resolution, the structural unit A is preferably a structural unit represented by the following formula A1, a structural unit represented by the formula A2, or a structural unit represented by the formula A3, and the structural unit represented by the formula A3 is preferably The constituent unit is better. The structural unit represented by the formula A3 is a structural unit having a carboxyl group protected by an acetal-type acid-decomposable group.

[Chemical formula 15]

In formula A1, R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹¹ and R ¹² represents an alkyl group or an aryl group, R ¹³ represents an alkyl group or an aryl group, and R ¹¹ Alternatively, R ¹² and R ¹³ may be linked to form a cyclic ether, R ¹⁴ represents a hydrogen atom or a methyl group, X ¹ represents a single bond or a divalent linking group, R ¹⁵ represents a substituent, and n represents an integer of 0-4.

In formula A2, R ²¹ and R ²² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ²¹ and R ²² is an alkyl group or an aryl group, R ²³ represents an alkyl group or an aryl group, and R ²¹ Or R ²² and R ²³ can be linked to form a cyclic ether, and R ²⁴ each independently represents a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, and a hydroxyalkyl group , arylcarbonyl, aryloxycarbonyl or cycloalkyl, and m represents an integer of 0-3.

In formula A3, R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ³¹ and R ³² is an alkyl group or an aryl group, R ³³ represents an alkyl group or an aryl group, and R ³¹ Or R ³² and R ³³ may be linked to form a cyclic ether, R ³⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or an aryl extended group.

In formula A3, when R ³¹ or R ³² is an alkyl group, the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms. In formula A3, when R ³¹ or R ³² is an aryl group, the aryl group is preferably a phenyl group. In formula A3, it is preferable that R ³¹ and R ³² are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. In formula A3, R ³³ is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. In formula A3, the alkyl group and aryl group represented by R ³¹ to R ³³ may have a substituent. In formula A3, R ³¹ or R ³² and R ³³ are preferably linked to form a cyclic ether. The number of ring members of the above-mentioned cyclic ether is preferably 5 or 6, more preferably 5. In formula A3, X ⁰ is preferably a single bond. The arylidene group may have a substituent. In Formula A3, it is preferable that R ³⁴ is a hydrogen atom from the viewpoint that the glass transition temperature (Tg) of the polymer X can be further lowered.

The content of the structural unit in which R ³⁴ in Formula A3 is a hydrogen atom is preferably 20% by mass or more with respect to the total mass of the structural unit A contained in the polymer X. The content of the structural unit in which R ³⁴ in the formula A3 in the structural unit A is a hydrogen atom can be confirmed by the intensity ratio of the peak intensities measured by ¹³ C-nuclear magnetic resonance spectrum (NMR) and calculated by a conventional method.

As a preferable aspect of Formula A1 - Formula A3, the paragraph 0044 - 0058 of International Publication No. 2018/179640 can be referred to.

In the formulas A1 to A3, from the viewpoint of sensitivity, the acid-decomposable group is preferably a group having a cyclic structure, more preferably a group having a tetrahydrofuran ring structure or a tetrahydropyran ring structure, and a group having a tetrahydrofuran The group of the ring structure is further preferred, and the tetrahydrofuranyl group is particularly preferred.

The polymer X may have one kind of constituent unit A alone, or may have two or more kinds of constituent units A.

The content of the structural unit A is preferably 10% by mass to 70% by mass, more preferably 15% by mass to 50% by mass, and particularly preferably 20% by mass to 40% by mass relative to the total mass of the polymer X. When the content of the structural unit A is within the above-mentioned range, the resolution is further improved. When the polymer X contains two or more types of structural units A, the content of the above-mentioned structural units A shall represent the total content of the two or more types of structural units A. The content of the structural unit A can be confirmed by the intensity ratio of the peak intensities calculated by the conventional method from the ¹³ C-NMR measurement.

-Constituent unit with an acid group- The polymer X may have a structural unit having an acid group (hereinafter, sometimes referred to as "constitutive unit B").

The structural unit B is a structural unit having an acid group not protected by an acid-decomposable group. That is, the structural unit B is a structural unit which has an acid group which does not have a protective group. Since the polymer X has the structural unit B, the sensitivity at the time of pattern formation is said to be good. Furthermore, since the polymer X has the structural unit B, it becomes easy to melt|dissolve in an alkaline developing solution in the image development process after exposure. Therefore, the development time is shortened.

The acid group in the structural unit B represents a proton dissociative group with a pKa of 12 or less. From the viewpoint of improving the sensitivity, the upper limit of the pKa of the acid group is preferably 10 or less, more preferably 6 or less. The lower limit of the pKa of the acid group is preferably -5 or more.

As an acid group, a carboxyl group, a sulfonamido group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, and a sulfonamido group are mentioned, for example. The acid group is preferably a carboxyl group or a phenolic hydroxyl group, more preferably a carboxyl group.

The polymer X may have a single type of the structural unit B, or may have two or more types of the structural unit B.

The content of the structural unit B is preferably 0.01% by mass to 20% by mass, more preferably 0.01% by mass to 10% by mass, and particularly preferably 0.1% by mass to 5% by mass relative to the total mass of the polymer X. When the content of the structural unit B is within the above-mentioned range, the analytical properties become more favorable. When the polymer X has two or more types of structural units B, the content of the above-mentioned structural units B shall be referred to as the total content of the two or more types of structural units B. The content of the structural unit B can be confirmed by the intensity ratio of the peak intensities calculated by the conventional method from the ¹³ C-NMR measurement.

-Other constituent units- It is preferable that the polymer X has other structural units (hereinafter, sometimes referred to as "constitutive unit C") other than the structural unit A and the structural unit B described above. Each characteristic of the polymer X can be adjusted by preparing at least one of the kind and content of the structural unit C. The polymer X has the structural unit C, so that the glass transition temperature, acid value, hydrophilicity and hydrophobicity of the polymer X can be easily adjusted.

Examples of monomers that form the structural unit C include styrenes, (meth)acrylic acid alkyl esters, (meth)acrylic acid cyclic alkyl esters, (meth)acrylic acid aryl esters, and unsaturated dimethacrylates. Carboxylic acid diesters, bicyclic unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids and unsaturated dicarboxylic acid anhydrides.

From the viewpoint of the adhesiveness with the substrate, the monomer forming the structural unit C is preferably an alkyl (meth)acrylate, and the alkyl (meth)acrylate having an alkyl group having 4 to 12 carbon atoms is more preferable. good. Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylate 2-ethylhexyl acrylate.

Examples of the structural unit C include those derived from styrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinyl benzoate, Ethyl vinylbenzoate, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, benzyl (meth)acrylate, cyclopentyl (meth)acrylate , (meth) cyclohexyl acrylate, (meth) acrylic acid isobornyl ester, acrylonitrile or ethylene glycol monoacetate mono (meth) acrylate structural unit. As a structural unit C, the structural unit derived from the compound described in Unexamined-Japanese-Patent No. 2004-264623 Paragraph 0021 - 0024 can also be mentioned.

From an analytical viewpoint, it is preferable that the structural unit C includes a structural unit having a basic group. As a basic group, the group which has a nitrogen atom is mentioned, for example. As a group which has a nitrogen atom, an aliphatic amine group, an aromatic amine group, and a nitrogen-containing heteroaromatic ring group are mentioned, for example. The basic group is preferably an aliphatic amine group.

The aliphatic amine group may be any one of the first-order amino group, the second-order amino group, and the third-order amino group, but from the viewpoint of analytical performance, the second-order amino group or the third-order amino group is better.

Examples of monomers that form a structural unit having a basic group include 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, 2-(dimethylamine methacrylate) base) ethyl, acrylic acid 2,2,6,6-tetramethyl-4-piperidinyl, methacrylic acid 2,2,6,6-tetramethyl-4-piperidinyl, acrylic acid 2,2, 6,6-Tetramethyl-4-piperidinyl, 2-(diethylamino)ethyl methacrylate, 2-(dimethylamino)ethyl acrylate, 2-(diethylamino)acrylate ) ethyl, N-(3-dimethylamino)propyl methacrylate, N-(3-dimethylamino)propyl acrylate, N-(3-diethylamino)propyl methacrylate , acrylic acid N-(3-diethylamino)propyl, methacrylic acid 2-(diisopropylamino)ethyl, methacrylic acid 2-morpholinoethyl, acrylic acid 2-morpholinoethyl , N-[3-(dimethylamino)propyl] acrylamide, 4-aminostyrene, 4-vinylpyridine, 2-vinylpyridine, 3-vinylpyridine, 1-vinylimidazole, 2-methyl-1-vinylimidazole, 1-allylimidazole and 1-vinyl-1,2,4-triazole. Among the above, 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate is preferable as a monomer that forms a structural unit having a basic group.

As the structural unit C, a structural unit having an aromatic ring or a structural unit having an alicyclic skeleton is preferable from the viewpoint of improving electrical properties. Examples of monomers that form these constituent units include styrene, α-methylstyrene, dicyclopentyl (meth)acrylate, cyclopentyl (meth)acrylate, and (meth)acrylic acid. Cyclohexyl, isobornyl (meth)acrylate and benzyl (meth)acrylate. Among the above, as the structural unit C, cyclohexyl (meth)acrylate is preferable.

The polymer X may have one kind of the structural unit C alone, or may have two or more kinds of the structural unit C.

The upper limit of the content of the structural unit C is preferably 90% by mass or less, more preferably 85% by mass or less, and particularly preferably 80% by mass or less, based on the total mass of the polymer X. The lower limit of the content of the structural unit C is preferably 10% by mass or more, and more preferably 20% by mass or more, with respect to the total mass of the polymer X. When content of the structural unit C is in the said range, the adhesiveness with a resolution and a board|substrate is further improved. When the polymer X has two or more types of structural units C, the content of the above-mentioned structural units C is set to represent the total content of the two or more types of structural units C. The content of the structural unit C can be confirmed by the intensity ratio of the peak intensities calculated by the conventional method from the ¹³ C-NMR measurement.

Preferred examples of the polymer X are shown below. However, the polymer X is not limited to the following examples. In addition, in order to obtain preferable physical properties, the ratio and weight average molecular weight of each constituent unit in the polymer X shown below are appropriately selected, respectively.

[Chemical formula 16]

-Glass transition temperature- The glass transition temperature (Tg) of the polymer X is preferably 90°C or lower, more preferably 20°C to 60°C, and particularly preferably 30°C to 50°C. When the positive-type photosensitive resin layer is formed using a transfer material to be described later, the glass transition temperature of the polymer X is within the above-mentioned range, and the transferability of the positive-type photosensitive resin layer is improved.

As a method of adjusting the Tg of the polymer X within the above-mentioned range, for example, a method using the FOX formula can be mentioned. According to the FOX formula, for example, the Tg of the target polymer X can be adjusted based on the Tg of the homopolymer of each constituent unit in the target polymer X and the mass fraction of each constituent unit.

Hereinafter, the FOX formula will be described using a copolymer having a first structural unit and a second structural unit as an example. Let the glass transition temperature of the homopolymer of the first structural unit be Tg1, the mass fraction of the first structural unit in the copolymer to be W1, and the glass transition temperature of the homopolymer of the second structural unit to be Tg2 . When the mass fraction of the second structural unit in the copolymer is set to W2, the glass transition temperature Tg0 (unit: K) of the copolymer having the first structural unit and the second structural unit can be estimated from the following formula . FOX formula: 1/Tg0=(W1/Tg1)+(W2/Tg2)

The Tg of the polymer can also be adjusted by adjusting the weight average molecular weight of the polymer.

-Acid value- From the viewpoint of analytical properties, the acid value of the polymer X is preferably 0 mgKOH/g to 50 mgKOH/g, more preferably 0 mgKOH/g to 20 mgKOH/g, and particularly preferably 0 mgKOH/g to 10 mgKOH/g.

The acid value of the polymer indicates the mass of potassium hydroxide required to neutralize the acid component per 1 g of the polymer. A specific measurement method will be described below. First, a measurement sample is dissolved in a mixed solvent (volume ratio: tetrahydrofuran/water=9/1) containing tetrahydrofuran and water. Using a potentiometric titration apparatus (for example, product name: AT-510, manufactured by KYOTO ELECTRONICS MANUFACTURING CO., LTD.), neutralization titration is performed on the obtained solution at 25°C with a 0.1 mol/L sodium hydroxide aqueous solution. The inflection point of the titration pH curve was used as the titration end point, and the acid value was calculated by the following formula. A=56.11×Vs×0.1×f/w A: Acid value (mgKOH/g) Vs: The amount of 0.1mol/L sodium hydroxide aqueous solution required for titration (mL) f: titration amount of 0.1mol/L sodium hydroxide aqueous solution w: Mass of measurement sample (g) (solid content conversion)

-Weight Average Molecular Weight- The weight average molecular weight (Mw) of the polymer X is preferably 60,000 or less in terms of the weight average molecular weight in terms of polystyrene. When the positive-type photosensitive resin layer is formed using the transfer material described later, since the weight average molecular weight of the polymer X is 60,000 or less, the positive-type photosensitive resin can be transferred at a low temperature (for example, 130° C. or less). Floor.

The weight average molecular weight of the polymer X is preferably 2,000 to 60,000, more preferably 3,000 to 50,000.

The ratio (dispersity) of the weight average molecular weight of the polymer X to the number average molecular weight of the polymer X is preferably 1.0 to 5.0, more preferably 1.05 to 3.5.

The weight average molecular weight of the polymer X can be measured by the GPC method (gel permeation chromatography). As the measurement device, various commercially available devices can be used. Hereinafter, the method for measuring the weight average molecular weight of the GPC-based polymer X will be specifically described. As a measuring apparatus, HLC (registered trademark)-8220GPC (manufactured by TOSOH CORPORATION) was used. As the column, TSKgel (registered trademark) Super HZM-M (4.6 mmID×15 cm, manufactured by TOSOH CORPORATION), Super HZ4000 (4.6 mmID×15 cm, manufactured by TOSOH CORPORATION), and Super HZ3000 (4.6 mmID×15 cm, manufactured by TOSOH CORPORATION) were used, respectively. manufactured) and each serial connector of Super HZ2000 (4.6mmID×15cm, manufactured by TOSOH CORPORATION). As the eluent, THF (tetrahydrofuran) was used. Regarding the measurement conditions, the sample concentration was set to 0.2 mass %, the flow rate was set to 0.35 mL/min, the sample injection amount was set to 10 μL, and the measurement temperature was set to 40°C. As a detector, a differential refractive index (RI) detector was used. The calibration curve uses the "standard sample TSK standard, polystyrene" manufactured by TOSOH CORPORATION: "F-40", "F-20", "F-4", "F-1", "A-5000", "A- 2500" and "A-1000" of 7 kinds of samples.

-content- From the viewpoint of high resolution, the content of the polymer X is preferably 50% by mass to 99.9% by mass, and more preferably 70% by mass to 98% by mass relative to the total mass of the positive photosensitive resin layer.

-Manufacturing method- There is no restriction|limiting as a manufacturing method of the polymer X, A well-known method can be utilized. For example, it is possible to polymerize the monomer for forming the constituent unit A, and further the monomer for forming the constituent unit B and the monomer for forming the constituent unit C as necessary by using a polymerization initiator in an organic solvent to make polymer X. The polymer X can also be produced by a so-called polymer reaction.

＜＜Other polymers＞＞ When the positive-type photosensitive resin layer includes a polymer having a structural unit having an acid group protected by an acid-decomposable group, in addition to the polymer having a structural unit having an acid group protected by an acid-decomposable group, the A polymer (hereinafter, sometimes referred to as "other polymer") which does not have a structural unit having an acid group protected by an acid-decomposable group may further be included.

As another polymer, polyhydroxystyrene is mentioned, for example. Commercially available polyhydroxystyrenes include SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F manufactured by SARTOMER, ARUFON UC-3000 manufactured by TOAGOSEI CO., LTD. , ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920 and ARUFON UC-3080, and Joncryl 690, Joncryl 678, Joncryl 67 and Joncryl 586 manufactured by BASF Corporation.

The positive photosensitive resin layer may contain one type of other polymer alone, or may contain two or more types of other polymers.

When the positive photosensitive resin layer contains other polymers, the content of the other polymers is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly 20% by mass or less, based on the total mass of the polymer components. good.

In the present invention, the "polymer component" is a general term for all the polymers contained in the positive photosensitive resin layer. For example, when the positive photosensitive resin layer contains the polymer X and other polymers, the polymer X and the other polymers are collectively referred to as a "polymer component". In addition, even if the compound corresponding to the crosslinking agent, the dispersing agent, and the surfactant mentioned later is a polymer compound, it is set as the thing which does not contain a polymer component.

The content of the polymer component is preferably 50% by mass to 99.9% by mass, and more preferably 70% by mass to 98% by mass relative to the total mass of the positive photosensitive resin layer.

＜＜Alkali-soluble resin (positive type)＞＞ The positive photosensitive resin layer preferably contains an alkali-soluble resin, more preferably contains an alkali-soluble resin and a quinonediazide compound, and particularly preferably contains a resin having a structural unit having a phenolic hydroxyl group and a quinonediazide compound.

As an alkali-soluble resin, the resin which has a hydroxyl group, a carboxyl group, or a sulfonic acid group in a main chain or a side chain is mentioned, for example. Examples of alkali-soluble resins include polyamide resins, polyhydroxystyrene, derivatives of polyhydroxystyrene, styrene-maleic anhydride copolymers, polyvinyl hydroxybenzoate, carboxyl group-containing (meth)acrylic resin and novolac resin. Preferable alkali-soluble resins include, for example, a polycondensate of m-/p-mixed cresol and formaldehyde, and a polycondensate of phenol, cresol and formaldehyde.

The alkali-soluble resin can have phenolic hydroxyl group (-Ar-OH), carboxyl group (-CO ₂ H), sulfonic acid group (-SO ₃ H), phosphoric acid group (-OPO ₃ H), sulfonamido group (-SO ₂ NH-R) or substituted sulfonamido-based acid groups (eg, activated amide imino, -SO ₂ NHCOR, -SO ₂ NHSO ₂ R and -CONHSO ₂ R). Here, Ar represents a divalent aryl group which may have a substituent, and R represents a hydrocarbon group which may have a substituent.

The novolak resin is obtained by condensing a phenolic compound and an aldehyde compound, for example, in the presence of an acid catalyst. As the phenolic compound, for example, o-, m- or p-cresol, 2,5-, 3,5- or 3,4-xylenol, 2,3,5-trimethylphenol, 2 - tert-butyl-5-methylphenol and tert-butyl hydroquinone. Examples of the aldehyde compound include aliphatic aldehydes (for example, formaldehyde, acetaldehyde, and glyoxal) and aromatic aldehydes (for example, benzaldehyde and salicylaldehyde). Examples of the acid catalyst include inorganic acids (eg, hydrochloric acid, sulfuric acid, and phosphoric acid), organic acids (eg, oxalic acid, acetic acid, and p-toluenesulfonic acid), and divalent metal salts (eg, zinc acetate). The condensation reaction can be carried out according to a conventional method. For example, the condensation reaction is carried out at a temperature of 60°C to 120°C under conditions of 2 hours to 30 hours. The condensation reaction can be carried out in a suitable solvent.

Among them, as the alkali-soluble resin, a resin having a structural unit having a phenolic hydroxyl group, such as a novolak resin, is preferable.

From the viewpoint of pattern formability, the weight average molecular weight of the alkali-soluble resin is preferably 5.0×10 ² to 2.0×10 ⁵ . From the viewpoint of pattern formability, the number average molecular weight of the alkali-soluble resin is preferably 2.0×10 ² to 1.0×10 ⁵ .

The positive-type photosensitive resin layer may contain a polycondensate (hereinafter, referred to as a "first polycondensate") of phenol and formaldehyde having an alkyl group having 3 to 8 carbon atoms as a substituent. Examples of the first polycondensate include polycondensates of tert-butylphenol and formaldehyde, polycondensates of octylphenol and formaldehyde described in the specification of US Pat. No. 4,123,279, and the like, and the positive photoreceptor layer may contain as a substituent A condensate of phenol and formaldehyde having an alkyl group having 3 to 8 carbon atoms (hereinafter, referred to as a "second polycondensate"). Examples of the second polycondensate include tertiary butylphenol formaldehyde resins, octylphenol formaldehyde resins, and the like described in the specification of US Pat. No. 4,123,279.

The positive-type photosensitive resin layer may contain one type or two or more types of alkali-soluble resins alone. The content of the alkali-soluble resin is preferably 30% by mass to 99.9% by mass, more preferably 40% by mass to 99.5% by mass, and particularly preferably 70% by mass to 99% by mass relative to the total mass of the positive photosensitive resin layer.

＜＜Photoacid generator＞＞ It is preferable that the positive photosensitive resin layer contains a photoacid generator as a photosensitive compound. Photoacid generators are compounds capable of generating acids by irradiation with activating light rays (eg, ultraviolet rays, extreme ultraviolet rays, X-rays, and electron beams).

As a photoacid generator, the compound which produces|generates an acid by sensing the activation light of wavelength 300nm or more, preferably wavelength 300nm - 450nm is preferable. Regarding the photoacid generator that does not directly sense activating light with a wavelength of 300 nm or more, if it is a compound that generates an acid by using a sensitizer in combination with activating light with a wavelength of 300 nm or more, it can also be preferably used in combination with a sensitizer. .

The photoacid generator is preferably a photoacid generator that generates an acid with a pKa of 4 or less, more preferably a photoacid generator that generates an acid with a pKa of 3 or less, and a photoacid generator that generates an acid with a pKa of 2 or less. Excellent. The lower limit of the pKa of the acid derived from the photoacid generator is not limited. The lower limit of the pKa of the acid derived from the photoacid generator is preferably, for example, -10.0 or more.

As a photoacid generator, an ionic photoacid generator and a nonionic photoacid generator are mentioned, for example.

As an ionic photoacid generator, an onium salt compound is mentioned, for example. As an onium salt compound, a diaryl iodonium salt compound, a triaryl perionium salt compound, and a quaternary ammonium salt compound are mentioned, for example. The ionic photoacid generator is preferably an onium salt compound, and particularly preferably at least one of a triaryl perionium salt compound and a diaryl iodonium salt compound.

As the ionic photoacid generator, the ionic photoacid generator described in paragraphs 0114 to 0133 of JP-A-2014-85643 can also be preferably used.

As a nonionic photoacid generator, a trichloromethyl-symmetric trisulfate compound, a diazomethane compound, an imine sulfonate compound, and an oxime sulfonate compound are mentioned, for example. From the viewpoints of sensitivity, resolution, and adhesion to the substrate, it is preferable that the nonionic photoacid generator is an oxime sulfonate compound.

Specific examples of the trichloromethyl mesitine compound, the diazomethane compound, and the imidate compound include compounds described in paragraphs 0083 to 0088 of JP 2011-221494 A. .

As the oxime sulfonate compound, those described in paragraphs 0084 to 0088 of International Publication No. 2018/179640 can be preferably used.

From the viewpoint of sensitivity and resolution, the photoacid generator is preferably at least one compound selected from the group consisting of an onium salt compound and an oxime sulfonate compound, and more preferably an oxime sulfonate compound.

As a preferable example of a photoacid generator, the photoacid generator which has the following structure is mentioned.

[Chemical formula 17]

As a photoacid generator which has absorption in wavelength 405nm, ADEKA ARKLS (registered trademark) SP-601 (made by ADEKA CORPORATION) is mentioned, for example.

From the viewpoint of heat resistance and dimensional stability, it is preferable that the positive photosensitive resin layer contains a quinonediazide compound as an acid generator (preferably a photoacid generator). The quinonediazide compound can be synthesized, for example, by subjecting a compound having a phenolic hydroxyl group to a condensation reaction with a quinonediazidesulfonyl halide in the presence of a dehydrohalogenating agent.

Examples of the quinonediazide compound include 1,2-benzoquinonediazide-4-sulfonate, 1,2-naphthoquinonediazide-4-sulfonate, and 1,2-naphthoquinone Diazide-5-sulfonate, 1,2-naphthoquinonediazide-6-sulfonate, 2,1-naphthoquinonediazide-4-sulfonate, 2,1-naphthoquinonediazide Nitrogen-5-sulfonic acid esters, 2,1-naphthoquinonediazide-6-sulfonic acid esters, sulfonic acid esters of other quinonediazide derivatives; 1,2-benzoquinonediazide-4-sulfonic acid Chlorine, 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 1,2-naphthoquinonediazide-6-sulfonic acid chloride, 2,1-Naphthoquinonediazide-4-sulfonic acid chloride, 2,1-naphthoquinonediazide-5-sulfonic acid chloride and 2,1-naphthoquinonediazide-6-sulfonic acid chloride.

The positive photosensitive resin layer may contain one type of photoacid generator alone, or may contain two or more types of photoacid generators. From the viewpoint of sensitivity and resolution, the content of the photoacid generator is preferably 0.1% by mass to 10% by mass, and more preferably 0.5% by mass to 5% by mass relative to the total mass of the positive photosensitive resin layer.

＜＜Other ingredients＞＞ The photosensitive resin layer may contain components other than the above.

-Surfactant- From the viewpoint of thickness uniformity, it is preferable that the photosensitive resin layer contains a surfactant. Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic (that is, nonionic) surfactants, and amphoteric surfactants, and nonionic surfactants are preferred. As the surfactant, for example, the surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Patent Laid-Open No. 2009-237362 can be mentioned.

As the surfactant, a fluorine-based surfactant or a silicone-based surfactant is preferable. Examples of commercially available fluorine-based surfactants include MEGAFACE (product name) F-171, F-172, F-173, F-176, F-177, F-141, F-142, F- 143, F-144, F-437, F-444, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, MFS-578, MFS-579, MFS-586, MFS-587, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS- 90, R-94, RS-72-K, DS-21 (manufactured by DIC Corporation above), Fluorad (product name) FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited above), Surflon (product name) S-382 , SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (the above are manufactured by AGC Inc.), PolyFox (product name) PF636, PF656, PF6320, PF6520, PF7002 (the above are manufactured by OMNOVA Solutions Inc.), Ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (the above are manufactured by NEOS Corporation), etc. As the fluorine-based surfactant, an acrylic-based compound can also be preferably used. The acrylic-based compound has a molecular structure having a functional group containing a fluorine atom, and when heat is applied, the functional group containing a fluorine atom is partially cleaved and the fluorine atom is volatilized. Examples of such fluorine-based surfactants include MEGAFACE (product name) DS series manufactured by DIC Corporation (Chemical Industry Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example MEGAFACE (product name) DS-21.

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. As the fluorine-based surfactant, an end-blocking polymer can also be used. The fluorine-based surfactant can also preferably use a fluorine-containing polymer compound, the fluorine-containing polymer compound comprising a structural unit derived from a (meth)acrylate compound having a fluorine atom and a Structural unit of a (meth)acrylate compound having 5 or more alkeneoxy groups (preferably, ethylideneoxy groups and propyleneoxy groups). As the fluorine-based surfactant, a fluoropolymer having an ethylenically unsaturated group in a side chain can also be used. As a commercial item of such a fluorine-type surfactant, MEGAFACE (product name) RS-101, RS-102, RS-718K, RS-72-K (the above are manufactured by DIC Corporation) etc. are mentioned.

Examples of nonionic surfactants include glycerin, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate) base, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol diethyl ether Laurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic (registered trademark) (product name) L10, L31, L61, L62, 10R5, 17R2, 25R2 (the above are manufactured by BASF Corporation ), Tetronic (product name) 304, 701, 704, 901, 904, 150R1 (the above are manufactured by BASF), Solsperse (product name) 20000 (the above is manufactured by Lubrizol Japan Limited.), NCW-101, NCW-1001, NCW-1002 (the above are manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN (product name) D-6112, D-6112-W, D-6315 (the above are manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (the above are manufactured by Nissin Chemical Co., Ltd.) and the like. In recent years, in consideration of environmental compatibility, compounds having a linear perfluoroalkyl group having a carbon number of 7 or more have been replaced by perfluorooctane acid (PFOA) and perfluorooctane sulfonic acid (PFOS). The surfactant is preferred.

Examples of the silicone-based surfactant include linear polymers composed of siloxane bonds, and modified siloxane polymers obtained by introducing organic groups to side chains or terminals. Specific examples of silicone-based surfactants include DOWSIL (product name) 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (the above are manufactured by Dow Corning Toray Silicone Co., Ltd.) and X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (the above are Shin-Etsu Chemical Co.,Ltd .manufactured), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc. above), BYK307, BYK323, BYK330 (manufactured by BYK Chemie Inc. above), etc.

The photosensitive resin layer may contain one type of surfactant alone, or two or more types may be contained. The content of the surfactant is preferably 0.001% by mass to 10% by mass, and more preferably 0.01% by mass to 3% by mass relative to the total mass of the photosensitive resin layer.

-additive- In addition to the above-mentioned components, the photosensitive resin layer may contain known additives as necessary. As an additive, a polymerization inhibitor, a sensitizer, a plasticizer, an alkoxysilane compound, and a solvent are mentioned, for example. The photosensitive resin layer may contain one type of each additive alone, or may contain two or more types. Examples of additives include metal oxide particles, antioxidants, dispersants, acid proliferators, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners and Organic or inorganic precipitation inhibitors. Preferable aspects of these additives are described in paragraphs 0165 to 0184 of Japanese Patent Laid-Open No. 2014-85643, respectively, and these contents are incorporated into this specification by reference.

The photosensitive resin layer may contain a polymerization inhibitor. As the polymerization inhibitor, a radical polymerization inhibitor is preferable. As the polymerization inhibitor, for example, the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784 can be mentioned. Among them, as the polymerization inhibitor, phenothiazine, phenoxine or 4-methoxyphenol is preferable. As another polymerization inhibitor, naphthylamine, cuprous chloride, nitrosophenylhydroxylamine aluminum salt, diphenylnitrosoamine, etc. are mentioned. In order not to impair the sensitivity of the photosensitive resin composition, as another polymerization inhibitor, nitrosophenylhydroxylamine aluminum salt is preferably used as the polymerization inhibitor.

The content of the polymerization inhibitor is preferably 0.01% by mass to 3% by mass, and more preferably 0.05% by mass to 1% by mass relative to the total mass of the photosensitive resin layer. From the viewpoint of imparting storage stability to the photosensitive resin composition, the content of the polymerization inhibitor is preferably 0.01 mass % or more. On the other hand, from the viewpoint of maintaining sensitivity, the content of the polymerization inhibitor is preferably 3 mass % or less.

The photosensitive resin layer may contain a sensitizer. The sensitizer is not particularly limited, and known sensitizers, dyes, and pigments can be used. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thiacone compounds, and acridone compounds. , oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (for example, 1,2,4-triazole), stilbene compounds, triazole compounds, thiophene compounds, naphthalene dicarboxylate Amine compounds, triarylamine compounds and aminoacridine compounds.

The photosensitive resin layer may contain one type of sensitizer alone, or may contain two or more types. When the photosensitive resin layer contains a sensitizer, the content of the sensitizer can be appropriately selected according to the purpose, but from the viewpoints of improving the sensitivity to a light source and improving the curing speed based on the balance between the polymerization speed and chain transfer, it is relatively The total mass of the photosensitive resin layer is preferably 0.01% by mass to 5% by mass, and more preferably 0.05% by mass to 1% by mass.

The photosensitive resin layer may contain at least one selected from the group consisting of a plasticizer and a heterocyclic compound. As the plasticizer and the heterocyclic compound, the compounds described in paragraphs 0097 to 0103 and paragraphs 0111 to 0118 of International Publication No. 2018/179640 can be mentioned.

The photosensitive resin layer, preferably a positive-type photosensitive resin layer, may contain an alkoxysilane compound. Examples of the alkoxysilane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-aminopropyltrimethoxysilane, -Glycidoxypropylalkyldialkoxysilane, γ-Methacryloyloxypropyltrialkoxysilane, γ-Methacryloyloxypropylalkyldialkoxysilane, γ-Methacryloyloxypropyldialkoxysilane - Chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β-(3,4-epoxycyclohexyl)ethyltrialkoxysilane and vinyltrialkoxysilane.

Among the above, the alkoxysilane compound is preferably a trialkoxysilane compound, and γ-glycidoxypropyltrialkoxysilane or γ-methacryloyloxypropyltrialkoxysilane is More preferably, γ-glycidyloxypropyltrialkoxysilane is further preferred, and 3-glycidyletherpropyltrimethoxysilane is particularly preferred.

The photosensitive resin layer may contain one type of alkoxysilane compound alone, or may contain two or more types of alkoxysilane compounds. From the viewpoints of adhesion to the substrate and etching resistance, the content of the alkoxysilane compound is preferably 0.1% by mass to 50% by mass, and preferably 0.5% by mass to 40% by mass relative to the total mass of the photosensitive resin layer. More preferably, 1.0 mass % - 30 mass % are especially preferable.

The photosensitive resin layer may contain a solvent. When the photosensitive resin layer is formed from the photosensitive resin composition containing a solvent, the solvent may remain in the photosensitive resin layer.

＜＜Impurities, etc＞＞ The photosensitive resin layer may contain a predetermined amount of impurities. Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof. Among them, halide ions, sodium ions, and potassium ions are easily mixed as impurities, so the content of impurities is preferably set to the following content.

The upper limit of the content of impurities in the photosensitive resin layer is preferably 80 ppm or less on a mass basis, more preferably 10 ppm or less, and further preferably 2 ppm or less. The lower limit of the content of impurities may be 1 ppb or more on a mass basis, or 0.1 ppm or more.

As a method of setting the impurities within the above range, selection of the content of the impurities as a raw material of the composition is small, prevention of contamination of impurities during the production of the photosensitive resin layer, and removal by washing are exemplified. By this method, the amount of impurities can be set within the above-mentioned range.

The amount of impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectroscopy, and ion chromatography, for example.

It is preferable that the content of the specific compound in the photosensitive resin layer is small. Specific compounds include benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylethyl acetate Amide and hexane, etc. The upper limit of the content of these specific compounds with respect to the total mass of the photosensitive resin layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less on a mass basis. The lower limit of the content of these specific compounds with respect to the total mass of the photosensitive resin layer can be 10 ppb or more and can be 100 ppb or more with respect to the total mass of the photosensitive resin layer on a mass basis. About these specific compounds, the content can be suppressed by the same method as the impurity of the above-mentioned metal. The content of these specific compounds can be quantified by a known measurement method.

From the viewpoint of improving reliability and lamination properties, the content of water in the photosensitive resin layer is preferably 0.01 to 1.0 mass %, more preferably 0.05 to 0.5 mass %.

＜＜Residual monomer＞＞ The photosensitive resin layer may contain the residual monomer corresponding to each structural unit of the said alkali-soluble resin. From the viewpoint of patternability and reliability, the upper limit of the content of residual monomers in each constituent unit of the alkali-soluble resin is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, relative to the total mass of the alkali-soluble resin. 500 mass ppm or less is more preferable. The lower limit of the content of the residual monomer in each constituent unit of the alkali-soluble resin is not particularly limited, but is preferably 1 mass ppm or more, and more preferably 10 mass ppm or more. From the viewpoints of patternability and reliability, the upper limit of the content of the residual monomer in each constituent unit of the alkali-soluble resin is preferably 3,000 mass ppm or less, and more preferably 600 mass ppm or less with respect to the total mass of the photosensitive resin layer. Preferably, 100 mass ppm or less is more preferable. The lower limit of the content of the residual monomer in each constituent unit of the alkali-soluble resin is not particularly limited, but is preferably 0.1 mass ppm or more, and more preferably 1 mass ppm or more.

When synthesizing an alkali-soluble resin by a polymer reaction, it is preferable that the residual monomer amount of the monomer is also in the above range. For example, in the case of synthesizing an alkali-soluble resin by reacting glycidyl acrylate in a carboxylic acid side chain, it is preferable to set the content of glycidyl acrylate in the above-mentioned range. The amount of residual monomers can be measured by known methods such as liquid chromatography and gas chromatography.

＜＜Properties, etc＞＞ The thickness of the photosensitive resin layer is preferably 0.1 μm to 300 μm, more preferably 0.2 μm to 100 μm, further preferably 0.5 μm to 50 μm, still more preferably 0.5 μm to 15 μm, and particularly preferably 0.5 μm to 10 μm , 0.5μm～8μm is the best. Thereby, the developability of the photosensitive resin layer is improved, and the analytical property can be improved. From the viewpoint of further exhibiting the analytical properties and the effects of the present invention, the layer thickness (thickness) of the photosensitive resin layer is preferably 10 μm or less, more preferably 5.0 μm or less, still more preferably 0.5 μm to 4.0 μm, and 0.5 μm or less. μm to 3.0 μm is particularly preferred. Regarding the layer thickness of each layer included in the photosensitive transfer material, the cross section in the direction perpendicular to the main surface of the photosensitive transfer material was observed with a scanning electron microscope (SEM: Scanning Electron Microscope), and the obtained The thickness of each layer was measured at 10 points or more from the observation image, and was measured by calculating the average value thereof.

From the viewpoint of more excellent adhesiveness, the lower limit of the transmittance of light having a wavelength of 365 nm of the photosensitive resin layer is preferably 10% or more, more preferably 30% or more, and more preferably 50% or more. The upper limit of the above-mentioned light transmittance is not particularly limited, but preferably 99.9% or less.

＜＜Formation method＞ The formation method of the photosensitive resin layer will not be specifically limited if it is a method which can form the layer containing the said component. As a method of forming the photosensitive resin layer, for example, in the case of a negative photosensitive resin layer, a method of preparing a photosensitive resin containing an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, a solvent, and the like is exemplified. The composition is formed by applying the photosensitive resin composition on the surface of the dummy support and the like, and drying the coating film of the photosensitive resin composition.

Examples of the photosensitive resin composition used for the formation of the photosensitive resin layer include alkali-soluble resins, polymerizable compounds, photopolymerization initiators, and compositions containing the above-mentioned optional components and solvents. In order to adjust the viscosity of the photosensitive resin composition and to facilitate the formation of the photosensitive resin layer, it is preferable that the photosensitive resin composition contains a solvent.

-Solvent- The solvent contained in the photosensitive resin composition is not particularly limited as long as it can dissolve or disperse the alkali-soluble resin, the polymerizable compound, the photopolymerization initiator, and the above-mentioned optional components, and known solvents can be used. Examples of the solvent include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (for example, methanol, ethanol, etc.), and ketone solvents (for example, acetone and methyl ethyl ketone). etc.), aromatic hydrocarbon solvents (for example, toluene, etc.), aprotic polar solvents (for example, N,N-dimethylformamide, etc.), cyclic ether solvents (for example, tetrahydrofuran, etc.), ester solvents, amides An amine solvent, a lactone solvent, and a mixed solvent containing two or more of these. In the case of producing a photosensitive transfer material having a dummy support, a thermoplastic resin layer, a water-soluble resin layer, a photosensitive resin layer and a protective film, the photosensitive resin composition contains a solvent selected from the group consisting of alkylene glycol ethers and At least one of the group of alkylene glycol ether acetate solvents is preferred. Among them, as the solvent contained in the photosensitive resin composition, at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, and a solvent including a ketone is included. and at least one mixed solvent from the group of cyclic ether solvents is more preferably, at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents A mixed solvent of three kinds, a ketone solvent and a cyclic ether solvent, is more preferable.

Examples of the alkylene glycol ether solvent include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, Dipropylene glycol monoalkyl ether and dipropylene glycol dialkyl ether. Examples of the alkylene glycol ether acetate solvent include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and diethylene glycol monoalkyl ether acetate. Propylene glycol monoalkyl ether acetate. As the solvent, the solvent described in the paragraphs 0092 to 0094 of International Publication No. 2018/179640 and the solvent described in the paragraph 0014 of JP-A No. 2018-177889 can be used, and these contents are incorporated in the present specification.

The photosensitive resin composition may contain one type of solvent alone, or may contain two or more types. The content of the solvent at the time of coating the photosensitive resin composition is preferably 50 parts by mass to 1,900 parts by mass, more preferably 100 parts by mass to 900 parts by mass, relative to 100 parts by mass of the total solid content in the photosensitive resin composition.

The preparation method of the photosensitive resin composition is not particularly limited. For example, a solution prepared by dissolving each component in the above-mentioned solvent is prepared in advance, and the obtained solution is mixed in a predetermined ratio to prepare a photosensitive resin. method of composition. From the viewpoint of particle removability, it is preferable to filter the photosensitive resin composition using a filter before forming the photosensitive resin layer. The pore size of the filter is preferably 0.2 μm to 10 μm, more preferably 0.2 μm to 7 μm, and even more preferably 0.2 μm to 5 μm. The material and shape of the filter are not particularly limited, and known ones can be used. It is preferable to carry out the above-mentioned filtration more than once, and it is also preferable to carry out a plurality of times.

The coating method of the photosensitive resin composition is not particularly limited, and may be coated by a known method. As a coating method, slot coating, spin coating, curtain coating, and inkjet coating are mentioned, for example. The photosensitive resin layer can be formed by apply|coating the photosensitive resin composition on the protective film mentioned later, and drying it.

It is preferable that the photosensitive transfer material in this invention has another layer between the said dummy support and the said photosensitive resin layer from a viewpoint of an analytical property and the peelability of a dummy support. As another layer, a water-soluble resin layer, a thermoplastic resin layer, a protective film, etc. are mentioned preferably. Among them, the photosensitive transfer material preferably has a water-soluble resin layer as the transfer layer, and more preferably has a thermoplastic resin layer and a water-soluble resin layer as the transfer layer.

[Water-soluble resin layer] When the photosensitive transfer material has a thermoplastic resin layer described later between the dummy support and the photosensitive resin layer, it is preferable to have a water-soluble resin layer between the thermoplastic resin layer and the photosensitive resin layer. The water-soluble resin layer can suppress the mixing of components when forming a plurality of layers and at the time of storage.

The water-soluble resin layer is preferably a water-soluble layer from the viewpoints of developability and suppression of component mixing during application of a plurality of layers and storage after application. In the present invention, "water solubility" means that the solubility in 100 g of water of pH 7.0 at a liquid temperature of 22°C is 0.1 g or more.

As a water-soluble resin layer, the oxygen-barrier layer which has an oxygen-barrier function which is described in Unexamined-Japanese-Patent No. 5-72724 as a "separation layer" is mentioned, for example. The water-soluble resin layer is an oxygen barrier layer, thereby improving the sensitivity during exposure, and as a result of reducing the time load of the exposure machine, the productivity is improved. The oxygen barrier layer used as the water-soluble resin layer may be appropriately selected from known layers. The oxygen barrier layer used as the water-soluble resin layer exhibits low oxygen permeability, and the oxygen barrier layer dispersed or dissolved in water or an aqueous alkali solution (a 1 mass % aqueous solution of sodium carbonate at 22° C.) is preferred. From the viewpoints of oxygen barrier properties, analytical properties, and pattern formability, it is preferable that the water-soluble resin layer contains an inorganic layered compound. The inorganic layered compound is a particle having a thin, flat shape, and examples thereof include mica compounds such as natural mica and synthetic mica, talc represented by the formula: 3MgO·4SiO·H ₂ O, band mica, Mongolian Destone, soapstone, lithium bentonite, zirconium phosphate, etc. Examples of mica compounds include those represented by the formula: A(B, C) _2-5 D ₄ O ₁₀ (OH, F, O) ₂ [wherein A is any one of K, Na, and Ca, and B and C is any of Fe(II), Fe(III), Mn, Al, Mg, and V, and D is Si or Al. ] represents the natural mica, synthetic mica and other mica groups.

Among the mica groups, examples of natural mica include muscovite, sodium mica, phlogopite, biotite, and lepidolite. Examples of synthetic mica include non-swellable mica such as fluorophlogopite KMg ₃ (AlSi ₃ O ₁₀ )F ₂ , potassium tetrasilica KMg _2.5 Si ₄ O ₁₀ )F ₂ , and the like; and Na tetracyclic mica NaMg _2.5 (Si _{4 ).} O ₁₀ ) F ₂ , Na or Li with mica (Na, Li) Mg ₂ Li (Si ₄ O ₁₀ ) F ₂ , montmorillonite Na or Li lithium bentonite (Na, Li) _1/8 Mg _2/5 Swellable mica such as Li _1/8 (Si ₄ O ₁₀ ) F ₂ and the like. Furthermore, synthetic bentonite is also useful.

As the shape of the inorganic layered compound, from the viewpoint of diffusion control, the thinner the thickness, the better, and the larger the plane size, the better, only if the smoothness of the coated surface and the transmittance of the activation light are not hindered. Therefore, the aspect ratio is preferably 20 or more, more preferably 100 or more, and particularly preferably 200 or more. The aspect ratio is the ratio of the length to the thickness of the particle, and can be measured, for example, from a projection of a micrograph based on the particle. The larger the aspect ratio, the higher the effect obtained.

Regarding the particle size of the inorganic layered compound, the average major diameter is preferably 0.3 μm to 20 μm, more preferably 0.5 μm to 10 μm, and particularly preferably 1 μm to 5 μm. The average thickness of the particles is preferably 0.1 μm or less, more preferably 0.05 μm or less, and particularly preferably 0.01 μm or less. Specifically, for example, when the swellable synthetic mica is a representative compound of the inorganic layered compound, as a preferable aspect of the swellable synthetic mica, the thickness is about 1 nm to 50 nm, and the surface size (long diameter) is 1 μm. ~20μm grade.

From the viewpoints of oxygen barrier properties, analytical properties, and pattern forming properties, the content of the inorganic layered compound is preferably 0.1% by mass to 50% by mass, and 1% by mass to 20% by mass relative to the total mass of the water-soluble resin layer. better.

It is preferable that the water-soluble resin layer contains resin. Examples of resins contained in the water-soluble resin layer include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, and gelatin. , vinyl ether resins, polyamide resins and their copolymers. The resin contained in the water-soluble resin layer is preferably a water-soluble resin.

From the viewpoint of suppressing mixing of components between a plurality of layers, the resin system contained in the water-soluble resin layer, the polymer A contained in the negative photosensitive resin layer, and the thermoplastic resin contained in the thermoplastic resin layer (ie, , alkali-soluble resins) are different resins are preferred.

From the viewpoints of oxygen barrier properties, developability, analytical properties, and pattern formation properties, it is preferable that the water-soluble resin layer contains a water-soluble compound, and it is more preferable that it contains a water-soluble resin. The water-soluble compound is not particularly limited, and is selected from the group consisting of water-soluble cellulose derivatives, polyhydric alcohols, and oxidative adducts of polyhydric alcohols from the viewpoints of oxygen barrier properties, developability, analytical properties, and pattern forming properties. , polyethers, phenol derivatives and amide compounds in the group of more than one compound is preferred, selected from including polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropyl cellulose and hydroxypropyl methyl At least one water-soluble resin in the group of cellulose is more preferable. Examples of water-soluble resins include water-soluble cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone, acrylamide resins, (meth)acrylate resins, polyethylene oxide resins, gelatin, and vinyl ethers. Resins, polyamide resins, and these copolymers. Among them, it is preferable that the water-soluble compound contains polyvinyl alcohol from the viewpoints of oxygen barrier properties, developability, analytical properties, and pattern forming properties, and it is more preferable that polyvinyl alcohol is contained. The degree of hydrolysis of polyvinyl alcohol is not particularly limited, but is preferably 73 mol % to 99 mol % from the viewpoints of oxygen barrier properties, developability, resolution, and pattern forming properties. From the viewpoints of oxygen barrier properties, developability, analytical properties, and pattern formation properties, it is preferable that polyvinyl alcohol contains vinylene as a monomer unit.

The water-soluble resin layer preferably contains polyvinyl alcohol, and more preferably contains polyvinyl alcohol and polyvinylpyrrolidone, from the viewpoints of oxygen barrier properties and suppression of mixing of components during application of multiple layers and storage after application. good.

The water-soluble resin layer may contain one kind or two or more kinds of resins alone.

The content ratio of the water-soluble compound in the water-soluble resin layer is 50% by mass relative to the total mass of the water-soluble resin layer, from the viewpoint of suppressing oxygen barrier properties and mixing of components when applying multiple layers and during storage after application. -100 mass% is preferable, 70 mass% to 100 mass% is more preferable, 80 mass% to 100 mass% is further preferable, and 90 mass% to 100 mass% is particularly preferable.

The water-soluble resin layer may contain additives as needed. As an additive, a surfactant is mentioned, for example.

The thickness of the water-soluble resin layer is not limited. The average thickness of the water-soluble resin layer is preferably 0.1 μm to 5 μm, and more preferably 0.5 μm to 3 μm. When the thickness of the water-soluble resin layer is within the above-mentioned range, the oxygen barrier properties are not lowered, the mixing of components when forming a plurality of layers and during storage can be suppressed, and the increase in the removal time of the water-soluble resin layer at the time of development can be suppressed. .

The method for forming the water-soluble resin layer is not limited as long as it can form a layer containing the above-mentioned components. As a method of forming the water-soluble resin layer, for example, a method of drying the coating film of the water-soluble resin layer composition after coating the water-soluble resin layer composition on the surface of the thermoplastic resin layer or the photosensitive resin layer is exemplified.

Examples of the water-soluble resin layer composition include resins and compositions containing arbitrary additives. The water-soluble resin layer composition preferably contains a solvent because the viscosity of the water-soluble resin layer composition is adjusted and the water-soluble resin layer is easily formed. The solvent is not limited as long as it can dissolve or disperse the resin. Preferably, the solvent is at least one selected from the group consisting of water and a water-miscible organic solvent, and more preferably, water or a mixed solvent of water and a water-miscible organic solvent.

Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin. The water-miscible organic solvent is preferably an alcohol having 1 to 3 carbon atoms, and more preferably methanol or ethanol.

[Thermoplastic resin layer] The photosensitive transfer material used in the present invention may have a thermoplastic resin layer. The photosensitive transfer material preferably has a thermoplastic resin layer between the dummy support and the photosensitive resin layer. The photosensitive transfer material has a thermoplastic resin layer between the dummy support and the photosensitive resin layer, thereby improving the followability to the adherend and suppressing the mixing of air bubbles between the adherend and the photosensitive transfer material. As a result, the adhesion between the layers is improved. improve.

It is preferable that the thermoplastic resin layer contains an alkali-soluble resin as the thermoplastic resin.

Examples of alkali-soluble resins include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formaldehyde, polyamide resins, polyester resins, Epoxy resin, polyacetal resin, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine and polyalkylene dialkylene alcohol.

From the viewpoint of developability and the adhesiveness of the layer adjacent to the thermoplastic resin layer, it is preferable that the alkali-soluble resin is an acrylic resin. Here, "acrylic resin" means having a structure selected from the group consisting of a constitutional unit derived from (meth)acrylic acid, a constitutional unit derived from (meth)acrylate, and a constitutional unit derived from (meth)acrylamide At least one of the resins.

In the acrylic resin, the total of the structural units derived from (meth)acrylic acid, the structural units derived from (meth)acrylates, and the structural units derived from (meth)acrylamide relative to the total mass of the acrylic resin The content ratio is preferably 50% by mass or more. In the acrylic resin, the ratio of the total content of the constituent units derived from (meth)acrylic acid and the constituent units derived from (meth)acrylate is preferably 30% by mass to 100% by mass relative to the total mass of the acrylic resin , 50% by mass to 100% by mass is more preferable.

The alkali-soluble resin is preferably a polymer having an acid group. As an acid group, a carboxyl group, a sulfo group, a phosphoric acid group, and a phosphonic acid group are mentioned, for example, a carboxyl group is preferable.

From the viewpoint of developability, 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. The upper limit of the acid value of the alkali-soluble resin is not limited. The upper limit of the acid value of the alkali-soluble resin is preferably 200 mgKOH/g or less, and more preferably 150 mgKOH/g or less.

There is no restriction|limiting in particular as a carboxyl group-containing acrylic resin with an acid value of 60 mgKOH/g or more, It can select and use suitably from a well-known resin. Examples of the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH/g or more include, for example, a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH/g or more in the polymer described in paragraph 0025 of Japanese Patent Laid-Open No. 2011-95716, Carboxyl group-containing acrylic resins having an acid value of 60 mgKOH/g or more in the polymers described in paragraphs 0033 to 0052 of JP 2010-237589 A and those described in paragraphs 0053 to 0068 of JP 2016-224162 A An acrylic resin containing a carboxyl group with an acid value of 60 mgKOH/g or more in the binder polymer.

The content ratio of the structural unit having a carboxyl group in the carboxyl group-containing acrylic resin relative to the total mass of the carboxyl group-containing acrylic resin is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and 12% by mass % to 30% by mass is particularly preferred.

From the viewpoint of developability and the adhesiveness of the layer adjacent to the thermoplastic resin layer, the alkali-soluble resin is an acrylic resin having a structural unit derived from (meth)acrylic acid, and is particularly preferred.

The alkali-soluble resin may have reactive groups. The reactive group may be, for example, a group capable of addition polymerization. As a reactive group, an ethylenically unsaturated group, a polycondensation-polymerizable group (for example, a hydroxyl group and a carboxyl group), and a polyaddition reactive group (for example, an epoxy group and a (blocked) isocyanate group) are mentioned, for example.

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

The thermoplastic resin layer may contain one type or two or more types of alkali-soluble resins alone.

From the viewpoints of developability and adhesiveness of the layer adjacent to the thermoplastic resin layer, the content ratio of the alkali-soluble resin is preferably 10% by mass to 99% by mass, and preferably 20% by mass to 90% by mass relative to the total mass of the thermoplastic resin layer. The mass % is more preferable, 40 mass % to 80 mass % is further preferable, and 50 mass % to 70 mass % is particularly preferable.

The thermoplastic resin layer contains a dye whose maximum absorption wavelength is 450 nm or more in the wavelength range of 400 nm to 780 nm during color development, and whose maximum absorption wavelength is changed by acid, alkali or radical (hereinafter, sometimes referred to as "dye B"). .) is preferred. The preferred aspect of the dye B is the same as the preferred aspect of the dye N described above, except for the point described later.

From the viewpoints of the visibility of the exposed part, the visibility of the non-exposed part, and the analytical properties, it is preferable that the dye B is a dye whose maximum absorption wavelength is changed by an acid or a radical, and a dye whose maximum absorption wavelength is changed by an acid for better.

From the viewpoints of the visibility of the exposed part and the visibility and resolution of the non-exposed part, the thermoplastic resin layer contains the dye B, the dye whose maximum absorption wavelength is changed by acid, and the compound that generates acid by light, which will be described later. better.

The thermoplastic resin layer may contain one type or two or more types of dyes B alone.

From the viewpoint of the visibility of the exposed part and the visibility of the non-exposed part, the content ratio of the dye B is preferably 0.2 mass % or more, more preferably 0.2 mass % to 6 mass %, with respect to the total mass of the thermoplastic resin layer. 0.2 mass % - 5 mass % are more preferable, and 0.25 mass % - 3.0 mass % are especially preferable.

Here, the content ratio of the dye B represents the content ratio of the dye when all the dyes B contained in the thermoplastic resin layer are in a color-developed state. Hereinafter, a method for quantifying the content ratio of the dye B will be described by taking a dye that develops color by radicals as an example. First, 2 solutions were prepared. Specifically, a solution in which a dye (0.001 g) was dissolved in methyl ethyl ketone (100 mL) and a solution in which a dye (0.01 g) was dissolved in methyl ethyl ketone (100 mL) were prepared. After adding IRGACURE OXE-01 (manufactured by BASF Corporation) as a photo-radical polymerization initiator to each of the obtained solutions, radicals were generated by irradiating light of 365 nm, and all the dyes were brought into a colored state. Next, using a spectrophotometer (UV3100, manufactured by SHIMADZU CORPORATION) in an atmospheric atmosphere, the absorbance of each solution at a liquid temperature of 25° C. was measured, and a calibration curve was prepared. Next, in place of the dye, the thermoplastic resin layer (0.1 g) was dissolved in methyl ethyl ketone, and the absorbance of the solution in which all the dye was developed was measured by the same method as above. Based on the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of the pigment contained in the thermoplastic resin layer was calculated according to the calibration curve.

The thermoplastic resin layer may contain a compound (hereinafter, sometimes referred to as "compound C") that generates an acid, a base, or a radical by light. Compound C is preferably a compound that accepts activating light (eg, ultraviolet and visible light) to generate acid, base or free radical. As compound C, well-known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators) can be mentioned. Compound C is preferably a photoacid generator.

From the viewpoint of resolution, it is preferable that the thermoplastic resin layer contains a photoacid generator. As a photoacid generator, the photocationic polymerization initiator which can be contained in the photosensitive resin layer mentioned above is mentioned, and the preferable aspect is the same except for the point mentioned later.

The photoacid generator preferably contains at least one selected from the group consisting of onium salt compounds and oxime sulfonate compounds from the viewpoints of sensitivity and resolution, and from the viewpoints of sensitivity, resolution and adhesion , it is more preferable to contain oxime sulfonate compounds.

It is also preferable that the photoacid generator is a photoacid generator having the following structure.

[Chemical formula 18]

The thermoplastic resin layer may contain a photobase generator. As the photobase generator, for example, 2-nitrobenzylcyclohexylcarbamate, trityl alcohol, O-aminocarbamoylhydroxyamide, O-aminocarbamoyloxime, [[(2 ,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine, 4-(methylthio) Benzyl)-1-methyl-1-morpholineethane, (4-morpholinobenzyl)-1-benzyl-1-dimethylaminopropane, N-(2-nitro benzyloxycarbonyl)pyrrolidine, hexamine cobalt(III) chloride tris(trityl borate), 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-dihydropyridine Acetyl-4-(2,4-dinitrophenyl)-1,4-dihydropyridine.

The thermoplastic resin layer may contain a photoradical polymerization initiator. As a photoradical polymerization initiator, the photoradical polymerization initiator which can be contained in the said photosensitive resin layer is mentioned, for example, and the preferable aspect is also the same.

The thermoplastic resin layer may contain one compound C or two or more compounds.

From the viewpoint of the visibility of the exposed part and the visibility and resolution of the non-exposed part, the content ratio of the compound C is preferably 0.1% by mass to 10% by mass, and preferably 0.5% by mass to 0.5% by mass relative to the total mass of the thermoplastic resin layer. 5 mass % is more preferable.

It is preferable that the thermoplastic resin layer contains a plasticizer from the viewpoints of resolution, adhesiveness and developability of the layer adjacent to the thermoplastic resin layer.

The molecular weight of the plasticizer (the molecular weight of the oligomer or polymer refers to the weight average molecular weight (Mw). Hereinafter, the same in this paragraph.) is preferably smaller than the molecular weight of the alkali-soluble resin. The molecular weight of the plasticizer is preferably 200 to 2,000.

The plasticizer is not limited as long as it is a compound that is compatible with the alkali-soluble resin and exhibits plasticity. From the viewpoint of imparting plasticity, a compound having an alkaneoxy group in the molecule of the plasticizer is preferable, and a polyalkylene glycol compound is more preferable. Preferably, the alkaneoxy group contained in the plasticizer has a polyethylene oxygen structure or a polypropylene oxygen structure.

From the viewpoint of resolution and storage stability, it is preferable that the plasticizer contains a (meth)acrylate compound. From the viewpoints of compatibility, resolution, and adhesiveness of the layer adjacent to the thermoplastic resin layer, the alkali-soluble resin is an acrylic resin, and it is more preferable that the plasticizer contains a (meth)acrylate compound.

As a (meth)acrylate compound used as a plasticizer, the (meth)acrylate compound described in the said ethylenically unsaturated compound is mentioned, for example. In the photosensitive transfer material, when the thermoplastic resin layer and the photosensitive resin layer are arranged in direct contact with each other, it is preferable that the thermoplastic resin layer and the photosensitive resin layer each contain the same (meth)acrylate compound. When the thermoplastic resin layer and the photosensitive resin layer respectively contain the same (meth)acrylate compound, diffusion of components between layers is suppressed, and storage stability is improved.

When the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, from the viewpoint of the adhesiveness between the thermoplastic resin layer and the adjacent layer, even in the exposed portion after exposure, (meth)acrylic acid It is also preferred that the ester compound is not polymerized.

In one embodiment, the (meth)acrylate compound used as a plasticizer has two or more in one molecule from the viewpoints of resolution, adhesiveness and developability of the layer adjacent to the thermoplastic resin layer. A (meth)acrylate compound of a (meth)acryloyl group is preferable.

In one embodiment, the (meth)acrylate compound used as a plasticizer is preferably a (meth)acrylate compound or a urethane (meth)acrylate compound having an acid group.

The thermoplastic resin layer may contain one type or two or more types of plasticizers alone.

From the viewpoints of resolution, adhesion of the layer adjacent to the thermoplastic resin layer, and developability, the content ratio of the plasticizer is preferably 1% by mass to 70% by mass relative to the total mass of the thermoplastic resin layer, and 10% by mass is preferred. %-60 mass % is more preferable, and 20-50 mass % is especially preferable.

From the viewpoint of thickness uniformity, it is preferable that the thermoplastic resin layer contains a surfactant. As a surfactant, for example, the surfactant which can be contained in the said photosensitive resin layer is mentioned, and the preferable aspect is also the same.

The thermoplastic resin layer may contain one type or two or more types of surfactants alone.

The content ratio of the surfactant is preferably 0.001% by mass to 10% by mass, and more preferably 0.01% by mass to 3% by mass relative to the total mass of the thermoplastic resin layer.

The thermoplastic resin layer may contain a sensitizer. As a sensitizer, the sensitizer which can be contained in the negative photosensitive resin layer mentioned above is mentioned, for example.

The thermoplastic resin layer may contain one type or two or more types of sensitizers alone.

From the viewpoint of improving the sensitivity to the light source, the visibility of the exposed part, and the visibility of the non-exposed part, the content ratio of the sensitizer is preferably 0.01% by mass to 5% by mass relative to the total mass of the thermoplastic resin layer, and is preferably 0.05% by mass. The mass % to 1 mass % is more preferable.

In addition to the above-mentioned components, the thermoplastic resin layer may contain known additives as necessary.

The thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese Patent Laid-Open No. 2014-85643. The contents of the above-mentioned publications are incorporated into this specification by reference.

The thickness of the thermoplastic resin layer is not limited. From the viewpoint of the adhesiveness of the layer adjacent to the thermoplastic resin layer, the lower limit of the average thickness of the thermoplastic resin layer is preferably 1 μm or more, more preferably 2 μm or more. The upper limit of the average thickness of the thermoplastic resin layer is not limited. From the viewpoint of developability and resolution, the upper limit of the average thickness of the thermoplastic resin layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less.

The method for forming the thermoplastic resin layer is not limited as long as it can form a layer containing the above-mentioned components. As a formation method of a thermoplastic resin layer, the method of apply|coating a thermoplastic resin composition to the surface of a dummy support body, and drying the coating film of a thermoplastic resin composition, for example is mentioned.

As a thermoplastic resin composition, the composition containing the above-mentioned components is mentioned, for example. In order to adjust the viscosity of the thermoplastic resin composition and make it easy to form the thermoplastic resin layer, it is preferable that the thermoplastic resin composition contains a solvent.

The solvent contained in the thermoplastic resin composition is not limited as long as it can dissolve or disperse the components contained in the thermoplastic resin layer. As a solvent, the solvent which can contain the photosensitive resin composition mentioned above is mentioned, and the preferable aspect is also the same.

The thermoplastic resin composition may contain one type or two or more types of solvents alone.

The content of the solvent in the thermoplastic resin composition is preferably 50 parts by mass to 1,900 parts by mass, more preferably 100 parts by mass to 900 parts by mass, relative to 100 parts by mass of the total solid content in the thermoplastic resin composition.

The preparation of the thermoplastic resin composition and the formation of the thermoplastic resin layer may be carried out in accordance with the above-mentioned preparation method of the photosensitive resin composition and the formation method of the negative photosensitive resin layer. For example, the thermoplastic resin composition is prepared by preparing a solution in which each component contained in the thermoplastic resin layer is dissolved in a solvent in advance, and mixing the obtained solutions in a predetermined ratio. Then, the thermoplastic resin layer can be formed by applying the obtained thermoplastic resin composition to the surface of the temporary support and drying the coating film of the thermoplastic resin composition. After forming the photosensitive resin layer on the protective film, a thermoplastic resin layer may be formed on the surface of the photosensitive resin layer.

[Protective film] It is preferable that the photosensitive transfer material has a protective film. In addition, a protective film is not included in the said transfer layer. It is preferable that the photosensitive resin layer is in direct contact with the protective film.

As a material which comprises a protective film, a resin film and paper are mentioned, From a viewpoint of strength and flexibility, a resin film is preferable. Examples of the resin film include polyethylene films, polypropylene films, polyethylene terephthalate films, cellulose triacetate films, polystyrene films, and polycarbonate films. Among them, as the resin film, a polyethylene film, a polypropylene film or a polyethylene terephthalate film is preferable.

The thickness (layer thickness) of the protective film is not particularly limited, but is preferably 5 μm to 100 μm, and more preferably 10 μm to 50 μm. The arithmetic mean roughness Ra of the surface on the opposite side to the photosensitive resin layer side in the protective film is the above-mentioned photosensitive resin layer in the protective film from the viewpoints of transportability, defect suppression properties of the resin pattern, and analytical properties. The arithmetic mean roughness Ra of the surface on the side is preferably less than or equal to the arithmetic mean roughness Ra of the surface on the side of the photosensitive resin layer in the protective film. The upper limit of the arithmetic mean roughness Ra of the surface on the opposite side to the photosensitive resin layer side in the protective film is preferably 300 nm or less, more preferably 100 nm or less, from the viewpoints of transportability and windability. 70 nm or less is more preferable, and 50 nm or less is particularly preferable. From the viewpoint of more excellent resolution, the upper limit of the arithmetic mean roughness Ra of the surface on the photosensitive resin layer side in the protective film is preferably 300 nm or less, more preferably 100 nm or less, more preferably 70 nm or less, and 50 nm or less. The following are excellent. When the Ra value of the surface of a protective film is in the said range, the uniformity of the layer thickness of the photosensitive resin layer and the resin pattern formed improves. The lower limit of the Ra value on the surface of the protective film is not particularly limited, and both sides are preferably 1 nm or more, more preferably 10 nm or more, and particularly preferably 20 nm or more. It is preferable that the peeling force of the protective film is smaller than that of the dummy support.

The photosensitive transfer material may include layers other than the above-mentioned layers (hereinafter, also referred to as "other layers"). As another layer, for example, a contrast enhancement layer can be mentioned. The contrast enhancement layer is described in paragraph 0134 of International Publication No. 2018/179640. The other layers are described in paragraphs 0194 to 0196 of Japanese Patent Application Laid-Open No. 2014-85643. The contents of these gazettes are incorporated into this specification.

The total thickness of the photosensitive transfer material is preferably 5 μm to 55 μm, more preferably 10 μm to 50 μm, and particularly preferably 20 μm to 40 μm. The total thickness of the photosensitive transfer material is measured according to the above-mentioned method of measuring the thickness of each layer. From the viewpoint of further exerting the effects of the present invention, the total thickness of the dummy support and each layer except the protective film in the photosensitive transfer material is preferably 20 μm or less, more preferably 10 μm or less, and still more preferably 8 μm or less. 2 μm or more and 8 μm or less are particularly preferred. From the viewpoint of further exerting the effects of the present invention, the total thickness of the photosensitive resin layer, the water-soluble resin layer and the thermoplastic resin layer in the photosensitive transfer material is preferably 20 μm or less, more preferably 10 μm or less, and 8 μm or less. More preferably, 2 μm or more and 8 μm or less are particularly preferred.

[Manufacturing method of photosensitive transfer material] The manufacturing method of the photosensitive transfer material used by this invention is not specifically limited, A well-known manufacturing method, for example, a well-known formation method of each layer can be used. Hereinafter, with reference to FIG. 1, the manufacturing method of the photosensitive transfer material used by this invention is demonstrated. However, the photosensitive transfer material used in the present invention is not limited to those having the configuration shown in FIG. 1 . FIG. 1 is a schematic cross-sectional view showing an example of the layer structure in one embodiment of the photosensitive transfer material used in the present invention. The photosensitive transfer material 20 shown in FIG. 1 has a structure in which a temporary support 11 , a thermoplastic resin layer 13 , a water-soluble resin layer 15 , a photosensitive resin layer 17 , and a protective film 19 are laminated in this order. The transfer layer 12 in FIG. 1 is the thermoplastic resin layer 13 , the water-soluble resin layer 15 , and the photosensitive resin layer 17 .

As a method for producing the above-mentioned photosensitive transfer material 20, for example, a method including a process in which the thermoplastic resin composition is coated on the surface of the temporary support 11, and then the coating film of the thermoplastic resin composition is dried to obtain a The process of forming the thermoplastic resin layer 12; the process of forming the water-soluble resin layer 15 by coating the water-soluble resin layer composition on the surface of the thermoplastic resin layer 13, and then drying the coating film of the water-soluble resin layer composition; The process of forming the photosensitive resin layer 16 by coating the photosensitive resin composition containing an ethylenically unsaturated compound on the surface of the water-soluble resin layer 15, and drying the coating film of the photosensitive resin composition. In the above-mentioned manufacturing method, it is preferable to use a thermoplastic resin composition, a water-soluble resin layer composition, and a photosensitive resin composition. The thermoplastic resin composition contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. The water-soluble resin layer composition contains at least one selected from the group consisting of water and a water-miscible organic solvent. The photosensitive resin composition contains at least one selected from the group consisting of a binder polymer, an ethylenically unsaturated compound, an alkylene glycol ether solvent, and an alkylene glycol ether acetate solvent. Thereby, it is possible to suppress the components contained in the thermoplastic resin layer 13 during the storage period of the laminate in which the water-soluble resin layer composition and/or the coating film having the water-soluble resin layer composition is coated on the surface of the thermoplastic resin layer 13 . Mixing with components contained in the water-soluble resin layer 15 . Furthermore, the components contained in the water-soluble resin layer 15 during the storage period of the layered product in which the photosensitive resin composition and/or the coating film having the photosensitive resin composition is coated on the surface of the water-soluble resin layer 15 can be suppressed from and Mixing of components contained in the photosensitive resin layer 16 .

The photosensitive transfer material 20 is produced by pressing the protective film 19 on the photosensitive resin layer 17 of the laminate produced by the above-described production method. As the manufacturing method of the photosensitive transfer material used in the present invention, it is preferable to manufacture the photosensitive transfer material 20 by including the step of providing the protective film 19 so as to be in contact with the second surface of the photosensitive resin layer 17 . The photosensitive transfer material 20 includes a dummy support 11 , a thermoplastic resin layer 13 , a water-soluble resin layer 15 , a photosensitive resin layer 17 , and a protective film 19 . After the photosensitive transfer material 20 is produced by the above-described production method, the photosensitive transfer material in the form of a roll can be produced and stored by winding up the photosensitive transfer material 20 . The photosensitive transfer material in the form of a roll can be directly supplied in this form to a step of laminating to a substrate by a roll-to-roll method, which will be described later.

The photosensitive transfer material used in the present invention can be preferably used for various applications requiring precise microfabrication based on photolithography. After patterning the photosensitive resin layer, the photosensitive resin layer may be etched as a film, or electroforming mainly by electroplating may be performed. The cured film obtained by patterning can be used as a permanent film, for example, as an interlayer insulating film, a wiring protection film, a wiring protection film with refractive index matching, and the like. The photosensitive transfer material used in the present invention can be preferably used for the formation of various wirings of semiconductor packages, printed substrates, sensor substrates, and the formation of touch panels, electromagnetic shielding materials, film heaters, and the like. It can be used for conductive films, liquid crystal sealing materials, structures in micromachines or microelectronics, etc.

As the photosensitive transfer material used in the present invention, the photosensitive resin layer is preferably a coloring resin layer containing a pigment. As the application of the colored resin layer, in addition to the above, for example, it is suitable for forming a liquid crystal display device (LCD) and a solid-state imaging device (eg, a charge-coupled device (CCD) and a complementary metal oxide semiconductor (CMOS). : Complementary Metal Oxide Semiconductor)] used for coloring pixels or black matrices such as color filters. The aspect other than the pigment in the colored resin layer is the same as the aspect described above.

＜Pigment＞ The photosensitive resin layer may be a colored resin layer containing a pigment. In recent years, a cover glass in which a black frame-shaped light-shielding layer is formed on the peripheral edge of the back surface of a transparent glass substrate or the like is sometimes attached to a liquid crystal display window included in an electronic device to protect the liquid crystal display window. In order to form such a light shielding layer, a colored resin layer can be used. The pigment may be appropriately selected according to the desired hue, and may be selected from black pigments, white pigments, and color pigments other than black and white. Among them, in the case of forming a black-based pattern, a black pigment can be preferably selected as the pigment.

As the black pigment, known black pigments (organic pigments, inorganic pigments, etc.) can be appropriately selected as long as the effects of the present invention are not impaired. Among them, from the viewpoint of optical density, for example, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, black lead, etc. are preferably used as black pigments, and carbon black is particularly preferred. As carbon black, from the viewpoint of surface resistance, carbon black in which at least a part of the surface is covered with resin is preferable.

From the viewpoint of dispersion stability, the particle diameter of the black pigment is preferably 0.001 μm to 0.1 μm, more preferably 0.01 μm to 0.08 μm, in terms of number average particle diameter. Here, the particle size refers to the diameter of a circle when the area of the pigment particle is obtained from a photographic image of the pigment particle taken with an electron microscope and a circle having the same area as the area of the pigment particle is considered, and the number-average particle size refers to an arbitrary 100 The average value obtained by obtaining the above-mentioned particle diameter for each particle and averaging the obtained 100 particle diameters.

As pigments other than black pigments, the white pigments described in paragraphs 0015 and 0114 of JP-A-2005-007765 can be used. Specifically, among the white pigments, as inorganic pigments, titanium oxide, zinc oxide, zinc white, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide or barium sulfate are preferred, and titanium oxide or zinc oxide is more preferred , titanium oxide is further preferred. As the inorganic pigment, rutile-type or anatase-type titanium oxide is more preferable, and rutile-type titanium oxide is particularly preferable. Silica treatment, alumina treatment, titania treatment, zirconium dioxide treatment, or organic substance treatment may be applied to the surface of the titanium oxide, and two or more kinds of treatments may be applied. Thereby, the catalytic activity of the titanium oxide is suppressed, and the heat resistance, the fading property, and the like are improved. From the viewpoint of reducing the thickness of the photosensitive resin layer after heating, as the surface treatment on the surface of titanium oxide, at least one of alumina treatment and zirconia treatment is preferable, and alumina treatment and zirconia treatment are preferred. Handling both is excellent.

When the photosensitive resin layer is a colored resin layer, it is also preferable that the photosensitive resin layer further contains a color pigment other than a black pigment and a white pigment from the viewpoint of transferability. When a color pigment is included, the particle diameter of the color pigment is preferably 0.1 μm or less, and more preferably 0.08 μm or less, from the viewpoint of more excellent dispersibility. Examples of color pigments include Victoria Pure Blue BO (Color Index: Color Index (C.I. hereinafter) 42595), Golden Amine (C.I. 41000), Grease Black HB (C.I. 26150), Monoright Yellow GT (C.I. Pigment Yellow 12), Permanent Yellow GR (C.I. Pigment Yellow 17), Permanent Yellow HR (C.I. Pigment Yellow 83), Permanent Magenta FBB (C.I. Pigment Red 146), Master Yeast Red ESB (C.I. Pigment Violet 19), Permanent Ruby FBH ( C.I. Pigment Red 11), Fastel Powder B Supra (C.I. Pigment Red 81), Monastrell Fast Blue (C.I. Pigment Blue 15), Monoright Fast Black B (C.I. Pigment Black 1) and carbon, C.I. Pigment Red 97, C.I. Pigment Red 122, C.I. Pigment Red 149, C.I. Pigment Red 168, C.I. Pigment Red 177, C.I. Pigment Red 180, C.I. Pigment Red 192, C.I. Pigment Red 215, C.I. Blue 15:1, C.I. Pigment Blue 15:4, C.I. Pigment Blue 22, C.I. Pigment Blue 60, C.I. Pigment Blue 64 and C.I. Pigment Violet 23, etc. Among them, C.I. Pigment Red 177 is preferable as the color pigment.

When the photosensitive resin layer contains a pigment, the content of the pigment is preferably more than 3 mass % and 40 mass % or less, more preferably more than 3 mass % and 35 mass % or less, with respect to the total mass of the photosensitive resin layer, More than 5 mass % and 35 mass % or less are more preferable, and 10 mass % or more and 35 mass % or less are especially preferable.

When the photosensitive resin layer contains pigments other than black pigments (white pigments and color pigments), the content of pigments other than black pigments is preferably 30% by mass or less, and 1 to 20% by mass relative to the total mass of the black pigments. More preferably, 3-15 mass % is more preferable.

In addition, when the photosensitive resin layer contains a black pigment and the photosensitive resin layer is formed from the photosensitive resin composition, it is preferable to introduce the black pigment (preferably carbon black) into the photosensitive resin composition in the form of a pigment dispersion liquid . The dispersion can be prepared by adding a mixture obtained by premixing a black pigment and a pigment dispersant in an organic solvent (or vehicle) and dispersing using a dispersing machine. The pigment dispersant may be selected according to the pigment and the solvent, and for example, a commercially available dispersant can be used. In addition, the medium liquid refers to the part of the medium in which the pigment is dispersed when used as a pigment dispersion liquid. The vehicle is liquid and contains a binder component that keeps the black pigment in a dispersed state, and a solvent component (organic solvent) that dissolves and dilutes the binder component.

Although it does not specifically limit as a dispersing machine, For example, well-known dispersing machines, such as a kneader, a roll mill, an attritor, a supermill, a dissolver, a homomixer, and a sand mixer, are mentioned. Furthermore, the above-mentioned mixture can be finely pulverized by mechanical pulverization using frictional force. Regarding the disperser and the fine pulverization, the description of the "Encyclopedia of Pigments" (by Asakura Kuni, 1st edition, Asakura Publishing Co., Ltd., 2000, pp. 438, 310) can be referred to.

(Manufacturing method of electronic components) The manufacturing method of the electronic component of this invention will not be specifically limited if it is the manufacturing method of the electronic component provided with the conductive pattern obtained by the manufacturing method of the conductive pattern of this invention.

The specific aspect of each process in the manufacturing method of an electronic device, the order of performing each process, etc. are as described in the above-mentioned section of "manufacturing method of a conductive element", and the preferred aspect is also the same. About the manufacturing method of an electronic element, except that the wiring for an electronic element is formed by the said method, what is necessary is just to refer to the manufacturing method of a well-known electronic element. The manufacturing method of an electronic component may include arbitrary steps (other steps) other than those described above.

The electronic components are not particularly limited, and preferred examples include semiconductor packages, printed circuit boards, various wiring formation applications for sensor substrates, touch panels, electromagnetic shielding materials, and conductive films such as film heaters. , liquid crystal sealing materials, structures in micromechanical or microelectronics collection. The above-mentioned resin pattern is preferably used as a permanent film in the above-mentioned electronic element, for example, an interlayer insulating film, a wiring protective film, a wiring protective film having refractive index matching, and the like. Among them, as an electronic component, a touch panel can be preferably mentioned in particular. As an electronic component, a flexible display device, especially a flexible touch panel can be mentioned preferably.

An example of the pattern of the mask used for manufacture of a touch panel is shown in FIG.2 and FIG.3. In the pattern A shown in FIG. 2 and the pattern B shown in FIG. 3, GR is a non-image part (light shielding part), EX is an image part (exposure part), and DL is what virtually shows the frame for alignment. In the manufacturing method of the touch panel, for example, the photosensitive resin layer is exposed through a mask having the pattern A shown in FIG. touch panel. Specifically, it can be produced by the method described in FIG. 1 of International Publication No. 2016/190405. In an example of the manufactured touch panel, the central part (pattern part for connection qualification) of the exposure part EX is a part where the transparent electrode (electrode for touch panel) is formed, and the peripheral part (thin line part) of the exposure part EX is formed. This is the part of the wiring where the peripheral extraction part is formed.

It is preferable to manufacture the electronic component which has at least the wiring for electronic components by the manufacturing method of the said electronic component, for example, it is preferable to manufacture the touch panel which has at least the wiring for touch panels. Preferably, the touch panel has a transparent substrate, electrodes and an insulating layer or a protective layer. As a detection method in a touch panel, well-known methods, such as a resistive film method, an electrostatic capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method, are mentioned. Among them, the electrostatic capacitance method is preferable.

Examples of the touch panel type include a so-called in-cell type (for example, those described in FIGS. 5 , 6 , 7 , and 8 of Japanese Patent Application Publication No. 2012-517051 ), a so-called out-cell type (for example, , those described in Figure 19 of Japanese Patent Laid-Open No. 2013-168125, and those described in Figures 1 and 5 of Japanese Patent Laid-Open No. 2012-89102), OGS (One Glass Solution: Single Glass Solution) type , TOL (Touch-on-Lens: Overlay Touch) type (for example, as described in FIG. 2 of Japanese Patent Application Laid-Open No. 2013-54727), various plug-in types (so-called GG, G1, G2, GFF, GF2, GF1 and G1F, etc.) and other configurations (for example, those described in FIG. 6 of Japanese Patent Laid-Open No. 2013-164871). As a touch panel, the thing described in the paragraph 0229 of Unexamined-Japanese-Patent No. 2017-120435 is mentioned, for example. [Example]

Hereinafter, embodiments of the present invention will be described in more detail with reference to Examples. Materials, usage amounts, ratios, processing contents, processing steps, and the like shown in the following examples can be appropriately changed without departing from the spirit of the embodiments of the present invention. Therefore, the scope of the embodiment of the present invention is not limited to the specific examples shown below. In addition, unless otherwise specified, "part" and "%" are based on mass.

The following abbreviations represent the following compounds, respectively. "A-1": propylene glycol monomethyl ether acetate solution of a copolymer of styrene/methacrylic acid/methyl methacrylate (solid content concentration: 30.0 mass %, ratio of each monomer: 52 mass %/29 Mass %/19 mass %, Mw: 70,000) "A-2": propylene glycol monomethyl ether acetate solution of benzyl methacrylate/methacrylic acid copolymer (solid content concentration: 30.0 mass %, ratio of each monomer: 80 mass %/20 mass %, Mw: 30,000, acid value: 153mgKOH/g) "A-3": KURARAY POVALPVA-205 (manufactured by Kuraray Co., Ltd.) "A-4": Polyvinylpyrrolidone K-30 (manufactured by NIPPON SHOKUBAI CO., LTD.) "B-1": BPE-500 (manufactured by Shin Nakamura Chemical Industry Co., LTD.) "B-2": NK EsterHD-N (manufactured by Shin Nakamura Chemical Industry Co., LTD.) "B-3": Sartmer SR454 (manufactured by Arkema) "B-4": NK EsterA-TMPT (manufactured by Shin Nakamura Chemical Industry Co., LTD.) "B-5": Dimethacrylate of polyethylene glycol with an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide added to both ends of bisphenol A, respectively "B-6": NK EsterA-9300-1CL (manufactured by Shin Nakamura Chemical Industry Co., LTD.) "B-7": NK EsterA-DCP (manufactured by Shin Nakamura Chemical Industry Co., LTD.) "B-8": 8UX-015A (manufactured by AISEI FINE CHEMICAL CO,.LTD.) "B-9": ARONIXTO-2349 (manufactured by TOAGOSEI CO., LTD.) "C-1": B-CIM (manufactured by KUROGANE KASEI Co., Ltd.) "C-2": SB-PI 701 (obtained from Sanyo Trading Co., Ltd.) "C-3": 4,4'-bis(dimethylamino)benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) "C-4": Coumarin 7 (manufactured by Tokyo Chemical Industry Co., Ltd.) "C-5": 3-Acetyl-7-(diethylamino)coumarin (manufactured by FUJIFILM Wako Pure Chemical Corporation) "D-1": TDP-G (manufactured by Kawaguchi Chemical Industry Co., LTD.) "D-2": 1-Phenyl-3-pyrazolidone (manufactured by FUJIFILM Wako Pure Chemical Corporation) "E-1": Colorless crystal violet (manufactured by Tokyo Chemical Industry Co., Ltd.) "E-2": N-phenylamine carboxylmethyl-N-carbonylmethylaniline (manufactured by FUJIFILM Wako Pure Chemical Corporation) "E-3": Solvent Yellow 56 (manufactured by Tokyo Chemical Industry Co., Ltd.) "E-4": Diethylamino-phenylsulfonyl-based ultraviolet absorber (manufactured by DAITO CHEMICAL CO., LTD.) "E-5": 1-Dodecanethiol (manufactured by Tokyo Chemical Industry Co., Ltd.) "E-6": Karenz MT (registered trademark) BD1 (manufactured by SHOWA DENKO K.K.) "E-7": Sulbutiamine (manufactured by Tokyo Chemical Industry Co., Ltd.) "E-8": Bis(2-benzylaminophenyl)disulfide (manufactured by Tokyo Chemical Industry Co., Ltd.) "E-9": VD-5 (manufactured by SHIKOKU CHEMICALS CORPORATION) "E-10": 1,2,4-triazole (manufactured by Tokyo Chemical Industry Co., Ltd.) "E-11": 1,2,3-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.) "E-12": Benzothiazole (manufactured by Tokyo Chemical Industry Co., Ltd.) "E-13": CBT-1 (manufactured by JOHOKU CHEMICAL CO.,LTD) "E-14": MEGAFACE F-552 (manufactured by DIC Corporation) "E-15": MEGAFACE F-444 (manufactured by DIC Corporation) "F-1": Methyl ethyl ketone (manufactured by SANKYO CHEMICAL Co., Ltd.) "F-2": Propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO K.K.) "F-3": Ion-exchanged water "F-4": Methanol (manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC.)

<Preparation of thermoplastic resin composition> The respective compounds described in Table 1 were mixed in the amounts described in Table 1 to prepare thermoplastic resin compositions 1a and 2a, respectively. In addition, the unit of the numerical value of each compound column described in Table 1 is a mass part.

[Table 1] Thermoplastic resin composition 1a 2a A-2 42.02 42.15 B-7 5.03 5.03 B-8 2.31 2.31 B-9 0.77 0.77 E-3 0.25 - E-4 - 0.10 E-14 0.03 0.03 F-1 40.08 40.10 F-2 9.51 9.51

<Preparation of water-soluble resin layer composition> Each compound described in Table 2 was mixed in the amounts described in Table 2 to prepare a water-soluble resin layer composition 1b. In addition, the unit of the numerical value of each compound column described in Table 2 is a mass part.

[Table 2] Water-soluble resin layer composition 1b A-3 3.22 A-4 1.49 E-15 0.0015 F-3 38.12 F-4 57.17

<Preparation of photosensitive resin composition> Each compound described in Table 3 or Table 4 was mixed in the amount described in Table 3 or Table 4, and the photosensitive resin compositions 1c to 30c and 1d were prepared, respectively. In addition, the unit of the numerical value of each compound column described in Table 3 and Table 4 is mass part.

[table 3] Photosensitive resin composition 1c 2c 3c 4c 5c 6c 7c 8c 9c 10c 11c 12c 13c 14c 15c 16c A-1 25.4 25.4 25.4 25.4 25.4 25.4 25.4 25.4 25.4 23.4 23.4 23.4 25.4 25.4 25.4 25.4 B-1 4.1 4.1 4.1 4.1 4.1 4.1 4.1 4.1 4.1 4.1 4.1 4.1 4.1 4.1 4.1 4.1 B-2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 B-3 - - - - - - - - - - - - - - - - B-4 - - - - - - - - - - - - - - - - B-5 - - - - - - - - - - - - - - - - B-6 - - - - - - - - - - - - - - - - C-1 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 C-2 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 - - - - C-3 - - - - - - - - - - - - 0.04 0.04 0.04 - C-4 - - - - - - - - - - - - - - - 0.04 C-5 - - - - - - - - - - - - - - - - D-1 0.0175 0.0175 0.0175 0.0175 0.0175 0.0175 0.0175 0.0175 0.0175 0.0175 0.0175 0.0175 0.0175 0.0175 0.0175 0.0175 D-2 0.0011 0.0011 0.0011 0.0011 0.0011 0.0011 0.0011 0.0011 0.0011 0.0011 0.0011 0.0011 0.0011 0.0011 0.0011 0.0011 E-1 0.051 0.051 0.051 0.051 0.051 0.051 0.051 0.051 0.051 0.051 0.051 0.051 0.051 0.051 0.051 0.051 E-2 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 E-5 0.15 - - - - - - - - - - - - - - - E-6 - 0.15 - - - - - - - - - - - - - - E-7 - - 0.15 - - - - - - 0.75 - - 0.75 - - 0.75 E-8 - - - 0.15 - - - - - - - - - - - - E-9 - - - - 0.15 - - - - - 0.75 - - 0.75 - - E-10 - - - - - 0.15 - - - - - 0.75 - - 0.75 - E-11 - - - - - - 0.15 - - - - - - - - - E-12 - - - - - - - 0.15 - - - - - - - - E-13 - - - - - - - - 0.15 - - - - - - - E-14 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 F-1 39.6 39.6 39.6 39.6 39.6 39.6 39.6 39.6 39.6 40.4 40.4 40.4 39.6 39.6 39.6 39.6 F-2 26.1 26.1 26.1 26.1 26.1 26.1 26.1 26.1 26.1 26.7 26.7 26.7 26.1 26.1 26.1 26.1 F-4 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2

[Table 4] Photosensitive resin composition 17c 18c 19c 20c 21c 22c 23c 24c 25c 26c 27c 28c 29c 30c 1d A-1 25.4 25.4 25.4 25.4 25.4 25.4 25.4 25.4 25.4 25.4 25.4 25.4 25.4 25.4 25.5 B-1 4.1 4.1 4.1 4.1 4.1 - - - - - - - - - 4.15 B-2 2.2 2.2 2.2 2.2 2.2 - - - - - - - - - 2.25 B-3 - - - - - 3.15 3.15 3.15 1.1 1.1 1.1 2.2 2.2 2.2 - B-4 - - - - - 3.15 3.15 3.15 1.1 1.1 1.1 - - - - B-5 - - - - - - - - 4.1 4.1 4.1 - - - - B-6 - - - - - - - - - - - 4.1 4.1 4.1 - C-1 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 C-2 - - - - - 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 C-3 - - - - - - - - - - - - - - - C-4 0.04 0.04 - - - - - - - - - - - - - C-5 - - 0.04 0.04 0.04 - - - - - - - - - - D-1 0.0175 0.0175 0.0175 0.0175 0.0175 0.0175 0.0175 0.0175 0.0175 0.0175 0.0175 0.0175 0.0175 0.0175 0.0175 D-2 0.0011 0.0011 0.0011 0.0011 0.0011 0.0011 0.0011 0.0011 0.0011 0.0011 0.0011 0.0011 0.0011 0.0011 0.0011 E-1 0.051 0.051 0.051 0.051 0.051 0.051 0.051 0.051 0.051 0.051 0.051 0.051 0.051 0.051 0.051 E-2 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 E-5 - - - - - - - - - - - - - - - E-6 - - - - - - - - - - - - - - - E-7 - - 0.75 - - 0.75 - - 0.75 - - 0.75 - - - E-8 - - - - - - - - - - - - - - - E-9 0.75 - - 0.75 - - 0.75 - - 0.75 - - 0.75 - - E-10 - 0.75 - - 0.75 - - 0.75 - - 0.75 - - 0.75 - E-11 - - - - - - - - - - - - - - - E-12 - - - - - - - - - - - - - - - E-13 - - - - - - - - - - - - - - - E-14 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 F-1 39.6 39.6 39.6 39.6 39.6 39.6 39.6 39.6 39.6 39.6 39.6 39.6 39.6 39.6 39.6 F-2 26.1 26.1 26.1 26.1 26.1 26.1 26.1 26.1 26.1 26.1 26.1 26.1 26.1 26.1 26.1 F-4 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2

<Preparation of photosensitive transfer material> On a dummy support (polyethylene terephthalate film, thickness: 16 μm, haze: 0.12%), a slit-shaped nozzle was used on the surface of the dummy support with a coating width of 1.0 m and a dry layer thickness of 3.0 The thermoplastic resin compositions described in Table 5 were applied in a manner of μm. The formed coating film of the thermoplastic resin composition was dried at 80° C. for 40 seconds to form a thermoplastic resin layer. Using a slit nozzle, the water-soluble resin layer composition described in Table 5 was applied on the surface of the formed thermoplastic resin layer with a coating width of 1.0 m and a layer thickness after drying of 1.2 μm. The coating film of the water-soluble resin layer composition was dried at 80° C. for 40 seconds to form an intermediate layer. On the surface of the formed water-soluble resin layer, using a slit nozzle, the photosensitive resin composition described in Table 5 was applied so that the coating width was 1.0 m and the layer thickness after drying was 5.0 μm. The photosensitive resin layer was formed by drying at 100 degreeC for 2 minutes. A protective film (polypropylene film, thickness: 12 μm) was bonded to the photosensitive resin layer to prepare a photosensitive transfer material.

A photosensitive transfer material was produced by combining the thermoplastic resin composition and the photosensitive resin composition described in Table 5, and the conductive pattern was produced and evaluated as follows.

(Examples 1 to 31) <Preparation of conductive base material> On a support (polyester film, Lumirer (registered trademark) #100-U34, manufactured by TORAY INDUSTRIES, INC.), it was applied by the inkjet method so that the coating width was 1.2 m and the dry film thickness was 1.0 μm. An ink containing silver nanoparticles and resin (DNS-0163I, manufactured by DAICEL CORPORATION) was calcined at 120° C. for 30 minutes to form a conductive substrate.

<Resolution evaluation> After peeling the protective film from the photosensitive transfer material to the conductive substrate prepared above, under the lamination conditions of a roll temperature of 100° C., a line pressure of 0.8 MPa, and a line speed of 3.0 m/min, the transfer film was attached. printing materials. For the attached photosensitive transfer material, the dummy support is not peeled off, and a glass mask having a line-and-space pattern (Duty ratio 1:1) with a line width of 3 μm to 40 μm is adhered to the dummy support and exposed to light. machine (M-1S, manufactured by MIKASA CO., LTD) for exposure. After being left to stand for 1 hour after exposure, the dummy support was peeled off, and the developer (28° C., 1.0% potassium carbonate aqueous solution) was sprayed and blown off to remove the uncured portion, and a resin pattern was produced. About the obtained sample, the ferric nitrate aqueous solution (30 degreeC, 40.0 mass %) was spray-blown off, and the conductive layer of the part which does not exist a resin pattern was removed. Furthermore, the tetramethylammonium hydroxide (TMAH) aqueous solution (2.38 mass %) of 40 degreeC was spray-removed, the residual resin pattern was removed, and the conductive pattern was produced.

The line and space patterns of the obtained samples were observed, the line width of the line pattern with the highest resolution was taken as the resolution of the sample, and the resolution was evaluated according to the following criteria. In addition, when the side wall part of a pattern has large roughness, or when a remarkable fold arises and it connects with the adjacent line pattern, the resolution evaluation is made E. As a resolution evaluation, A to C are preferable, A or B is more preferable, and A is particularly preferable. -Evaluation criteria- A: 8μm or less B: More than 8 μm and 10 μm or less C: More than 10 μm and 20 μm or less D: more than 20μm

＜Cross-cut adhesion evaluation＞ In the same manner as in the resolution evaluation, the photosensitive transfer material was bonded to the conductive substrate. After peeling off the dummy support, cross-cutting was performed by the method described in JIS K5600-5-6 (1999), and the adhesiveness to the base material was evaluated from the residual state of the photosensitive resin layer after peeling off the tape. The cross-section adhesiveness was evaluated in 6 steps of 0 to 5 described in the above-mentioned JIS standard, and the smaller the number, the better the adhesiveness. If the adhesiveness is good, the photosensitive resin layer is less likely to be peeled from the conductive base material in the photolithography process, and therefore, improvement in quality and yield can be expected. As for the evaluation of cross-cut adhesion, 4 or less is preferable, 2 or less is more preferable, and 1 or less is particularly preferable.

Table 5 shows the detailed evaluation results of the photosensitive transfer materials used in the respective examples.

[table 5] Photosensitive transfer material thermoplastic resin composition Soluble resin composition Photosensitive resin composition Cross-cut adhesion evaluation Resolution evaluation Example 1 1 1a 1b 1c 4 C Example 2 2 1a 1b 2c 4 C Example 3 3 1a 1b 3c 2 B Example 4 4 1a 1b 4c 2 C Example 5 5 1a 1b 5c 2 B Example 6 6 1a 1b 6c 2 B Example 7 7 1a 1b 7c 4 C Example 8 8 1a 1b 8c 3 B Example 9 9 1a 1b 9c 3 B Example 10 10 1a 1b 10c 1 A Example 11 11 1a 1b 11c 0 A Example 12 12 1a 1b 12c 0 A Example 13 13 1a 1b 13c 2 B Example 14 14 1a 1b 14c 2 B Example 15 15 1a 1b 15c 2 B Example 16 16 2a 1b 16c 2 B Example 17 17 2a 1b 17c 2 B Example 18 18 2a 1b 18c 2 B Example 19 19 2a 1b 19c 2 B Example 20 20 2a 1b 20c 2 B Example 21 twenty one 2a 1b 21c 2 B Example 22 twenty two 1a 1b 22c 3 C Example 23 twenty three 1a 1b 23c 3 C Example 24 twenty four 1a 1b 24c 3 C Example 25 25 1a 1b 25c 3 C Example 26 26 1a 1b 26c 3 C Example 27 27 1a 1b 27c 3 C Example 28 28 1a 1b 28c 3 B Example 29 29 1a 1b 29c 3 B Example 30 30 1a 1b 30c 3 B Example 31 31 1a 1b 1d 4 C

As shown in the above-mentioned Table 5, the conductive pattern excellent in the analytical property was obtained by the manufacturing method of the conductive pattern of Examples 1-31. In the manufacturing method of the conductive pattern of Examples 1-31, the adhesiveness of the resin pattern obtained was excellent also.

(Example 32) <Preparation of conductive base material> According to the method described in paragraphs 0057 to 0064 of US Patent Application Publication No. 2019/0103200, and with the formulation of Example 1 described in TABLE 1, an ink containing silver nanoparticles and ethyl cellulose was prepared. The average primary particle size of the silver nanoparticles was 121 nm. On a support (polyester film, Lumirer (registered trademark) #125-X10S, manufactured by TORAY INDUSTRIES, INC.), the ink obtained above was applied to a dry film thickness of 1.0 μm by an ink jet method, and Baking was performed for 30 minutes at 150 degreeC, and the electroconductive base material was formed. Using the photosensitive transfer material used in Example 1, the obtained conductive substrate was evaluated in the same manner as in Example 1. The evaluation results of the resolution evaluation and the cross-section adhesion evaluation were the same as in Example 1, respectively.

(Example 33) <Preparation of conductive base material> According to the method described in paragraph 0051 of Japanese Patent Publication No. 2015-506061, an ink containing silver nanoparticles and polyester resin was prepared with the formulation of Example 2 described in Table 1. The average primary particle size of the silver nanoparticles was 114 nm. On the support (polyester film, Lumirer (registered trademark) #125-X10S, manufactured by TORAY INDUSTRIES, INC. ), the dry film thickness was set to 1.0 by the method described in paragraph 0051 of Japanese Patent Application Publication No. 2015-506061 The ink obtained above was screen-printed in a μm manner, and calcined at 190° C. for 60 minutes to form a conductive substrate. Using the photosensitive transfer material used in Example 1, the obtained conductive substrate was evaluated in the same manner as in Example 1. The evaluation results of the resolution evaluation and the cross-section adhesion evaluation were the same as in Example 1, respectively.

(Comparative Example 1) On a support (polyester film, Lumirer (registered trademark) #100-U34, manufactured by TORAY INDUSTRIES, INC.), using an inkjet head for a plate-to-plate setter (SJ02A, manufactured by Hitachi Koki Co., Ltd.), Silver nanoparticle and resin ink (DNS-0163I, manufactured by DAI-CELL-ALLNEX LTD.) was used to print fine line patterns. The obtained pattern was calcined at 120° C. for 30 minutes to prepare a conductive pattern. The pattern resolution was changed by changing the type of inkjet head and discharge conditions. The highest resolution was 48 μm, and the evaluation result of the resolution evaluation was D.

[Comparative Example 2] On a support (polyester film, Lumirer (registered trademark) #100-U34, manufactured by TORAY INDUSTRIES, INC.), using a plate-to-plate setting machine (SJ02A, manufactured by Hitachi Koki Co., Ltd.) with an ink jet head In Example 32, the thin line pattern was printed using the same ink. The obtained pattern was calcined at 120° C. for 30 minutes to prepare a conductive pattern. The pattern resolution was changed by changing the type of inkjet head and discharge conditions. The highest resolution was 64 μm, and the evaluation result of the resolution evaluation was D.

11: Pseudo support 12: transfer layer 13: Thermoplastic resin layer 15: Water-soluble resin layer 17: Photosensitive resin layer 19: Protective film 20: Photosensitive transfer material DL: Virtually show the framer for alignment EX: Image section (exposure section) GR: Non-image part (shading part)

FIG. 1 is a schematic diagram showing an example of the structure of a photosensitive transfer material. FIG. 2 is a schematic plan view showing the pattern A. FIG. FIG. 3 is a schematic plan view showing the pattern B. FIG.

11: Pseudo support

12: transfer layer

13: Thermoplastic resin layer

15: Water-soluble resin layer

17: Photosensitive resin layer

19: Protective film

20: Photosensitive transfer material

Claims (17)

A method of manufacturing a conductive pattern, comprising: Step 1 of forming a conductive layer comprising metal nanomaterials and resin on a part or the entire surface of the support; Step 2 of forming a photosensitive resin layer on the aforementioned conductive layer; an exposure step of exposing the aforementioned photosensitive resin layer; Removal step 1 of removing unnecessary parts from the exposed photosensitive resin layer and forming a resin pattern; and Removal step 2 of removing the aforementioned conductive layer in the portion where the aforementioned resin pattern is not formed and obtaining a conductive pattern. The method for manufacturing a conductive pattern according to claim 1, wherein The aforementioned metal nanomaterials include silver nanomaterials. The method for manufacturing a conductive pattern according to claim 1 or claim 2, wherein The aforementioned metal nanomaterials are particles having an average primary particle diameter of 1 nm to 200 nm. The method for manufacturing a conductive pattern according to claim 1 or claim 2, wherein The said photosensitive resin layer contains an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator. The method for manufacturing a conductive pattern according to claim 1 or claim 2, wherein The said photosensitive resin layer contains a polymer which has a structural unit which has an acid group protected by an acid-decomposable group, and a photoacid generator. The method for manufacturing a conductive pattern according to claim 1 or claim 2, wherein The said photosensitive resin layer contains the resin provided with the structural unit which has a phenolic hydroxyl group, and a quinonediazide compound. The method for manufacturing a conductive pattern according to claim 1 or claim 2, wherein The said photosensitive resin layer contains the compound which has an unshared electron pair. The method for manufacturing a conductive pattern according to claim 7, wherein The compound having the aforementioned unshared electron pair is a heterocyclic compound. The method for manufacturing a conductive pattern according to claim 1 or claim 2, wherein The above-mentioned forming step 2 is a step of forming the above-mentioned photosensitive resin layer by contacting and transferring the photosensitive transfer material on the above-mentioned conductive layer. The method for manufacturing a conductive pattern according to claim 1 or claim 2, wherein The aforementioned forming step 2 is a step of forming an intermediate layer and a photosensitive resin layer on the aforementioned conductive layer. The method for manufacturing a conductive pattern according to claim 1 or claim 2, wherein The exposure in the aforementioned exposure step is performed by contact exposure. The method for manufacturing a conductive pattern according to claim 1 or claim 2, wherein The exposure in the aforementioned exposure step is performed by direct drawing exposure. The method for manufacturing a conductive pattern according to claim 1 or claim 2, wherein The exposure in the aforementioned exposure step is performed by projection exposure. The method for manufacturing a conductive pattern according to claim 1 or claim 2, wherein The removal of the unnecessary parts in the removal step 1 is performed by a developer. The method for manufacturing a conductive pattern according to claim 1 or claim 2, wherein The removal of the conductive layer in the removal step 2 is performed by wet etching. The method for manufacturing a conductive pattern according to claim 1 or claim 2, wherein The removal of the conductive layer in the removal step 2 is performed by dry etching. A method of manufacturing an electronic component, comprising a conductive pattern obtained by the method of manufacturing a conductive pattern according to any one of claim 1 to claim 16.

Images