WO2022054599A1

WO2022054599A1 - Photosensitive transfer material, method for producing resin pattern, etching method, and method for manufacturing electronic device

Info

Publication number: WO2022054599A1
Application number: PCT/JP2021/031365
Authority: WO
Inventors: 洋行海鉾; 隆志有冨; 一真両角
Original assignee: 富士フイルム株式会社
Priority date: 2020-09-14
Filing date: 2021-08-26
Publication date: 2022-03-17
Also published as: CN116018262A; JPWO2022054599A1; JP7479487B2

Abstract

Provided is a photosensitive transfer material having a temporary support body, a photosensitive resin layer, and a protective film in that order. γb ≥ γc is satisfied, when: the surface energy of a surface of the temporary support body which is opposite the photosensitive resin layer side is γb (mN/m); and the surface energy of a surface of the protective film which is opposite the photosensitive resin layer side is γc (mN/m). Also provided are: a method for producing a resin pattern using the photosensitive transfer material; an etching method; and a method for manufacturing an electronic device.

Description

Photosensitive transfer material, resin pattern manufacturing method, etching method, and electronic device manufacturing method

The present disclosure relates to a photosensitive transfer material, a method for manufacturing a resin pattern, an etching method, and a method for manufacturing an electronic device.

In display devices equipped with a touch panel such as a capacitance type input device (organic electroluminescence (EL) display device, liquid crystal display device, etc.), the electrode pattern corresponding to the sensor of the visual recognition part, the peripheral wiring part, and the wiring of the take-out wiring part are wired. The conductive layer pattern such as is provided inside the touch panel.
Generally, in forming a patterned layer, the number of steps for obtaining the required pattern shape is small, so a layer of a photosensitive resin composition provided on an arbitrary substrate using a photosensitive transfer material is used. On the other hand, a method of developing after exposure through a mask having a desired pattern is widely used.

Further, as a conventional photosensitive transfer material, those described in JP-A-2019-128445 are known. Patent Document 1 has a photosensitive layer, an adhesive layer, and a temporary support in this order on a protective film, the photosensitive layer contains particles, and the photosensitive layer and the adhesive layer come into contact with each other. The photosensitive layer and the adhesive layer can be peeled off, and the surface of the photosensitive layer after peeling the photosensitive layer and the adhesive layer has irregularities formed by the particles. The transfer material is described.

An object to be solved by one embodiment of the present disclosure is to provide a photosensitive transfer material capable of obtaining a resin pattern with few defects even when the photosensitive resin layer is exposed via a temporary support. be.
Further, an object to be solved by another embodiment of the present disclosure is to provide a method for producing a resin pattern using the above-mentioned photosensitive transfer material, an etching method, and a method for producing an electronic device.

The disclosure includes the following aspects:
<1> The temporary support, the photosensitive resin layer, and the protective film are provided in this order, and the surface energy of the surface of the temporary support opposite to the photosensitive resin layer side is γb (mN / m). A photosensitive transfer material that satisfies γb ≧ γc when the surface energy of the surface of the protective film opposite to the photosensitive resin layer side is γc (mN / m).
<2> The photosensitive transfer material according to <1>, wherein the temporary support has a thickness of 20 μm or less.
<3> The photosensitive transfer material according to <1> or <2>, wherein the thickness of the photosensitive resin layer is 10 μm or less.
<4> The photosensitive transfer material according to any one of <1> to <3>, which further has another layer between the temporary support and the photosensitive resin layer.
<5> The photosensitive transfer material according to any one of <1> to <4>, wherein the haze value of the temporary support is less than 1.0%.
<6> The photosensitive transfer material according to any one of <1> to <5>, wherein the temporary support has a peeling force of 0.5 mN / mm or more.
<7> The photosensitive according to any one of <1> to <6>, wherein the arithmetic average roughness Ra value of the surface of the temporary support opposite to the photosensitive resin layer side is 50 nm or less. Sex transfer material.
<8> The photosensitive property according to any one of <1> to <7>, wherein the arithmetic average roughness Ra value of the surface of the protective film opposite to the photosensitive resin layer side is 50 nm or less. Transfer material.
<9> The photosensitive transfer material according to any one of <1> to <8>, wherein the value of γb-γc is more than 0 mN / m and 50 mN / m or less.
<10> The photosensitive transfer material according to any one of <1> to <9>, wherein the value of γb-γc is 2 mN / m or more and 30 mN / m or less.
<11> The photosensitive transfer material according to any one of <1> to <10>, wherein the value of γb-γc is 7 mN / m or more and 20 mN / m or less.
<12> The photosensitive transfer material according to any one of <1> to <11>, which is a roll-shaped photosensitive transfer material.
<13> With respect to the step of peeling the protective film from the photosensitive transfer material according to any one of <1> to <12> and the temporary support in the photosensitive transfer material from which the protective film has been peeled off. The outermost layer on the side having the photosensitive resin layer was brought into contact with the substrate having the conductive layer and bonded to each other, and the photosensitive resin layer was exposed to a pattern through the temporary support. A method for producing a resin pattern, which comprises a step of developing the photosensitive resin layer to form a resin pattern and the process of forming the resin pattern in this order.
<14> A region in which the resin pattern is not arranged in the laminated body in which the substrate, the conductive layer, and the resin pattern manufactured by the method for manufacturing the resin pattern according to <13> are laminated in this order. The etching method including the step of etching the said conductive layer in.
<15> With respect to the step of peeling the protective film from the photosensitive transfer material according to any one of <1> to <12> and the temporary support in the photosensitive transfer material from which the protective film has been peeled off. The outermost layer on the side having the photosensitive resin layer was brought into contact with the substrate having the conductive layer and bonded to each other, and the photosensitive resin layer was exposed to a pattern through the temporary support. A method for manufacturing an electronic device having the resin pattern, comprising the steps of developing the photosensitive resin layer to form a resin pattern in this order.

According to one embodiment of the present disclosure, it is possible to provide a photosensitive transfer material that can obtain a resin pattern with few defects even when the photosensitive resin layer is exposed via a temporary support.
Further, according to another embodiment of the present disclosure, it is possible to provide a method for manufacturing a resin pattern using the above-mentioned photosensitive transfer material, an etching method, and a method for manufacturing an electronic device.

FIG. 1 is a schematic view showing an example of the configuration of the photosensitive transfer material of the first embodiment. FIG. 2 is a schematic view showing an example of the configuration of the photosensitive transfer material of the second embodiment. FIG. 3 is a schematic plan view showing the pattern A. FIG. 4 is a schematic plan view showing the pattern B.

Hereinafter, the contents of the present disclosure will be described. Although the description will be given with reference to the attached drawings, the reference numerals may be omitted.
Further, the numerical range represented by using "-" in the present specification means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
Further, in the present specification, "(meth) acrylic" represents both acrylic and methacrylic, or either, and "(meth) acrylate" represents both acrylate and methacrylate, or either, and "(meth) acrylate". ) Acryloyl "represents both acryloyl and / or methacryloyl.
Further, in the present specification, the amount of each component in the composition is the sum of the plurality of applicable substances present in the composition when a plurality of the substances corresponding to each component are present in the composition, unless otherwise specified. Means quantity.
In the present specification, the term "process" is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution includes those having no substituent as well as those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
As used herein, the term "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Further, as the light used for exposure, generally, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams (active energy rays) are used. Can be mentioned.
Further, the chemical structural formula in the present specification may be described by a simplified structural formula in which a hydrogen atom is omitted.
In the present specification, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.
Further, in the present specification, a combination of two or more preferred embodiments is a more preferred embodiment.
Further, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present specification are columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all are trade names manufactured by Toso Co., Ltd.). The molecular weight is detected by the solvent THF (tetrahydrofuran) and the differential refractometer by the gel permeation chromatography (GPC) analyzer used, and is converted by using polystyrene as a standard substance.
As used herein, the term "total solid content" refers to the total mass of the components excluding the solvent from the total composition of the composition. Further, the "solid content" is a component excluding the solvent as described above, and may be, for example, a solid or a liquid at 25 ° C.

(Photosensitive transfer material)
The photosensitive transfer material according to the present disclosure has a temporary support, a photosensitive resin layer, and a protective film in this order, and the surface energy of the surface of the temporary support opposite to the photosensitive resin layer side. Is γb (mN / m), and γb ≧ γc is satisfied when the surface energy of the surface of the protective film opposite to the photosensitive resin layer side is γc (mN / m).

In a wiring formation process using a conventional photosensitive transfer material as described in JP-A-2019-128445, a photosensitive resin layer bonded to a substrate having a conductive layer is exposed via a temporary support. The present inventors have found that the obtained resin pattern is defective due to the foreign matter adhering to the temporary support.
As a result of detailed studies by the present inventors, the present inventors have found that by adopting the above embodiment, a resin pattern having few defects can be obtained even when the photosensitive resin layer is exposed via a temporary support. Found.
In the photosensitive transfer material according to the present disclosure, the surface energy of the surface of the temporary support opposite to the photosensitive resin layer side is γb (mN / m), and the surface energy of the temporary support is the same as that of the photosensitive resin layer side of the protective film. Satisfies γb ≧ γc when the surface energy of the opposite surface is γc (mN / m). As a result, although the detailed mechanism is unknown, the temporary support and the protective film come into contact with each other by laminating the photosensitive transfer material or winding the photosensitive transfer material in a roll shape, and the temporary support is described above. Foreign matter such as dust adhering to the body moves to the protective film and is removed from the temporary support, so that even when the photosensitive resin layer is exposed through the temporary support. It is estimated that a resin pattern with few defects can be obtained.
The "defect" of the resin pattern in the present disclosure is a defective shape of the resin pattern. When the wiring is manufactured by using the resin pattern having the above defect as an etching mask, the wiring due to the defect is broken (open) or the wiring is connected to each other (short circuit). In particular, the higher the definition of the pattern, the greater the effect.

The photosensitive transfer material according to the present disclosure has a surface energy of γb (mN / m) on the surface of the temporary support opposite to the photosensitive resin layer side, and is different from the photosensitive resin layer side of the protective film. Satisfies γb ≧ γc when the surface energy of the opposite surface is γc (mN / m).
The method for adjusting the surface energy of the temporary support and the protective film is not particularly limited, but the type of resin used, the composition of additives and the like, the surface treatment, the stretching treatment, the formation of a particle-containing layer and the like described later, etc. Method can be mentioned.

In the present disclosure, the surface energy (unit: mN / m) of the temporary support or the protective film is calculated by the following method.
On the measurement surface of the temporary support or protective film, the contact angles of two types of liquids, pure water and methylene iodide, were measured in an atmosphere of room temperature of 23 ° C and relative humidity of 50% to 60%. Measure 3 points by (Kyowa Interface Science Co., Ltd.). The average value of the measured values obtained for each liquid is taken as the contact angle of each of the two types of liquids. Using the contact angles of the two obtained liquids, the surface energy γ (= γ ^d) , which is the sum of the dispersion force γ ^d , the polarity force γ ^p , and the dispersion force and the polarity force, is obtained by the geometric mean method based on Owns-Wendt. + Γ ^p ) is calculated.
A specific calculation method is shown. The meaning of each symbol is shown below. When γ _SL is the tension at the interface between the solid and the liquid, the following mathematical formula (1) holds.
γ _SL : Surface free energy of film surface and known liquid γ _S : Surface free energy of known liquid γ _L : Surface free energy of known liquid γ _S ^d : Dispersive force component of surface free energy of film surface γ _S ^p : Polarity component of surface free energy of film surface γ _L ^d : Dispersive force component of surface free energy of known liquid γ _L ^p : Polar force component of surface free energy of known liquid γ _SL = γ _S + γ _L -2 ( γ _S ^d・ γ _L ^d ) ^1/2 -2 (γ _S ^p・ γ _L ^p ) ^1/2・・・ Equation (1)
Further, the state when the smooth solid surface and the droplet are in contact with each other at the contact angle (θ) is expressed by the following equation (Young's equation).
γ _S = γ _SL + γ _L cos θ ・・・ Equation (2)
By combining these mathematical formulas (1) and (2), the following equation is obtained.
(Γ _s ^d・ γ _L ^d ) ^1/2 + (γ _s ^p・ γ _L ^p ) ^1/2 (= γ _L (1 + cos θ) / 2 ... Equation (3)
Actually, the contact angle (θ) of two kinds of liquids, pure water and methylene iodide, the surface energy γ _L of the known liquid, and each component (γ _L ^d , γ _L ^p ) are calculated in the formula (3). Substitute and solve simultaneous equations.
As a result, the surface energy (γ _S ) of the film is calculated.

In the photosensitive transfer material according to the present disclosure, the value of γb-γc is the defect suppressing property of the resin pattern and the resolution property (hereinafter, simply “resin pattern defect suppressing property” when exposed via a temporary support. From the viewpoint of "resolvability"), it is preferably more than 0 mN / m and 50 mN / m or less, more preferably 2 mN / m or more and 30 mN / m or less, and 7 mN / m or more and 20 mN. It is particularly preferable that it is / m or less.

In the photosensitive transfer material according to the present disclosure, the value of the surface energy γb on the surface of the temporary support opposite to the photosensitive resin layer side is determined from the viewpoint of defect suppression and resolvability of the resin pattern. , 30 mN / m to 70 mN / m, more preferably 40 mN / m to 65 mN / m, and particularly preferably 45 mN / m to 60 mN / m.

In the photosensitive transfer material according to the present disclosure, the value of the surface energy γc on the surface of the protective film opposite to the photosensitive resin layer side is determined from the viewpoint of defect suppression property and resolution property of the resin pattern. It is preferably 20 mN / m to 65 mN / m, more preferably 25 mN / m to 55 mN / m, and particularly preferably 30 mN / m to 45 mN / m.

The photosensitive transfer material according to the present disclosure has a temporary support, a photosensitive resin layer, and a protective film in this order.
Further, the photosensitive transfer material according to the present disclosure may have another layer between the temporary support and the photosensitive resin layer, between the photosensitive resin layer and the protective film, and the like.
The photosensitive transfer material according to the present disclosure is preferably a roll-shaped photosensitive transfer material from the viewpoint of further exerting the effect in the present disclosure.

An example of the embodiment of the photosensitive transfer material according to the present disclosure is shown below, but the present invention is not limited thereto.
(1) "Temporary support / photosensitive resin layer / refractive index adjusting layer / protective film"
(2) "Temporary support / photosensitive resin layer / protective film"
(3) "Temporary support / water-soluble resin layer / photosensitive resin layer / protective film"
(4) "Temporary support / thermoplastic resin layer / water-soluble resin layer / photosensitive resin layer / protective film"
In each of the above configurations, the photosensitive resin layer is preferably a negative photosensitive resin layer. It is also preferable that the photosensitive resin layer is a colored resin layer. The photosensitive transfer material according to the present disclosure may be used as a photosensitive transfer material for a wiring protective film or as a photosensitive transfer material for an etching resist, as will be described later.
When the photosensitive transfer material for a wiring protective film is used, the configuration of the photosensitive transfer material is preferably, for example, the configuration of (1) or (2) described above.
Further, in the case of using a photosensitive transfer material for an etching resist, the composition of the photosensitive transfer material is preferably, for example, the above-mentioned configurations (2) to (4).

In the case of a photosensitive transfer material having another layer on the side opposite to the temporary support side of the photosensitive resin layer, the sum of the other layers arranged on the side opposite to the temporary support side of the photosensitive resin layer. The thickness is preferably 0.1% to 30%, more preferably 0.1% to 20%, based on the thickness of the photosensitive resin layer.

Hereinafter, the photosensitive transfer material according to the present disclosure will be described with reference to an example of a specific embodiment. The photosensitive transfer material of the first embodiment below has a configuration that can be suitably used as a photosensitive transfer material for an etching resist, and the photosensitive transfer material of the second embodiment below is photosensitive for a wiring protective film. It is a configuration that can be suitably used for a transfer material.

[[Photosensitive transfer material of the first embodiment]]
Hereinafter, the photosensitive transfer material of the first embodiment will be described with an example.
The photosensitive transfer material 20 shown in FIG. 1 includes a temporary 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. Have in order.
Further, the photosensitive transfer material 20 shown in FIG. 1 has a form in which the thermoplastic resin layer 13 and the water-soluble resin layer 15 are arranged, but the thermoplastic resin layer 13 and the water-soluble resin layer 15 may not be arranged. ..
Hereinafter, each element constituting the photosensitive transfer material of the first embodiment will be described.

[Temporary support]
The photosensitive transfer material used in the present disclosure has a temporary support.
The temporary support is a support that supports a photosensitive resin layer or a laminate containing the photosensitive resin layer and is removable.

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

Examples of the material constituting the temporary support include a glass substrate, a resin film and paper, and a resin film is preferable from the viewpoint of strength, flexibility and light transmission.
Examples of the resin film include polyethylene terephthalate (PET) film, cellulose triacetate film, polystyrene film and polycarbonate film. Among them, PET film is preferable, and biaxially stretched PET film is more preferable.

The thickness (layer thickness) of the temporary support is not particularly limited, and the strength as the support, the flexibility required for bonding to the circuit wiring forming substrate, and the light required in the first exposure step are not particularly limited. From the viewpoint of transparency, it may be selected according to the material.
The thickness of the temporary support is preferably in the range of 5 μm to 100 μm, more preferably in the range of 10 μm to 50 μm, further preferably in the range of 10 μm to 20 μm, and in the range of 10 μm to 16 μm from the viewpoint of ease of handling and versatility. Especially preferable.
The thickness of the temporary support is preferably 50 μm or less, more preferably 25 μm or less, and more preferably 20 μm or less, from the viewpoint of defect suppression, resolution, and linearity of the resin pattern. Especially preferable.

Further, it is preferable that the film used as the temporary support is free from deformation such as wrinkles, scratches, defects and the like.
From the viewpoint of pattern formation during pattern exposure via the temporary support and transparency of the temporary support, it is preferable that the number of fine particles, foreign substances, defects, precipitates, etc. contained in the temporary support is small. The number of fine particles, foreign substances and defects having a diameter of 1 μm or more is preferably 50 pieces / 10 mm ² or less, more preferably 10 pieces / 10 mm ² or less, and further preferably 3 pieces / 10 mm ² or less. , 0 pieces / 10 mm ² is particularly preferable.

From the viewpoint of defect suppression and resolution of the resin pattern and transparency of the temporary support, it is preferable that the haze of the temporary support is small. Specifically, the haze value of the temporary 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 disclosure is measured by a haze meter (NDH-2000, manufactured by Nippon Denshoku Kogyo Co., Ltd.) by a method according to JIS K 7105: 1981.

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

The arithmetic average roughness Ra of the surface of the temporary support opposite to the photosensitive resin layer side is the photosensitive of the temporary support from the viewpoints of transportability, defect suppression of the resin pattern, and resolution. It is preferable that the surface has an arithmetic average roughness Ra or more on the resin layer side.
The arithmetic average roughness Ra of the surface of the temporary support opposite to the photosensitive resin layer side is preferably 100 nm or less from the viewpoints of transportability, defect suppression of the resin pattern, and resolution. , 50 nm or less, more preferably 20 nm or less, and particularly preferably 10 nm or less.
The arithmetic average roughness Ra of the surface of the temporary support on the photosensitive resin layer side is preferably 100 nm or less from the viewpoint of peelability of the temporary support, defect suppression of the resin pattern, and resolution. , 50 nm or less, more preferably 20 nm or less, and particularly preferably 10 nm or less.
Further, the value of the arithmetic average roughness Ra of the surface of the temporary support on the side opposite to the photosensitive resin layer side was subtracted from the value of the arithmetic average roughness Ra of the surface of the temporary support on the side of the photosensitive resin layer. The value is preferably 0 nm to 10 nm, and more preferably 0 nm to 5 nm, from the viewpoints of transportability, defect suppression property of the resin pattern, and resolution.

The arithmetic average roughness Ra of the surface of the temporary support or the protective film in the present disclosure shall be measured by the following method.
Using a three-dimensional optical profiler (New View7300, manufactured by Zygo), the surface of the temporary support or the protective film is measured under the following conditions to obtain the surface profile of the film.
As the measurement / analysis software, Microscope Application of MetroPro ver8.3.2 is used. Next, the Surface Map screen is displayed by the above analysis software, and the histogram data is obtained in the Surface Map screen. From the obtained histogram data, the arithmetic mean roughness is calculated, and the Ra value of the surface of the temporary support or the protective film is obtained.
When the temporary support or the protective film is attached to the photosensitive resin layer or the like, the temporary support or the protective film may be peeled off from the photosensitive resin layer, and the Ra value of the surface on the peeled side may be measured.

The peeling force of the temporary support, specifically, the peeling force between the temporary support and the photosensitive resin layer or the thermoplastic resin layer is when the wound laminate is transported again by the roll-to-roll method. From the viewpoint of suppressing the peeling of the temporary support due to the adhesion between the vertically stacked laminates and the laminate, it is preferably 0.5 mN / mm or more, preferably 0.5 mN / mm to 2.0 mN / mm. Is more preferable.

The peeling force of the temporary support in the present disclosure shall be measured as follows.
A copper layer having a thickness of 200 nm is produced on a polyethylene terephthalate (PET) film having a thickness of 100 μm by a sputtering method, and a PET substrate with a copper layer is produced.
The protective film is peeled off from the produced photosensitive transfer material, and laminated on the PET substrate with a copper layer under laminating conditions of a laminating roll temperature of 100 ° C., a linear pressure of 0.6 MPa, and a linear velocity (laminating rate) of 1.0 m / min. Next, after attaching a tape (PINTACK manufactured by Nitto Denko Corporation) to the surface of the temporary support, a laminate having at least the temporary support and the photosensitive resin layer on a PET substrate with a copper layer is 70 mm × 10 mm. Cut to make a sample. The PET substrate side of the sample is fixed on the sample table.
Using a tensile compression tester (SV-55, manufactured by Imada Seisakusho Co., Ltd.), pull the tape in the direction of 180 degrees at 5.5 mm / sec to obtain a photosensitive resin layer or a thermoplastic resin layer and a temporary support. The force required for peeling (peeling force) is measured.

Preferred embodiments of the provisional support include, for example, paragraphs 0017 to 0018 of JP-A-2014-85643, paragraphs 0019 to 0026 of JP-A-2016-27363, and paragraphs 0041 to 0057 of International Publication No. 2012/081680. , Paragraphs 0029 to 0040 of International Publication No. 2018/179370, paragraphs 0012 to paragraph 0032 of JP-A-2019-101405, and the contents of these publications are incorporated in the present specification.

〔Protective film〕
The photosensitive transfer material has a protective film.
It is preferable that the photosensitive resin layer and the protective film are in direct contact with each other.

Examples of the material constituting the protective film include a resin film and paper, and a resin film is preferable from the viewpoint of strength and flexibility.
Examples of the resin film include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Of these, polyethylene film, polypropylene film, or 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, more preferably 10 μm to 50 μm.
The arithmetic mean roughness Ra of the surface of the protective film opposite to the surface opposite to the photosensitive resin layer side is the photosensitive resin layer of the protective film from the viewpoints of transportability, defect suppression of the resin pattern, and resolution. It is preferably equal to or less than the arithmetic mean roughness Ra of the side surface, and more preferably smaller than the arithmetic average roughness Ra of the surface on the photosensitive resin layer side of the protective film.
The arithmetic average roughness Ra of the surface of the protective film opposite to the photosensitive resin layer side is preferably 300 nm or less, more preferably 100 nm or less, still more preferably 70 nm or less, from the viewpoint of transportability and winding property. It is particularly preferably 50 nm or less.
The arithmetic average roughness Ra of the surface of the protective film on the photosensitive resin layer side is preferably 300 nm or less, more preferably 100 nm or less, further preferably 70 nm or less, and further preferably 50 nm or less, from the viewpoint of excellent resolution. Is particularly preferred. It is considered that the Ra value on the surface of the protective film is in the above range to improve the uniformity of the layer thickness of the photosensitive resin layer and the formed resin pattern.
The lower limit of the Ra value on the surface of the protective film is not particularly limited, but it is preferably 1 nm or more, more preferably 10 nm or more, and particularly preferably 20 nm or more on both sides.
Further, the peeling force of the protective film is preferably smaller than the peeling force of the temporary support.

[Photosensitive resin layer]
The photosensitive transfer material according to the present disclosure has a photosensitive resin layer.
The photosensitive resin layer may be a negative type photosensitive resin layer or a positive type photosensitive resin layer, but the solubility of the exposed part in the developing solution is lowered by the exposure, and the non-exposed part is developed by the development. It is preferably a negative photosensitive resin layer to be removed.
The photosensitive resin layer preferably contains an alkali-soluble resin, a polymerizable compound (preferably an ethylenically unsaturated compound), and a photopolymerization initiator. Based on the total mass of the photosensitive resin layer, the alkali-soluble resin: 10 mass. %-90% by mass; Ethylene unsaturated compound: 5% by mass-70% by mass; and photopolymerization initiator: 0.01% by mass to 20% by mass.
Hereinafter, each component will be described in order.

<Alkali-soluble resin>
The photosensitive resin layer preferably contains an alkali-soluble resin.
In the present specification, "alkali-soluble" means that the solubility of sodium carbonate in 100 g of a 1% by mass aqueous solution at 22 ° C. is 0.1 g or more.
The alkali-soluble resin is not particularly limited, and examples thereof include known alkali-soluble resins used for etching resists.
Further, the alkali-soluble resin is preferably a binder polymer.
The alkali-soluble resin is preferably an alkali-soluble resin having an acid group.
Among them, the alkali-soluble resin is preferably polymer A, which will be described later.

-Polymer A-
The alkali-soluble resin preferably contains the polymer A.
The acid value of the polymer A is preferably 220 mgKOH / g or less, more preferably less than 200 mgKOH / g, and more preferably 190 mgKOH / g, from the viewpoint of better resolution by suppressing the swelling of the photosensitive resin layer by the developing solution. Less than is more preferred.
The lower limit of the acid value of the polymer A is not particularly limited, but from the viewpoint of better developability, 60 mgKOH / g or more is preferable, 120 mgKOH / g or more is more preferable, 150 mgKOH / g or more is further preferable, and 170 mgKOH / g or more is more preferable. Especially preferable.

The acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample.
In the present specification, the unit is described as mgKOH / g. The acid value can be calculated, for example, from the average content of acid groups in the compound.
The acid value of the polymer A may be adjusted according to the type of the structural unit constituting the polymer A and the content of the structural unit containing the acid group.

The weight average molecular weight of the polymer A is preferably 5,000 to 500,000. It is preferable that the weight average molecular weight is 500,000 or less from the viewpoint of improving the resolvability and the developability. The weight average molecular weight is more preferably 100,000 or less, further preferably 60,000 or less, and particularly preferably 50,000 or less. On the other hand, setting the weight average molecular weight of the polymer A to 5,000 or more is the property of the developed aggregate and the properties of the unexposed film such as edge fuse property and cut chip property in the case of a photosensitive resin laminate. It is preferable from the viewpoint of controlling. The weight average molecular weight of the polymer A is more preferably 10,000 or more, further preferably 20,000 or more, and particularly preferably 30,000 or more. The edge fuse property refers to the degree of ease with which the photosensitive resin layer protrudes from the end face of the roll when the photosensitive transfer material is wound into a roll. The cut chip property refers to the degree of ease of chip flying when the unexposed film is cut with a cutter. If this chip adheres to the upper surface of the photosensitive resin laminate or the like, it will be transferred to the mask in a later exposure step or the like, causing a defective product. The dispersity of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, and even more preferably 1.0 to 4.0. It is more preferably 0.0 to 3.0. In the present disclosure, 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).

The photosensitive resin layer may contain a monomer component having an aromatic hydrocarbon group as the polymer A from the viewpoint of suppressing line width thickening or deterioration of resolution when the focal position is deviated during exposure. preferable. Examples of such aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The content ratio of the monomer component having an aromatic hydrocarbon group in the polymer A is preferably 20% by mass or more, preferably 30% by mass or more, based on the total mass of all the monomer components. More preferably, it is more preferably 40% by mass or more, particularly preferably 45% by mass or more, and most preferably 50% by mass or more. The upper limit is not particularly limited, but is preferably 95% by mass or less, and more preferably 85% by mass or less. When a plurality of types of the polymer A were contained, the content ratio of the monomer component having an aromatic hydrocarbon group was determined as a weight average value.

Examples of the monomer having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinyl). Benzoic acid, styrene dimer, styrene trimmer, etc.). Of these, a monomer having an aralkyl group or styrene is preferable. In one embodiment, when the monomer component having an aromatic hydrocarbon group in the polymer A is styrene, the content ratio of the styrene monomer component is 20% by mass based on the total mass of all the monomer components. It is preferably ~ 50% by mass, more preferably 25% by mass to 45% by mass, further preferably 30% by mass to 40% by mass, and particularly preferably 30% by mass to 35% by mass. preferable.

Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group), a substituted or unsubstituted benzyl group and the like, and a substituted or unsubstituted benzyl group is preferable.

Examples of the monomer having a phenylalkyl group include phenylethyl (meth) acrylate and the like.

Examples of the monomer having a benzyl group include (meth) acrylate having a benzyl group, for example, benzyl (meth) acrylate, chlorobenzyl (meth) acrylate and the like; vinyl monomers having a benzyl group, for example, vinylbenzyl chloride and vinylbenzyl. Examples include alcohol. Of these, benzyl (meth) acrylate is preferable. In one embodiment, 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 total of all the monomer components. Based on the mass, it is preferably 50% by mass to 95% by mass, more preferably 60% by mass to 90% by mass, further preferably 70% by mass to 90% by mass, and 75% by mass to 90% by mass. It is particularly preferably 90% by mass.

The polymer A containing a monomer component having an aromatic hydrocarbon group includes a monomer having an aromatic hydrocarbon group, at least one of the first monomers described below, and / or a second described below. It is preferably obtained by polymerizing with at least one of the monomers of.

The polymer A containing no monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the first monomers described later, and at least the first monomer. It is more preferable to obtain it by copolymerizing one kind with at least one kind of the second monomer described later.

The first monomer is a monomer having a carboxy group in the molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic acid anhydride, maleic acid semi-ester and the like. Among these, (meth) acrylic acid is preferable.
The content ratio of the first monomer in the polymer A is preferably 5% by mass to 50% by mass, preferably 10% by mass to 40% by mass, based on the total mass of all the monomer components. Is more preferable, and 15% by mass to 30% by mass is further 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. The copolymerization ratio of 10% by mass or more is preferable from the viewpoint of exhibiting good developability and controlling edge fuseability, more preferably 15% by mass or more, still more preferably 20% by mass or more. .. It is preferable to set the copolymerization ratio to 50% by mass or less from the viewpoint of high resolution and the shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern, and from these viewpoints, 35% by mass. The following is more preferable, 30% by mass or less is further preferable, and 27% by mass or less is particularly preferable.

The second monomer is a monomer that 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, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , Tart-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and other (meth) acrylates; vinyl acetate And the like, esters of vinyl alcohols; as well as (meth) acrylonitrile and the like. Of these, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-butyl (meth) acrylate are preferable, and methyl (meth) acrylate is particularly preferable.
The content ratio of the second monomer in the polymer A is preferably 5% by mass to 60% by mass, preferably 15% by mass to 50% by mass, based on the total mass of all the monomer components. Is more preferable, and 20% by mass to 45% by mass is further preferable.

It is preferable to contain a monomer having an aralkyl group and / or styrene as a monomer from the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position is deviated during exposure. For example, a copolymer containing methacrylic acid, benzyl methacrylate and styrene, a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate and styrene and the like are preferable.
In one embodiment, the polymer A contains 25% by mass to 40% by mass of a monomer component having an aromatic hydrocarbon group, 20% by mass to 35% by mass of the first monomer component, and a second unit amount. It is preferably a polymer containing 30% by mass to 45% by mass of a body component. In another embodiment, the polymer preferably contains 70% by mass to 90% by mass of a 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 a branched structure or an alicyclic structure in the side chain. Further, the polymer A may have a linear structure in the side chain. Introducing a branched structure or an alicyclic structure into the side chain of polymer A 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. Can be done. 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 i-propyl (meth) acrylic acid and (meth) acrylic acid. i-Butyl, (meth) acrylate s-butyl, (meth) acrylate t-butyl, (meth) acrylate i-amyl, (meth) acrylate t-amyl, (meth) acrylate sec-iso-amyl , 2-octyl (meth) acrylate, 3-octyl (meth) acrylate, t-octyl (meth) acrylate and the like. Among these, i-propyl (meth) acrylate, i-butyl (meth) acrylate, or t-butyl methacrylate are preferable, and i-propyl methacrylate or t-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 alicyclic hydrocarbon group and a monomer having a polycyclic alicyclic hydrocarbon group, and the number of carbon atoms (number of carbon atoms) can be mentioned. Examples thereof include (meth) acrylates having 5 to 20 alicyclic hydrocarbon groups. More specific examples include, for example, (meth) acrylic acid (bicyclo [2.2.1] heptyl-2), (meth) acrylic acid-1-adamantyl, (meth) acrylic acid-2-adamantyl, (meth). ) Acrylic acid-3-methyl-1-adamantyl, (meth) acrylate-3,5-dimethyl-1-adamantyl, (meth) acrylate-3-ethyladamantyl, (meth) acrylate-3-methyl-5 -Ethyl-1-adamantyl, (meth) acrylic acid-3,5,8-triethyl-1-adamantyl, (meth) acrylic acid-3,5-dimethyl-8-ethyl-1-adamantyl, (meth) acrylic acid 2-Methyl-2-adamantyl, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, octahydro-4,7-mentanoinden-5 (meth) acrylate -Il, octahydro-4,7-mentanoinden-1-ylmethyl (meth) acrylate, -1-mentyl (meth) acrylate, tricyclodecane (meth) acrylate, -3-hydroxy (meth) acrylate -2,6,6-trimethyl-bicyclo [3.1.1] heptyl, (meth) acrylic acid-3,7,7-trimethyl-4-hydroxybicyclo [4.1.0] heptyl, (meth) acrylic Examples thereof include acid (nor) bornyl, (meth) acrylate isobornyl, (meth) acrylate fentyl, (meth) acrylate-2,2,5-trimethylcyclohexyl, and (meth) acrylate cyclohexyl. Among these (meth) acrylic acid esters, (meth) acrylic acid cyclohexyl, (meth) acrylic acid (nor) boronyl, (meth) acrylic acid isobornyl, (meth) acrylic acid-1-adamantyl, (meth) acrylic acid- 2-adamantyl, fentyl (meth) acrylate, 1-mentyl (meth) acrylate, or tricyclodecane (meth) acrylate is preferred, cyclohexyl (meth) acrylate, (nor) bornyl, (meth) acrylate, Isobornyl (meth) acrylate, -2-adamantyl (meth) acrylate, or tricyclodecane (meth) acrylate are particularly preferred.

The polymer A can be used alone or in combination of two or more. When two or more kinds are mixed and used, two kinds of polymer A containing a monomer component having an aromatic hydrocarbon group may be mixed and used, or a monomer component having an aromatic hydrocarbon group may be used. It is preferable to use a mixture of the polymer A containing the polymer A and the polymer A containing no monomer component having an aromatic hydrocarbon group. In the latter case, the ratio of the polymer A containing the monomer component having an aromatic hydrocarbon group to the total amount of the polymer A is preferably 50% by mass or more, preferably 70% by mass or more. It is more preferably 80% by mass or more, and more preferably 90% by mass or more.

In the synthesis of the polymer A, a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile is added to a solution obtained by diluting the one or more monomers described above with a solvent such as acetone, methyl ethyl ketone and isopropanol. Is preferably added in an appropriate amount and heated and stirred. In some cases, a part of the mixture is added dropwise to the reaction solution for synthesis. After completion of the reaction, a solvent may be further added to adjust the concentration to a desired level. As the synthesis means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

The glass transition temperature Tg of the polymer A is preferably 30 ° C. or higher and 135 ° C. or lower. By using the polymer A having a Tg of 135 ° C. or lower in the photosensitive resin layer, it is possible to suppress line width thickening and deterioration of resolution when the focal position is deviated during exposure. From this viewpoint, the Tg of the polymer A is more preferably 130 ° C. or lower, further preferably 120 ° C. or lower, and particularly preferably 110 ° C. or lower. Further, it is preferable to use the polymer A having a Tg of 30 ° C. or higher from the viewpoint of improving the edge fuse resistance. From this viewpoint, the Tg of the polymer A is more preferably 40 ° C. or higher, further preferably 50 ° C. or higher, particularly preferably 60 ° C. or higher, and most preferably 70 ° C. or higher. ..

The photosensitive resin layer may contain a resin other than the alkali-soluble resin.
Resins other than the alkali-soluble resin include acrylic resin, styrene-acrylic copolymer (however, the styrene content is 40% by mass or less), polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, and polyamide. Examples thereof include resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines, and polyalkylene glycols.

The alkali-soluble resin may be used alone or in combination of two or more.
The ratio of the alkali-soluble resin to the total mass of the photosensitive resin layer is preferably in the range of 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, and further preferably 40% by mass to 40% by mass. It is 60% by mass. It is preferable that the ratio of the alkali-soluble resin to the photosensitive resin layer is 90% by mass or less from the viewpoint of controlling the developing time. On the other hand, it is preferable to set the ratio of the alkali-soluble resin to the photosensitive resin layer to 10% by mass or more from the viewpoint of improving the edge fuse resistance.

<Polymerizable compound>
The photosensitive resin layer preferably contains a polymerizable compound. In the present specification, the "polymerizable compound" means a compound that polymerizes under the action of a polymerization initiator described later, and is different from the above-mentioned alkali-soluble resin.

The polymerizable group of the polymerizable compound is not particularly limited as long as it is a group involved in the polymerization reaction, and has, for example, an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group and a maleimide group. Groups; and groups having a cationically polymerizable group such as an epoxy group and an oxetane group can be mentioned.
As the polymerizable group, a group having an ethylenically unsaturated group is preferable, and an acryloyl group or a methacryloyl group is more preferable.
The polymerizable compound preferably contains an ethylenically unsaturated compound, and more preferably contains a (meth) acrylate compound.

An ethylenically unsaturated compound is a compound having one or more ethylenically unsaturated groups.
The photosensitive resin layer preferably contains a bifunctional or higher functional ethylenically unsaturated compound as the ethylenically unsaturated compound.
Here, the bifunctional or higher functional ethylenically unsaturated compound means a compound having two or more ethylenically unsaturated groups in one molecule.
As the ethylenically unsaturated group, a (meth) acryloyl group is more preferable.
As the ethylenically unsaturated compound, a (meth) acrylate compound is preferable.

The ethylenically unsaturated compound may contain a compound having two or more ethylenically unsaturated groups (polyfunctional ethylenically unsaturated compound) in one molecule because the photosensitive resin layer has better photosensitivity. preferable.
Further, the number of ethylenically unsaturated groups contained in one molecule of the ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and 2 or less in terms of excellent resolution and peelability. More preferred.

The photosensitive resin layer is bifunctional or trifunctional having two or three ethylenically unsaturated groups in one molecule in that the photosensitive resin layer has a better balance between photosensitivity, resolution and peelability. It is preferable to contain an ethylenically unsaturated compound, and more preferably to contain a bifunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule.
The content of the bifunctional ethylenically unsaturated compound in the photosensitive resin layer with respect to the content of the ethylenically unsaturated compound is preferably 60% by mass or more, more preferably more than 70% by mass, and more preferably 90, from the viewpoint of excellent peelability. More preferably by mass% or more. The upper limit is not particularly limited and may be 100% by mass. That is, all the ethylenically unsaturated compounds contained in the photosensitive resin layer may be bifunctional ethylenically unsaturated compounds.
Further, as the ethylenically unsaturated compound, a (meth) acrylate compound having a (meth) acryloyl group as a polymerizable group is preferable.

-Ethylene unsaturated compound B1-
The photosensitive resin layer preferably 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.

The mass ratio of the content of the ethylenically unsaturated compound B1 to the content of the ethylenically unsaturated compound in the photosensitive resin layer is preferably 40% by mass or more, preferably 50% by mass, from the viewpoint of better resolution. % Or more, more preferably 55% by mass or more, and particularly preferably 60% by mass or more. The upper limit is not particularly limited, but from the viewpoint of peelability, 99% by mass or less is preferable, 95% by mass or less is more preferable, 90% by mass or less is further preferable, and 85% by mass or less is particularly preferable.

Examples of the aromatic ring contained in the ethylenically unsaturated compound B1 include an aromatic hydrocarbon ring such as a benzene ring, a naphthalene ring and an anthracene ring, a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring and a pyridine ring. Aromatic heterocycles and fused rings thereof are mentioned, and aromatic hydrocarbon rings are preferable, and benzene rings are more preferable. The aromatic ring may have a substituent.
The ethylenically unsaturated compound B1 may have only one aromatic ring or may have two or more aromatic rings.

The ethylenically unsaturated compound B1 preferably has a bisphenol structure from the viewpoint of improving the resolution by suppressing the swelling of the photosensitive resin layer by the developing solution.
Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis (4-hydroxyphenyl) propane) and a bisphenol derived from bisphenol F (2,2-bis (4-hydroxyphenyl) methane). Examples thereof include an F structure and a bisphenol B structure derived from bisphenol B (2,2-bis (4-hydroxyphenyl) butane), and a bisphenol A structure is preferable.

Examples of the ethylenically unsaturated compound B1 having a bisphenol structure include a compound having a bisphenol structure and two polymerizable groups (preferably (meth) acryloyl groups) bonded to both ends of the bisphenol structure.
Both ends of the bisphenol structure and the two polymerizable groups may be directly bonded or may be bonded via one or more alkyleneoxy groups. As the alkyleneoxy group added to both ends of the bisphenol structure, an ethyleneoxy group or a propyleneoxy group is preferable, and an ethyleneoxy group is more preferable. The number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16 per molecule, more preferably 6 to 14.
The ethylenically unsaturated compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP-A-2016-224162, and the contents described in this publication are incorporated in the present specification.

As the ethylenically unsaturated compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferable, and 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane is more preferable.
Examples of the 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane include 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane (FA-324M, Hitachi Chemical Co., Ltd.). Co., Ltd.), 2,2-bis (4- (methacryloxyethoxypropoxy) phenyl) propane, 2,2-bis (4- (methacryloxypentethoxy) phenyl) propane (BPE-500, Shin-Nakamura Chemical Industry Co., Ltd. ( , 2,2-Bis (4- (methacryloxydeccaethoxytetrapropoxy) phenyl) propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis (4- (methacryloxypentadeca) Ethoxy) phenyl) propane (BPE-1300, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane (BPE-200, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) ), And ethoxylated (10) bisphenol A diacrylate (NK ester A-BPE-10, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).

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

In the formula (Bis), R ₁ and R ₂ independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , and n ₁ and n ₃ are independent, respectively. In addition, n 1 + n 3 is an integer of 1 to 39, n ₁ + n ₃ is an integer of 2 to 40, n ₂ and n ₄ are independently integers of 0 to 29, and n ₂ + n ₄ is an integer of 0 to 40. It is an integer of 30, and the sequence of repeating units of-(AO)-and-(BO)-may be random or block. In the case of a block, either − (A—O) − or − (BO) − may be on the bisphenol structure side.
In one embodiment, n ₁ + n ₂ + n ₃ + n ₄ is preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 12. Further, 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 alone or in combination of two or more.
The content of the ethylenically unsaturated compound B1 in the photosensitive resin layer is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the photosensitive resin layer, from the viewpoint of better resolution. preferable. The upper limit is not particularly limited, but is preferably 70% by mass or less, more preferably 60% by mass or less, from the viewpoint of transferability and edge fusion (a phenomenon in which the components in the photosensitive resin layer exude from the edges of the photosensitive transfer material). preferable.

The photosensitive resin layer may contain an ethylenically unsaturated compound other than the above-mentioned ethylenically unsaturated compound B1.
The ethylenically unsaturated compound other than the ethylenically unsaturated compound B1 is not particularly limited and can be appropriately selected from known compounds. For example, a compound having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compound), a bifunctional ethylenically unsaturated compound having no aromatic ring, and a trifunctional or higher ethylenically unsaturated compound. Examples include compounds.

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

Examples of the bifunctional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, urethane di (meth) acrylate, and trimethylolpropane diacrylate. Be done.
Examples of the alkylene glycol di (meth) acrylate include tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and tricyclodecanedimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). ), 1,9-Nonandiol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) ), Ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di (meth) acrylate.
Examples of the polyalkylene glycol di (meth) acrylate include polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di (meth) acrylate.
Examples of the urethane di (meth) acrylate include propylene oxide-modified urethane di (meth) acrylate, and ethylene oxide and propylene oxide-modified urethane di (meth) acrylate. Examples of commercially available products include 8UX-015A (manufactured by Taisei Fine Chemical Industry Co., Ltd.), UA-32P (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., Ltd.). Can be mentioned.

Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, and trimethylolpropane tri (meth). Examples thereof include acrylates, trimethylolpropane tetra (meth) acrylates, trimethylolethanetri (meth) acrylates, isocyanuric acid tri (meth) acrylates, glycerintri (meth) acrylates, and alkylene oxide modifications thereof.
Here, "(tri / tetra / penta / hexa) (meth) acrylate" is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate. , "(Tri / tetra) (meth) acrylate" is a concept that includes tri (meth) acrylate and tetra (meth) acrylate. In one embodiment, the photosensitive resin layer preferably contains the above-mentioned ethylenically unsaturated compound B1 and a trifunctional or higher ethylenically unsaturated compound, and the above-mentioned ethylenically unsaturated compound B1 and two or more trifunctional or higher. It is more preferable to contain the ethylenically unsaturated compound of. In this case, the mass ratio of the ethylenically unsaturated compound B1 to the trifunctional or higher ethylenically unsaturated compound is (total mass of the ethylenically unsaturated compound B1): (total mass of the trifunctional or higher ethylenically unsaturated compound). = 1: 1 to 5: 1, more preferably 1.2: 1 to 4: 1, and even more preferably 1.5: 1 to 3: 1.
Further, in one embodiment, the photosensitive resin layer preferably contains the above-mentioned ethylenically unsaturated compound B1 and two or more trifunctional ethylenically unsaturated compounds.

Examples of the alkylene oxide-modified product of the trifunctional or higher ethylenically unsaturated compound include caprolactone-modified (meth) acrylate compound (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd. and A manufactured by Shin Nakamura Chemical Industry Co., Ltd. -9300-1CL, etc.), alkylene oxide-modified (meth) acrylate compound (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin Nakamura Chemical Industry Co., Ltd., EBECRYL manufactured by Daicel Ornex Co., Ltd. (Registered trademark) 135, etc.), ethoxylated glycerin triacrylate (A-GLY-9E, etc. manufactured by Shin Nakamura Chemical Industry Co., Ltd.), Aronix (registered trademark) TO-2349 (manufactured by Toa Synthetic Co., Ltd.), Aronix M- 520 (manufactured by Toa Synthetic Co., Ltd.) and Aronix M-510 (manufactured by Toa Synthetic Co., Ltd.) can be mentioned.

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

The value of the ratio Mm / Mb of the content Mm of the ethylenically unsaturated compound and the content Mb of the alkali-soluble resin in the photosensitive resin layer may be 1.0 or less from the viewpoint of resolution and linearity. It is more preferably 0.9 or less, and particularly preferably 0.5 or more and 0.9 or less.
Further, the ethylenically unsaturated compound in the photosensitive resin layer preferably contains a (meth) acrylic compound from the viewpoint of curability and resolvability.
Further, the ethylenically unsaturated compound in the photosensitive resin layer contains a (meth) acrylic compound from the viewpoint of curability, resolution and linearity, and the (meth) acrylic compound contained in the photosensitive resin layer. It is more preferable that the content of the acrylic compound with respect to the total mass is 60% by mass or less.

The molecular weight (weight average molecular weight (Mw) when having a distribution) of the ethylenically unsaturated compound containing the ethylenically unsaturated compound B1 is preferably 200 to 3,000, more preferably 280 to 2,200, and 300. -2,200 is more preferable.

The polymerizable compound (particularly, the ethylenically unsaturated compound) may be used alone or in combination of two or more.
The content of the polymerizable compound (particularly, the ethylenically unsaturated compound) in the photosensitive resin layer is preferably 10% by mass to 70% by mass, preferably 20% by mass to 60% by mass, based on the total mass of the photosensitive resin layer. More preferably, 20% by mass to 50% by mass is further preferable.

<Photopolymerization initiator>
The photosensitive resin layer preferably contains a photopolymerization initiator.
The photopolymerization initiator is a compound that initiates the polymerization of an ethylenically unsaturated compound by receiving active light such as ultraviolet rays, visible light and X-rays. The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.
Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferable.

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

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

Examples of the photoradical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p, p'-dimethoxybenzyl), and TAZ-110 (trade name:). Midori Kagaku Co., Ltd.), Benzoinone, TAZ-111 (trade name: Midori Kagaku Co., Ltd.), Radical OXE01, OXE02, OXE03, OXE04 (BASF), Omnirad 651 and 369 (trade name: IGM Resins B.V.) , And 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Kasei Kogyo Co., Ltd.) Be done.

Examples of commercially available photoradical polymerization initiators include 1- [4- (phenylthio) phenyl] -1,2-octanedione-2- (O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-. 01, manufactured by BASF), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] etanone-1- (O-acetyloxime) (trade name: IRGACURE OXE-02, BASF), IRGACURE OXE-03 (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-morpholinopropane-1-one (Product name: Omnirad 907, IGM Resins B.V.) , 2-Hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one (trade name: Omnirad 127, IGM Resins B. V.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (trade name: Omnirad 369, IGM Resins B.V.), 2-hydroxy-2-methyl- 1-Phenylpropan-1-one (trade name: Omnirad 1173, manufactured by IGM Resins B.V.), 1-hydroxycyclohexylphenylketone (trade name: Omnirad 184, manufactured by IGM Resins B.V.), 2,2- Dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651, manufactured by IGM Resins BV), 2,4,6-trimethylbenzoyl-diphenylphosphinoxide (trade name: Omnirad TPO H,) IGM Resins B.V.), Bis (2,4,6-trimethylbenzoyl) phenylphosphinoxide (trade name: Omnirad 819, IGM Resins B.V.), Oxime ester-based photopolymerization initiator ( Product name: Lunar 6, manufactured by DKSH Japan Co., Ltd., 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbisimidazole (2- (2-chlorophenyl) -4) , 5-Diphenylimidazole dimer ) (Product name: B-CIM, manufactured by Hampford) and 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer (trade name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.). ..

The photocationic polymerization initiator (photoacid generator) is a compound that generates an acid by receiving active light rays. As the photocationic polymerization initiator, a compound that is sensitive to active light having a wavelength of 300 nm or more, preferably a wavelength of 300 to 450 nm and generates an acid is preferable, but its chemical structure is not limited. In addition, a photocationic polymerization initiator that is not directly sensitive to active light with a wavelength of 300 nm or more is also a sensitizer if it is a compound that is sensitive to active light with a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. Can be preferably used in combination with.
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 an acid having a pKa of 2 or less is used. The generated photocationic polymerization initiator is particularly preferred. The lower limit of pKa is not particularly defined, but is preferably -10.0 or higher, for example.

Examples of the photocationic polymerization initiator include an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator.
Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.
As the ionic photocationic polymerization initiator, the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of JP-A-2014-85643 may be used.

Examples of the nonionic photocationic polymerization initiator include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. As the trichloromethyl-s-triazines, the diazomethane compound and the imide sulfonate compound, the compounds described in paragraphs 0083 to 886 of JP-A-2011-22149 may be used. Further, as the oxime sulfonate compound, the compound described in paragraphs 0084 to 0088 of International Publication No. 2018/179640 may be used.

The photosensitive resin layer may contain one type of photopolymerization initiator alone or two or more types.
The content of the photopolymerization initiator in the photosensitive resin layer is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total mass of the photosensitive resin layer. 0% by mass or more is more preferable. The upper limit is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the photosensitive resin layer.

<Dye>
The photosensitive resin layer preferably contains a dye from the viewpoints of visibility of the exposed and non-exposed areas, pattern visibility after development, and resolution, and the maximum in the wavelength range of 400 nm to 780 nm at the time of color development. It is more preferable to contain a dye having an absorption wavelength of 450 nm or more and whose maximum absorption wavelength is changed by an acid, a base, or a radical (also referred to simply as “dye N”). When the dye N is contained, the detailed mechanism is unknown, but the adhesion to the adjacent layer (for example, the temporary support and other adjacent layers) is improved, and the resolution is more excellent.

In the present specification, the term "the maximum absorption wavelength is changed by an acid, a base or a radical" means that the dye in a color-developing state is decolorized by an acid, a base or a radical, and the dye in a decolorized state is an acid. It may mean any aspect of a mode in which a color is developed by a base or a radical, or a mode in which a dye in a color-developing state changes to a color-developing state of another hue.
Specifically, the dye N may be a compound that changes its color from the decolorized state by exposure and may be a compound that changes its color from the decolorized state by exposure. In this case, it may be a dye whose color development or decolorization state is changed by the acid, base or radical generated and acted on in the photosensitive resin layer by exposure, and the state in the photosensitive resin layer by the acid, base or radical. It may be a dye whose color development or decolorization state changes by changing (for example, pH). Further, it may be a dye that changes its color development or decolorization state by directly receiving an acid, a base or a radical as a stimulus without going through exposure.

Among them, the dye N is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by a radical, from the viewpoint of visibility and resolution of an exposed portion and a non-exposed portion.
The photosensitive resin layer may contain both a dye whose maximum absorption wavelength is changed by radicals as dye N and a photoradical polymerization initiator from the viewpoint of visibility and resolution of exposed and unexposed parts. preferable.
Further, from the viewpoint of visibility of the exposed portion and the non-exposed portion, the dye N is preferably a dye that develops color by an acid, a base, or a radical.

As an example of the color development mechanism of the dye N in the present disclosure, a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator) or a photobase generator is added to the photosensitive resin layer, and photoradical polymerization is performed after exposure. Examples thereof include an embodiment in which a radical-reactive dye, an acid-reactive dye or a base-reactive dye (for example, a leuco dye) is colored by a radical, an acid or a base generated from an initiator, a photocationic polymerization initiator or a photobase generator.

From the viewpoint of visibility of the exposed and non-exposed areas, the dye N preferably has a maximum absorption wavelength of 550 nm or more in the wavelength range of 400 nm to 780 nm at the time of color development, more preferably 550 nm to 700 nm. It is more preferably ~ 650 nm.
Further, the dye N may have only one maximum absorption wavelength in the wavelength range of 400 nm to 780 nm at the time of color development, or may have two or more. When the dye N has two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm at the time of color development, the maximum absorption wavelength having the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.

The maximum absorption wavelength of the dye N is transmitted through a solution containing the dye N (liquid temperature 25 ° C.) in the range of 400 nm to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) in an atmospheric atmosphere. It is obtained by measuring the spectrum and detecting the wavelength at which the light intensity becomes the minimum (maximum absorption wavelength).

Examples of the dye that develops or decolorizes by exposure include leuco compounds.
Examples of the dye to be decolorized by exposure include leuco compounds, diarylmethane dyes, oxadin dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes and anthraquinone dyes.
As the dye N, a leuco compound is preferable from the viewpoint of visibility of the exposed portion and the non-exposed portion.

Examples of the leuco compound include a leuco compound having a triarylmethane skeleton (triarylmethane dye), a leuco compound having a spiropyran skeleton (spiropylan dye), a leuco compound having a fluorane skeleton (fluorane dye), and a diarylmethane skeleton. Leuco compounds (diarylmethane dyes), leuco compounds having a rhodamine lactam skeleton (lodamine lactam dyes), leuco compounds having an indrill phthalide skeleton (indolyl phthalide dyes), and leuco auramine skeletons. Examples thereof include leuco compounds (leuco auramine-based dyes) having a leuco compound.
Of these, triarylmethane-based dyes or fluorane-based dyes are preferable, and leuco compounds (triphenylmethane-based dyes) or fluorane-based dyes having a triphenylmethane skeleton are more preferable.

The leuco compound preferably has a lactone ring, a surujin ring, or a sultone ring from the viewpoint of visibility of the exposed portion and the non-exposed portion. As a result, the lactone ring, sultin ring, or sulton ring of the leuco compound is reacted with the radical generated from the photoradical polymerization initiator or the acid generated from the photocationic polymerization initiator to change the leuco compound into a closed ring state. The color can be decolorized or the leuco compound can be changed to an open ring state to develop a color. The leuco compound has a lactone ring, a sultone ring or a sultone ring, and a compound in which the lactone ring, the sultone ring or the sultone ring is opened by a radical or an acid to develop color is preferable, and the compound has a lactone ring and is formed by a radical or an acid. A compound in which the lactone ring is opened to develop color is more preferable.

Examples of the dye N include the following dyes and leuco compounds.
Specific examples of dyes among dyes N include Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuxin, Methyl Violet 2B, Kinaldine Red, Rose Bengal, Metanyl Yellow, Timor Sulfophthalein, Xylenol Blue, and Methyl. Orange, Paramethyl Red, Congofred, Benzopurpurin 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malakite Green, Parafuxin, Victoria Pure Blue-Naphthalene Sulfate, Victoria Pure Blue BOH Tsuchiya Chemical Industry Co., Ltd.), Oil Blue # 603 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Pink # 312 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Industry Co., Ltd.), Oil Scarlet # 308 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red OG (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Industry Co., Ltd.), Oil Green # 502 (manufactured by Orient Chemical Industry Co., Ltd.) ), Spiron Red BEH Special (manufactured by Hodoya Chemical Industry Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulfordamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxy Anilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N, N-bis (hydroxyethyl) amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylamino Examples thereof include phenylimino-5-pyrazolone and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

Specific examples of the leuco compound among the dyes N include p, p', p "-hexamethyltriaminotriphenylmethane (leucocrystal violet), Pergascript Blue SRB (manufactured by Ciba Geigy), crystal violet lactone, and malakite green lactone. Benzoyl leucomethylene blue, 2- (N-phenyl-N-methylamino) -6- (N-p-trill-N-ethyl) aminofluorane, 2-anilino-3-methyl-6- (N-ethyl-p) -Truizino) fluorane, 3,6-dimethoxyfluorane, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluorane, 3- (N-cyclohexyl-N-methyl) Amino) -6-methyl-7-anilinofluorane, 3- (N, N-diethylamino) -6-methyl-7-anilinofluorane, 3- (N, N-diethylamino) -6-methyl-7 -Xylidinofluorane, 3- (N, N-diethylamino) -6-methyl-7-chlorofluorane, 3- (N, N-diethylamino) -6-methoxy-7-aminofluorane, 3- (N) , N-diethylamino) -7- (4-chloroanilino) fluorane, 3- (N, N-diethylamino) -7-chlorofluorane, 3- (N, N-diethylamino) -7-benzylaminofluorane, 3- (N, N-diethylamino) -7,8-benzofluorolane, 3- (N, N-dibutylamino) -6-methyl-7-anilinofluorane, 3- (N, N-dibutylamino) -6 -Methyl-7-xylidinofluolane, 3-piperidino-6-methyl-7-anilinofluolane, 3-pyrrolidino-6-methyl-7-anilinofluolane, 3,3-bis (1-ethyl- 2-Methylindole-3-yl) phthalide, 3,3-bis (1-n-butyl-2-methylindole-3-yl) phthalide, 3,3-bis (p-dimethylaminophenyl) -6-dimethyl Aminophthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-zaphthalide, 3- (4-diethylaminophenyl) -3-( 1-Ethyl-2-methylindol-3-yl) phthalide and 3', 6'-bis (diphenylamino) spirisobenzofuran-1 (3H), 9'-[9H] xanthene-3-one. Be done.

The dye N is preferably a dye whose maximum absorption wavelength is changed by radicals from the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, and is a dye that develops color by radicals. Is more preferable.
As the dye N, leuco crystal violet, crystal violet lactone, brilliant green, or Victoria pure blue-naphthalene sulfonate is preferable.

The dye may be used alone or in combination of two or more.
The content of the dye is preferably 0.1% by mass or more with respect to the total mass of the photosensitive resin layer from the viewpoints of visibility of the exposed and non-exposed areas, pattern visibility after development, and resolution. , 0.1% by mass to 10% by mass, more preferably 0.1% by mass to 5% by mass, and particularly preferably 0.1% by mass to 1% by mass.
The content of the dye N is 0.1% by mass with respect to the total mass of the photosensitive resin layer from the viewpoints of visibility of the exposed portion and the non-exposed portion, pattern visibility after development, and resolution. The above is preferable, 0.1% by mass to 10% by mass is more preferable, 0.1% by mass to 5% by mass is further preferable, and 0.1% by mass to 1% by mass is particularly preferable.

The content of the dye N means the content of the dye when all of the dye N contained in the photosensitive resin layer is in a colored state. Hereinafter, a method for quantifying the content of dye N will be described by taking a dye that develops color by radicals as an example.
Two kinds of solutions in which 0.001 g or 0.01 g of the dye is dissolved in 100 mL of methyl ethyl ketone are prepared. Irgacure OXE01 (trade name, BASF Japan, Inc.), a photoradical polymerization initiator, is added to each of the obtained solutions, and radicals are generated by irradiating with light of 365 nm to bring all the dyes into a colored state. Then, in an atmospheric atmosphere, the absorbance of each solution having a liquid temperature of 25 ° C. is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), and a calibration curve is prepared.
Next, the absorbance of the solution in which all the dyes are developed is measured by the same method as above except that 3 g of the photosensitive resin layer is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the photosensitive resin layer, the content of the dye contained in the photosensitive resin layer is calculated based on the calibration curve.

<Thermal crosslinkable compound>
The photosensitive resin layer preferably contains a heat-crosslinkable compound from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. In this specification, the thermally crosslinkable compound having an ethylenically unsaturated group described later is not treated as a polymerizable compound, but is treated as a thermally crosslinkable compound.
Examples of the heat-crosslinkable compound include a methylol compound and a blocked isocyanate compound. Of these, 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.
Since the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when the resin and / or the polymerizable compound has at least one of the hydroxy group and the carboxy group, the hydrophilicity of the formed film decreases. When a film obtained by curing a photosensitive resin layer is used as a protective film, the function tends to be enhanced.
The blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) 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 associated with the deprotection reaction of the blocked isocyanate when measured by DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter".
As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments, Inc. can be preferably used. However, the differential scanning calorimeter is not limited to this.

Examples of the blocking agent having a dissociation temperature of 100 ° C. to 160 ° C. include active methylene compounds [malonic acid diester (dimethyl malonate, diethyl malonate, din-butyl malonate, di2-ethylhexyl malonic acid, etc.)] and oxime compounds. (A compound having a structure represented by -C (= N-OH)-in a molecule such as formaldehyde, acetaldoxime, acetoxime, methylethylketooxime, and cyclohexanoneoxime) can be mentioned.
Among these, the blocking agent having a dissociation temperature of 100 ° C. to 160 ° C. preferably contains, for example, an oxime compound from the viewpoint of storage stability.

The blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the membrane and improving the adhesion to the transferred body.
The blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by subjecting hexamethylene diisocyanate to isocyanurate to protect it.
Among the blocked isocyanate compounds having an isocyanurate structure, the compound having an oxime structure using an oxime compound as a blocking agent is easier to set the dissociation temperature in a preferable range and reduces the development residue than the compound having no oxime structure. It is preferable from the viewpoint of ease.

The blocked isocyanate compound may have a polymerizable group.
The polymerizable group is not particularly limited, and a known polymerizable group can be used, and a radically polymerizable group is preferable.
Examples of the polymerizable group include an ethylenically unsaturated group such as a (meth) acryloxy group, a (meth) acrylamide 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) acryloxy group is more preferable, and an acryloxy group is further preferable.

As the blocked isocyanate compound, a commercially available product can be used.
Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP (all manufactured by Showa Denko KK), and blocks. Examples thereof include the Duranate series of molds (for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Co., Ltd.).
Further, as the blocked isocyanate compound, a compound having the following structure can also be used.

The heat-crosslinkable compound may be used alone or in combination of two or more.
When the photosensitive resin layer contains a heat-crosslinkable compound, the content of the heat-crosslinkable compound is preferably 1% by mass to 50% by mass, preferably 5% by mass to 30% by mass, based on the total mass of the photosensitive resin layer. Is more preferable.

<Other ingredients>
The photosensitive resin layer may contain components other than the above-mentioned alkali-soluble resin, ethylenically unsaturated compound, photopolymerization initiator, dye, and heat-crosslinkable compound.

-Surfactant-
The photosensitive resin layer preferably contains a surfactant from the viewpoint of thickness uniformity.
Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic (nonionic) surfactants, and amphoteric surfactants, and nonionic surfactants are preferable.
Examples of the surfactant include paragraphs 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Patent Application Laid-Open No. 2009-237362.

As the surfactant, a fluorine-based surfactant or a silicone-based surfactant is preferable.
Commercially available products of fluorine-based surfactants include, for example, Megafuck (trade names) F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143. , F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F -557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, MFS-578, MFS -579, MFS-586, MFS-587, EXP. MFS-628, EXP. MFS-631, EXP. MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (above, manufactured by DIC Co., Ltd.), Florard (trade name) FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Co., Ltd.), Surflon (trade name) S-382, SC-101, SC-103 , SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC Co., Ltd.), PolyFox (trade name) PF636, PF656, PF6320, PF6520. , PF7002 (above, manufactured by OMNOVA), Footgent (trade name) 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F (above, manufactured by NEOS Co., Ltd.), U-120E (Unichem Co., Ltd.) and the like. Will be.
Further, the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cut off and the fluorine atom volatilizes when heat is applied. Can be suitably used. As such a fluorine-based surfactant, Megafuck (trade name) DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)) For example, Megafuck (trade name) DS-21 can be mentioned.

Further, 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, a block polymer can also be used. The fluorine-based surfactant has a structural unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth). A fluorine-containing polymer compound containing a structural unit derived from an acrylate compound can also be preferably used.
As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used. Megafuck (trade name) RS-101, RS-102, RS-718K, RS-72-K (all manufactured by DIC Corporation) and the like can be mentioned.

Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ethers, polyoxyethylene stearyl ethers, etc. Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic (trade name) L10, L31, L61, L62, 10R5, 17R2 , 25R2 (above, manufactured by BASF), Tetronic (trade name) 304, 701, 704, 901, 904, 150R1, HYDROPALAT WE 3323 (above, manufactured by BASF), Solspers (trade name) 20000 (above, Nippon Loubri) Zol Co., Ltd.), NCW-1001, NCW-1001, NCW-1002 (all manufactured by Fujifilm Wako Junyaku Co., Ltd.), Pionin (trade name) D-1105, D-6112, D-6112-W , D-6315 (above, manufactured by Takemoto Yushi Co., Ltd.), Orfin E1010, Surfinol 104, 400, 440 (above, manufactured by Nissin Chemical Industry Co., Ltd.) and the like.
As the fluorine-based surfactant, from the viewpoint of improving environmental suitability, compounds having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), may be used. It is preferably a surfactant derived from an alternative material.

Examples of the silicone-based surfactant include a linear polymer composed of a siloxane bond and a modified siloxane polymer having an organic group introduced into a side chain or a terminal.
Specific examples of the silicone-based surfactant include EXP. S-309-2, EXP. S-315, EXP. S-503-2, EXP. S-505-2 (all manufactured by DIC Co., Ltd.), DOWNIL (trade name) 8032 ADDITIVE, Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (all manufactured by Toray Dow Corning Co., Ltd.), X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF -640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002, KP-101KP-103, KP-104, KP -105, KP-106, KP-109, KP-109, KP-112, KP-120, KP-121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322 , KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, KP-652 (all manufactured by Shin-Etsu Chemical Industry Co., Ltd.) ), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, BYK323 (all manufactured by Big Chemie) and the like can be mentioned.

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

-Additive-
In addition to the above components, the photosensitive resin layer may contain known additives, if necessary.
Examples of the additive include a polymerization inhibitor, a sensitizer, a plasticizer, a heterocyclic compound, benzotriazoles, carboxybenzotriazoles, pyridines (isonicotinamide, etc.), purine bases (adenine, etc.), and a solvent. Can be mentioned. The photosensitive resin layer may contain one type of each additive alone, or may contain two or more types of each additive.

The photosensitive resin layer may contain a polymerization inhibitor. As the polymerization inhibitor, a radical polymerization inhibitor is preferable.
Examples of the polymerization inhibitor include the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784. Of these, phenothiazine, phenoxazine or 4-methoxyphenol is preferable. Examples of other polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like. It is preferable to use a nitrosophenylhydroxyamine aluminum salt as a polymerization inhibitor so as not to impair the sensitivity of the photosensitive resin composition.

Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, and the like. Examples thereof include bis (N-2-ethylhexyl) aminomethylene-1,2,3-triltriazole, bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole and the like. The

Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2-ethylhexyl) aminomethylene. Examples thereof include carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole and the like. As the carboxybenzotriazoles, for example, a commercially available product such as CBT-1 (manufactured by Johoku Chemical Industry Co., Ltd., trade name) can be used.

The total content of the polymerization inhibitor, benzotriazols, and carboxybenzotriazols is preferably 0.01% by mass to 3% by mass, based on the total mass of the photosensitive resin layer. It is more preferably 05% by mass to 1% by mass. It is preferable that the content is 0.01% by mass or more from the viewpoint of imparting storage stability to the photosensitive resin composition. On the other hand, it is preferable to set the content to 3% by mass or less from the viewpoint of maintaining the sensitivity and suppressing the decolorization of the dye.

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, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, and triazole compounds (for example,). 1,2,4-triazole), stylben compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridin compounds.

The photosensitive resin layer may contain one type of sensitizer alone, or may contain two or more types of sensitizer.
When the photosensitive resin layer contains a sensitizer, the content of the sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving the sensitivity to the light source and improving the curing rate by balancing the polymerization rate and the chain transfer. Therefore, 0.01% by mass to 5% by mass is preferable, and 0.05% by mass to 1% by mass is more preferable with respect to the total mass of the photosensitive resin layer.

The photosensitive resin layer may contain at least one selected from the group consisting of a plasticizer and a heterocyclic compound.
Examples of the plasticizer and the heterocyclic compound include the compounds described in paragraphs 097 to 0103 and 0111 to 0118 of International Publication No. 2018/179640.

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

The photosensitive resin layer includes metal oxide particles, antioxidants, dispersants, acid growth agents, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, and thickeners. , Cross-linking agents, and known additives such as organic or inorganic anti-precipitation agents may be further contained.
Additives contained in the photosensitive resin layer are described in paragraphs 0165 to 0184 of JP-A-2014-85643, and the contents of this publication are incorporated in the present specification.

<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. Of these, halide ions, sodium ions, and potassium ions are likely to be mixed as impurities, so the following content is preferable.

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

Examples of the method for keeping impurities within the above range include selecting a raw material for the composition having a low content of impurities, preventing contamination of the photosensitive resin layer at the time of producing the photosensitive resin layer, and cleaning and removing the impurities. Be done. By such a method, the amount of impurities can be kept within the above range.

Impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

The content of compounds such as benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N, N-dimethylformamide, N, N-dimethylacetamide, and hexane in the photosensitive resin layer may be low. preferable. The content of these compounds with respect to the total mass of the photosensitive resin layer is preferably 100 ppm or less, more preferably 20 ppm or less, still more preferably 4 ppm or less on a mass basis.
The lower limit can be 10 ppb or more and 100 ppb or more with respect to the total mass of the photosensitive resin layer on a mass basis. The content of these compounds can be suppressed in the same manner as the above-mentioned metal impurities. Further, it can be quantified by a known measurement method.

The water content in the photosensitive resin layer is preferably 0.01% by mass to 1.0% by mass, more preferably 0.05% by mass to 0.5% by mass, from the viewpoint of improving reliability and laminating property. ..

<Residual monomer>
The photosensitive resin layer may contain a residual monomer corresponding to each structural unit of the alkali-soluble resin described above.
The content of the residual monomer is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, and 500 mass ppm or less with respect to the total mass of the alkali-soluble resin from the viewpoint of patterning property and reliability. Is more preferable. The lower limit is not particularly limited, but 1 mass ppm or more is preferable, and 10 mass ppm or more is more preferable.
The residual monomer of each structural unit of the alkali-soluble resin is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, based on the total mass of the photosensitive resin layer from the viewpoint of patterning property and reliability. , 100 mass ppm or less is more preferable. The lower limit is not particularly limited, but is preferably 0.1 mass ppm or more, and more preferably 1 mass ppm or more.

The amount of residual monomer of the monomer when synthesizing the alkali-soluble resin by the polymer reaction is also preferably in the above range. For example, when glycidyl acrylate is reacted with the carboxylic acid side chain to synthesize an alkali-soluble resin, the content of glycidyl acrylate is preferably in the above range.
The amount of the residual monomer can be measured by a known method such as liquid chromatography and gas chromatography.

<Physical characteristics, 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, further preferably 0.5 μm to 15 μm, and even more preferably 0.5 μm to 10 μm. Is particularly preferable, and 0.5 μm to 8 μm is most preferable. As a result, the developability of the photosensitive resin layer is improved, and the resolvability can be improved.
Further, in one embodiment, 0.5 μm to 5 μm is preferable, 0.5 μm to 4 μm is more preferable, and 0.5 μm to 3 μm is further preferable.
Further, the layer thickness of the photosensitive resin layer is preferably 10 μm or less, more preferably 8 μm or less, from the viewpoint of resolvability.
The layer thickness of each layer of the photosensitive transfer material is based on the observation image obtained by observing the cross section in the direction perpendicular to the main surface of the photosensitive transfer material with a scanning electron microscope (SEM). It is measured by measuring the thickness of each layer at 10 points or more and calculating the average value thereof.

Further, from the viewpoint of excellent adhesion, the transmittance of light having a wavelength of 365 nm in the photosensitive resin layer is preferably 10% or more, preferably 30% or more, and more preferably 50% or more. The upper limit is not particularly limited, but is preferably 99.9% or less.

<Formation method>
The method for forming the photosensitive resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components.
As a method for forming the photosensitive resin layer, for example, a photosensitive resin composition containing an alkali-soluble resin, an ethylenically unsaturated compound, a photopolymerization initiator, a solvent and the like is prepared, and the surface of the temporary support or the like is photosensitive. Examples thereof include a method of applying the resin composition and drying the coating film of the photosensitive resin composition to form the resin composition.

Examples of the photosensitive resin composition used for forming the photosensitive resin layer include a composition containing an alkali-soluble resin, an ethylenically unsaturated compound, a photopolymerization initiator, the above-mentioned optional components and a solvent.
The photosensitive resin composition preferably contains a solvent in order to adjust the viscosity of the photosensitive resin composition and facilitate the formation of the photosensitive resin layer.

-solvent-
The solvent contained in the photosensitive resin composition is not particularly limited as long as it can dissolve or disperse an alkali-soluble resin, an ethylenically unsaturated compound, a photopolymerization initiator and the above optional components, and a known solvent is used. can.
Examples of the solvent include an alkylene glycol ether solvent, an alkylene glycol ether acetate solvent, an alcohol solvent (methanol, ethanol, etc.), a ketone solvent (acetone, methyl ethyl ketone, etc.), an aromatic hydrocarbon solvent (toluene, etc.), and an aprotonic polar solvent. Examples thereof include (N, N-dimethylformamide, etc.), cyclic ether solvents (tetratetra, etc.), ester solvents, amide solvents, lactone solvents, and mixed solvents containing two or more of these.
When a photosensitive transfer material including a temporary support, a thermoplastic resin layer, a water-soluble resin layer, a photosensitive resin layer and a protective film is produced, the photosensitive resin composition is prepared from an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. It is preferable to contain at least one selected from the group. Among them, a mixed solvent containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent and at least one selected from the group consisting of a ketone solvent and a cyclic ether solvent is more preferable. A mixed solvent containing at least one selected from the group consisting of a glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent, and at least three types of 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 dipropylene glycol monoalkyl ether acetate.
As the solvent, the solvent described in paragraphs 0092 to 0094 of International Publication No. 2018/179640 and the solvent described in paragraph 0014 of JP-A-2018-177789 may be used, and the contents thereof are described in the present specification. Incorporated into the book.

The photosensitive resin composition may contain one type of solvent alone, or may contain two or more types of solvent.
The content of the solvent when the photosensitive resin composition is applied is preferably 50 parts by mass to 1,900 parts by mass, preferably 100 parts by mass to 900 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. The part is more preferable.

The method for preparing the photosensitive resin composition is not particularly limited. For example, a solution in which each component is dissolved in the above solvent is prepared in advance, and the obtained solution is mixed at a predetermined ratio to prepare the photosensitive resin composition. There is a method of preparing.
The photosensitive resin composition is preferably filtered using a filter having a pore size of 0.2 μm to 30 μm before forming the photosensitive resin layer.

The method for applying the photosensitive resin composition is not particularly limited, and the photosensitive resin composition may be applied by a known method. Examples of the coating method include slit coating, spin coating, curtain coating and inkjet coating.
Further, the photosensitive resin layer may be formed by applying the photosensitive resin composition on a protective film described later and drying it.

Further, the photosensitive transfer material in the present disclosure preferably has another layer between the temporary support and the photosensitive resin layer from the viewpoint of resolution and peelability of the temporary support. ..
As the other layer, a thermoplastic resin layer, a water-soluble resin layer and the like are preferably mentioned.
Above all, it is preferable to have a thermoplastic resin layer and a water-soluble resin layer as the other layers.

[Thermoplastic resin layer]
The photosensitive transfer material according to the present disclosure may have a thermoplastic resin layer. The photosensitive transfer material preferably has a thermoplastic resin layer between the temporary support and the photosensitive resin layer. By having the thermoplastic resin layer between the temporary support and the photosensitive resin layer, the photosensitive transfer material has improved followability to the adherend, and bubbles between the adherend and the photosensitive transfer material are improved. This is because the adhesion between the layers is improved as a result of suppressing the mixing.

The thermoplastic resin layer preferably contains an alkali-soluble resin as the thermoplastic resin.

Examples of the alkali-soluble resin include acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, epoxy resin, polyacetal resin, and polyhydroxystyrene resin. Examples thereof include polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines, and polyalkylene glycols.

The alkali-soluble resin is preferably an acrylic resin from the viewpoint of developability and adhesion to the layer adjacent to the thermoplastic resin layer. Here, the "acrylic resin" is selected from the group consisting of a structural unit derived from (meth) acrylic acid, a structural unit derived from (meth) acrylic acid ester, and a structural unit derived from (meth) acrylic acid amide. It means a resin having at least one kind.

In the acrylic resin, the ratio of the total content of the structural unit derived from (meth) acrylic acid, the structural unit derived from (meth) acrylic acid ester, and the structural unit derived from (meth) acrylic acid amide is the ratio of the total content of the acrylic resin. It is preferably 50% by mass or more with respect to the total mass. In the acrylic resin, the ratio of the total content of the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid ester is 30% by mass to 100% by mass with respect to the total mass of the acrylic resin. %, More preferably 50% by mass to 100% by mass.

Further, the alkali-soluble resin is preferably a polymer having an acid group. Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group, and a carboxy 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 carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more. The upper limit of acid value is not limited. The acid value of the alkali-soluble resin is preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less.

The carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more is not limited and can be appropriately selected from known resins and used. Examples of the carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more include a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the polymers described in paragraph 0025 of JP-A-2011-95716. Acrylic resin containing a carboxy group having an acid value of 60 mgKOH / g or more among the polymers described in paragraphs 0033 to 0052 of JP-A-2010-237589, and paragraphs 0053 to paragraph 0068 of JP-A-2016-224162. Among the binder polymers of the above, a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more can be mentioned.

The content ratio of the structural unit having a carboxy group in the carboxy group-containing acrylic resin is preferably 5% by mass to 50% by mass, preferably 10% by mass to 40% by mass, based on the total mass of the carboxy group-containing acrylic resin. It is more preferable to have it, and it is particularly preferable that it is 12% by mass to 30% by mass.

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

The alkali-soluble resin may have a reactive group. The reactive group may be, for example, a group capable of addition polymerization. Examples of the reactive group include an ethylenically unsaturated group, a polycondensable group (for example, a hydroxy group and a carboxy group), and a polyaddition reactive group (for example, an epoxy group and a (block) isocyanate group). Be done.

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 kind alone or two or more kinds of alkali-soluble resins.

The content ratio of the alkali-soluble resin may be 10% by mass to 99% by mass with respect to the total mass of the thermoplastic resin layer from the viewpoint of developability and adhesion to the layer adjacent to the thermoplastic resin layer. It is preferably 20% by mass to 90% by mass, more preferably 40% by mass to 80% by mass, and particularly preferably 50% by mass to 70% by mass.

The thermoplastic resin layer has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 nm to 780 nm at the time of color development, and the maximum absorption wavelength is changed by an acid, a base, or a radical (hereinafter referred to as “dye B”). In some cases), it is preferable to include. The preferred embodiment of the dye B is the same as the preferred embodiment of the dye N described above, except for the points described later.

The dye B is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical from the viewpoints of visibility of the exposed portion, visibility of the unexposed portion, and resolution, and the maximum absorption wavelength is changed by the acid. It is more preferable that the dye is a radical.

The thermoplastic resin layer is a dye whose maximum absorption wavelength is changed by an acid as the dye B and a compound which generates an acid by light, which will be described later, from the viewpoints of the visibility of the exposed part, the visibility of the non-exposed part, and the resolution. And, preferably.

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

The content ratio of the dye B is preferably 0.2% by mass or more, preferably 0.2% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of the visibility of the exposed portion and the visibility of the non-exposed portion. It is more preferably% to 6% by mass, further preferably 0.2% by mass to 5% by mass, and particularly preferably 0.25% by mass to 3.0% by mass.

Here, the content ratio of the dye B means the content ratio of the dye when all of the dye B contained in the thermoplastic resin layer is in a colored 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. Two solutions are prepared by dissolving the dye (0.001 g) and the dye (0.01 g) in methyl ethyl ketone (100 mL). IRGACURE OXE-01 (BASF) is added to each of the obtained solutions as a photoradical polymerization initiator, and then radicals are generated by irradiating with light of 365 nm to bring all the dyes into a colored state. Next, in an atmospheric atmosphere, the absorbance of each solution having a liquid temperature of 25 ° C. is measured using a spectrophotometer (UV3100, Shimadzu Corporation) to prepare a calibration curve. Next, the absorbance of the solution in which all the dyes are colored is measured by the same method as above except that the thermoplastic resin layer (0.1 g) is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of the dye contained in the thermoplastic resin layer is calculated based on the calibration curve.

The thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical by light (hereinafter, may be referred to as "compound C"). Compound C is preferably a compound that receives active light rays (for example, ultraviolet rays and visible light rays) to generate an acid, a base, or a radical. Examples of the compound C include known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators). Compound C is preferably a photoacid generator.

The thermoplastic resin layer preferably contains a photoacid generator from the viewpoint of resolution. Examples of the photoacid generator include a photocationic polymerization initiator that may be contained in the negative-type photosensitive resin layer described above, and the same preferred embodiments are used except for the points described below.

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

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

The thermoplastic resin layer may contain a photobase generator. Examples of the photobase generator include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, and bis [ [(2-Nitrobenzyl) Oxy] carbonyl] Hexane 1,6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoetan, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane , N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexaammine cobalt (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2,6 -Dimethyl-3,5-diacetyl-4- (2-nitrophenyl) -1,4-dihydropyridine, and 2,6-dimethyl-3,5-diacetyl-4- (2,4-dinitrophenyl) -1, Examples include 4-dihydropyridine.

The thermoplastic resin layer may contain a photoradical polymerization initiator. Examples of the photoradical polymerization initiator include a photoradical polymerization initiator that may be contained in the above-mentioned negative photosensitive resin layer, and the preferred embodiment is also the same.

The thermoplastic resin layer may contain one kind alone or two or more kinds of compound C.

The content ratio of the compound C is 0.1% by mass to 10% by mass with respect to the total mass of the thermoplastic resin layer from the viewpoint of the visibility of the exposed portion, the visibility of the non-exposed portion, and the resolution. It is preferably 0.5% by mass to 5% by mass, and more preferably 0.5% by mass.

The thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion to a layer adjacent to the thermoplastic resin layer, and developability.

The molecular weight of the plasticizer (the molecular weight of the oligomer or polymer is the weight average molecular weight (Mw); the same applies hereinafter 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 develops plasticity by being compatible with an alkali-soluble resin. From the viewpoint of imparting plasticity, the plasticizer is preferably a compound having an alkyleneoxy group in the molecule, and more preferably a polyalkylene glycol compound. The alkyleneoxy group contained in the plasticizer preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.

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

Examples of the (meth) acrylate compound used as a plasticizer include the (meth) acrylate compound described in the ethylenically unsaturated compound. In the photosensitive transfer material, when the thermoplastic resin layer and the negative type photosensitive resin layer are arranged in direct contact with each other, the thermoplastic resin layer and the negative type photosensitive resin layer are each the same (meth) acrylate compound. It is preferable to include. This is because the thermoplastic resin layer and the negative photosensitive resin layer each contain the same (meth) acrylate compound, so that the diffusion of components between the layers is suppressed and the storage stability is improved.

When the thermoplastic resin layer contains a (meth) acrylate compound as a plasticizer, the (meth) acrylate compound may not polymerize even in the exposed portion after exposure from the viewpoint of adhesion to the layer adjacent to the thermoplastic resin layer. preferable.

In certain embodiments, the (meth) acrylate compound used as a plasticizer has two or more (meth) acrylate compounds in one molecule from the viewpoints of resolution, adhesion to a layer adjacent to the thermoplastic resin layer, and developability. It is preferably a (meth) acrylate compound having a (meth) acryloyl group.

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

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

The content ratio of the plasticizer is 1% by mass to 70% by mass with respect to the total mass of the thermoplastic resin layer from the viewpoints of resolution, adhesion to the layer adjacent to the thermoplastic resin layer, and developability. It is preferably present, more preferably 10% by mass to 60% by mass, and particularly preferably 20% by mass to 50% by mass.

The thermoplastic resin layer preferably contains a surfactant from the viewpoint of thickness uniformity. Examples of the surfactant include a surfactant that may be contained in the negative photosensitive resin layer described above, and the preferred embodiment is also the same.

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

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

The thermoplastic resin layer may contain a sensitizer. Examples of the sensitizer include the sensitizer that may be contained in the negative photosensitive resin layer described above.

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

The content ratio of the sensitizer is 0.01% by mass to 5% by mass with respect to the total mass of the thermoplastic resin layer from the viewpoint of improving the sensitivity to the light source, the visibility of the exposed portion, and the visibility of the non-exposed portion. %, More preferably 0.05% by mass to 1% by mass.

The thermoplastic resin layer may contain known additives in addition to the above components, if necessary.

Further, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of JP-A-2014-85643. The contents of the above gazette are incorporated herein by reference.

The thickness of the thermoplastic resin layer is not limited. The average thickness of the thermoplastic resin layer is preferably 1 μm or more, and more preferably 2 μm or more, from the viewpoint of adhesion to the layer adjacent to the thermoplastic resin layer. The upper limit of the average thickness of the thermoplastic resin layer is not limited. From the viewpoint of developability and resolvability, 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 is a method capable of forming a layer containing the above components. Examples of the method for forming the thermoplastic resin layer include a method in which the thermoplastic resin composition is applied to the surface of the temporary support and the coating film of the thermoplastic resin composition is dried.

Examples of the thermoplastic resin composition include compositions containing the above components. The thermoplastic resin composition preferably contains a solvent in order to adjust the viscosity of the thermoplastic resin composition and facilitate the formation of the thermoplastic resin layer.

The solvent contained in the thermoplastic resin composition is not limited as long as it is a solvent capable of dissolving or dispersing the components contained in the thermoplastic resin layer. Examples of the solvent include a solvent that may be contained in the above-mentioned photosensitive resin composition, and the preferred embodiment is also the same.

The thermoplastic resin composition may contain one kind alone or two or more kinds of solvents.

The content ratio of the solvent in the thermoplastic resin composition is preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass to 900 parts by mass with respect to 100 parts by mass of the total solid content in the thermoplastic resin composition. It is more preferable that it is a part.

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

[Water-soluble resin layer]
The photosensitive transfer material preferably has a water-soluble resin layer between the thermoplastic resin layer and the photosensitive resin layer. According to the water-soluble resin layer, it is possible to suppress the mixing of components when forming a plurality of layers and during storage.

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

Examples of the water-soluble resin layer include an oxygen blocking layer having an oxygen blocking function, which is described as a “separation layer” in JP-A-5-72724. Since the water-soluble resin layer is an oxygen blocking layer, the sensitivity at the time of exposure is improved, the time load of the exposure machine is reduced, and as a result, the productivity is improved. The oxygen blocking layer used as the water-soluble resin layer may be appropriately selected from known layers. The oxygen blocking layer used as the water-soluble resin layer is preferably an oxygen blocking layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (1% by mass aqueous solution of sodium carbonate at 22 ° C.). ..

The water-soluble resin layer preferably contains a resin. Examples of the resin contained in the water-soluble resin layer include polyvinyl alcohol-based resin, polyvinylpyrrolidone-based resin, cellulose-based resin, acrylamide-based resin, polyethylene oxide-based resin, gelatin, vinyl ether-based resin, polyamide resin, and their co-weight. Coalescence is mentioned. The resin contained in the water-soluble resin layer is preferably a water-soluble resin.

The resin contained in the water-soluble resin layer is the polymer A contained in the negative photosensitive resin layer and the thermoplastic resin (alkali soluble) contained in the thermoplastic resin layer from the viewpoint of suppressing the mixing of the components between the plurality of layers. It is preferable that the resin is different from any of the resins).

The water-soluble resin layer preferably contains polyvinyl alcohol, and contains polyvinyl alcohol and polyvinylpyrrolidone, from the viewpoint of oxygen blocking property and suppressing mixing of components during application and storage after application. It is more preferable to include it.

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

The content ratio of the resin in the water-soluble resin layer is based on the total mass of the water-soluble resin layer from the viewpoint of oxygen blocking property and suppressing mixing of components during application of a plurality of layers and storage after application. , 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, further preferably 80% by mass to 100% by mass, and 90% by mass to 100% by mass. It is particularly preferable to have.

Further, the water-soluble resin layer may contain an additive if necessary. Examples of the additive include a surfactant.

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, more preferably 0.5 μm to 3 μm. When the thickness of the water-soluble resin layer is within the above range, the oxygen barrier property is not deteriorated, the mixing of components during formation of a plurality of layers and storage can be suppressed, and the mixing of components during development can be suppressed. It is possible to suppress an increase in the removal time of the water-soluble resin layer.

The method for forming the water-soluble resin layer is not limited as long as it is a method capable of forming a layer containing the above components. As a method for forming the water-soluble resin layer, for example, the composition for the water-soluble resin layer is applied to the surface of the thermoplastic resin layer or the negative photosensitive resin layer, and then the coating film of the composition for the water-soluble resin layer is applied. There is a method of drying.

Examples of the composition for the water-soluble resin layer include a resin and a composition containing any additive. The composition for the water-soluble resin layer preferably contains a solvent in order to adjust the viscosity of the composition for the water-soluble resin layer and facilitate the formation of the water-soluble resin layer. The solvent is not limited as long as it is a solvent that can dissolve or disperse the resin. The solvent is preferably 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.

The photosensitive transfer material may include a layer other than the above-mentioned layer (hereinafter, also referred to as “other layer”). Examples of other layers include a contrast enhancement layer.
The contrast enhancement layer is described in paragraph 0134 of WO 2018/179640. Further, the other layers are described in paragraphs 0194 to 0196 of JP-A-2014-85643. The contents of these publications are incorporated herein.

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 by a method according to the above-mentioned method for measuring the thickness of each layer.
The total thickness of each layer of the photosensitive transfer material excluding the temporary support and the protective film is preferably 20 μm or less, more preferably 10 μm or less, and 8 μm or less from the viewpoint of further exerting the effect in the present disclosure. It is more preferably 2 μm or more and 8 μm or less.
Further, 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, preferably 10 μm or less, from the viewpoint of further exerting the effect in the present disclosure. Is more preferable, and it is more preferably 8 μm or less, and particularly preferably 2 μm or more and 8 μm or less.

[Manufacturing method of photosensitive transfer material]
The method for producing the photosensitive transfer material according to the present disclosure is not particularly limited, and a known production method, for example, a known method for forming each layer can be used.
Hereinafter, a method for producing a photosensitive transfer material according to the present disclosure will be described with reference to FIG. 1. However, the photosensitive transfer material according to the present disclosure is not limited to the one having the structure shown in FIG.
FIG. 1 is a schematic cross-sectional view showing an example of a layer structure in one embodiment of the photosensitive transfer material according to the present disclosure. In the photosensitive transfer material 20 shown in FIG. 1, a temporary 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 are laminated in this order. Has a structure.

As a method for producing the photosensitive transfer material 20, for example, a thermoplastic resin composition is applied to the surface of the temporary support 11 and then the coating film of the thermoplastic resin composition is dried to obtain a thermoplastic resin layer. A step of forming the water-soluble resin layer 12 and a step of applying the water-soluble resin layer composition to the surface of the thermoplastic resin layer 13 and then drying the coating film of the water-soluble resin layer composition to form the water-soluble resin layer 15. A step of applying a photosensitive resin composition containing a binder polymer and an ethylenically unsaturated compound to the surface of the water-soluble resin layer 15 and then drying the coating film of the photosensitive resin composition to form the photosensitive resin layer 16. A method including and can be mentioned.
In the above production method, it is selected from the group consisting of a thermoplastic resin composition containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, and a water- and water-miscible organic solvent. A photosensitive resin layer composition containing at least one of the above, and at least one selected from the group consisting of a binder polymer, an ethylenically unsaturated compound, and an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. It is preferable to use a sex resin composition. As a result, the water-soluble resin layer composition is applied to the surface of the thermoplastic resin layer 13 and / or is contained in the thermoplastic resin layer 13 during the storage period of the laminate having the coating film of the water-soluble resin layer composition. Mixing of the component to be made and the component contained in the water-soluble resin layer 15 can be suppressed, and the photosensitive resin composition can be applied to the surface of the water-soluble resin layer 15 and / or the photosensitive resin composition. It is possible to suppress the mixing of the component contained in the water-soluble resin layer 15 and the component contained in the photosensitive resin layer 16 during the storage period of the laminate having the coating film.

The photosensitive transfer material 20 is manufactured by pressing the protective film 19 onto the photosensitive resin layer 17 of the laminate manufactured by the above manufacturing method.
The method for producing the photosensitive transfer material used in the present disclosure includes a step of providing a protective film 19 so as to be in contact with the second surface of the photosensitive resin layer 17, whereby the temporary support 11 and the thermoplastic resin layer 13 are provided. It is preferable to manufacture the photosensitive transfer material 20 including the transfer layer 12 including the water-soluble resin layer 15 and the photosensitive resin layer 17, and the protective film 19.
After the photosensitive transfer material 20 is manufactured by the above-mentioned manufacturing method, the photosensitive transfer material 20 may be wound up to prepare and store the photosensitive transfer material in the form of a roll. The photosensitive transfer material in roll form can be provided as it is in the bonding process with the substrate in the roll-to-roll method described later.

The photosensitive transfer material according to the present disclosure can be suitably used for various applications requiring precision microfabrication by photolithography. After patterning the photosensitive resin layer, the photosensitive resin layer may be used as a coating for etching, or electroforming may be performed mainly by electroplating. Further, the cured film obtained by patterning may be used as a permanent film, or may be used, for example, as an interlayer insulating film, a wiring protective film, a wiring protective film having an index matching layer, or the like. Further, the photosensitive transfer material according to the present disclosure is used in the fields of semiconductor packages, printed circuit boards, various wiring forming applications for sensor boards, touch panels, electromagnetic wave shielding materials, conductive films such as film heaters, liquid crystal sealing materials, micromachines or microelectronics. It can be suitably used for applications such as formation of a structure in.

Further, as the photosensitive transfer material of the first embodiment, an embodiment in which the photosensitive resin layer is a colored resin layer containing a pigment is also preferably mentioned.
In addition to the above, the colored resin layer is used for, for example, a liquid crystal display (LCD) and a color used for a solid-state image sensor [for example, a CCD (charge-coupled device) and a CMOS (complementary metal oxide semiconductor)]. It is suitable for forming colored pixels such as filters or a black matrix.
The embodiments other than the pigment in the colored resin layer are the same as those described above.

<Pigment>
The photosensitive resin layer may be a colored resin layer containing a pigment.
In recent years, liquid crystal display windows of electronic devices may be provided with a cover glass having a black frame-shaped light-shielding layer formed on the peripheral edge of the back surface of a transparent glass substrate or the like in order to protect the liquid crystal display window. be. A colored resin layer can be used to form such a light-shielding layer.
The pigment may be appropriately selected according to the desired hue, and can be selected from black pigments, white pigments, and chromatic pigments other than black and white. Above all, when forming a black pattern, a black pigment is preferably selected as the pigment.

As the black pigment, a known black pigment (organic pigment, inorganic pigment, etc.) can be appropriately selected as long as the effect in the present disclosure is not impaired. Among them, from the viewpoint of optical density, examples of the black pigment include carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, graphite and the like, and carbon black is particularly preferable. As the carbon black, from the viewpoint of surface resistance, carbon black having at least a part of the surface coated with a resin is preferable.

From the viewpoint of dispersion stability, the particle size 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 size.
Here, the particle size refers to the diameter of the circle when the area of the pigment particles is obtained from the photographic image of the pigment particles taken with an electronic microscope and the circle having the same area as the area of the pigment particles is considered, and the number average particle size. Is an average value obtained by obtaining the above particle size for any 100 particles and averaging the obtained 100 particle sizes.

As the pigment other than the black pigment, the white pigment described in paragraphs 0015 and 0114 of JP-A-2005-007765 can be used as the white pigment. Specifically, among the white pigments, as the inorganic pigment, titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate is preferable, and titanium oxide or zinc oxide is more preferable. Titanium oxide is preferable, and titanium oxide is more preferable. As the inorganic pigment, rutile-type or anatase-type titanium oxide is more preferable, and rutile-type titanium oxide is particularly preferable.
Further, the surface of titanium oxide may be treated with silica, alumina, titania, zirconia, or an organic substance, or may be subjected to two or more treatments. As a result, the catalytic activity of titanium oxide is suppressed, and heat resistance, fading and the like are improved.
From the viewpoint of reducing the thickness of the photosensitive resin layer after heating, at least one of alumina treatment and zirconia treatment is preferable as the surface treatment of the surface of titanium oxide, and both alumina treatment and zirconia treatment are particularly preferable.

When the photosensitive resin layer is a colored resin layer, it is also preferable that the photosensitive resin layer further contains a chromatic pigment other than the black pigment and the white pigment from the viewpoint of transferability. When a chromatic pigment is contained, the particle size of the chromatic pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, in that the dispersibility is more excellent.
Examples of chromatic pigments include Victoria Pure Blue BO (Color Index (hereinafter CI) 42595), Auramine (CI41000), Fat Black HB (CI26150), and Monolite. -Ero GT (CI Pigment Ellow 12), Permanent Ellow GR (CI Pigment Ellow 17), Permanent Yellow HR (CI Pigment Ellow 83), Permanent Carmine FBB (C) I. Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11), Fastel Pink B Supra (CI Pigment) Red 81), Monastral First Blue (CI Pigment Blue 15), Monolite First Black B (CI Pigment Black 1) and Carbon, C.I. I. Pigment Red 97, C.I. I. Pigment Red 122, C.I. I. Pigment Red 149, C.I. I. Pigment Red 168, C.I. I. Pigment Red 177, C.I. I. Pigment Red 180, C.I. I. Pigment Red 192, C.I. I. Pigment Red 215, C.I. I. Pigment Green 7, C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 22, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 64, and C.I. I. Pigment Violet 23 and the like. Above all, C.I. I. Pigment Red 177 is preferred.

When the photosensitive resin layer contains a pigment, the content of the pigment is preferably more than 3% by mass and 40% by mass or less, more preferably more than 3% by mass and 35% by mass or less, based on the total mass of the photosensitive resin layer. It is more preferably more than 5% by mass and 35% by mass or less, and particularly preferably 10% by mass or more and 35% by mass or less.

When the photosensitive resin layer contains a pigment other than the black pigment (white pigment and chromatic pigment), the content of the pigment other than the black pigment is preferably 30% by mass or less, preferably 1% by mass or more, based on the black pigment. 20% by mass is more preferable, and 3% by mass to 15% by mass is further preferable.

When the photosensitive resin layer contains a black pigment and the photosensitive resin layer is formed of a photosensitive resin composition, the black pigment (preferably carbon black) has a photosensitive resin composition in the form of a pigment dispersion. It is preferable to introduce it into a product.
The dispersion liquid may be prepared by adding a mixture obtained by premixing a black pigment and a pigment dispersant to an organic solvent (or vehicle) and dispersing it with a disperser. The pigment dispersant may be selected depending on the pigment and the solvent, and for example, a commercially available dispersant can be used. The vehicle refers to a portion of the medium in which the pigment is dispersed when the pigment is dispersed, and is a liquid, a binder component that holds the black pigment in a dispersed state, and a solvent component that dissolves and dilutes the binder component. (Organic solvent) and.

The disperser is not particularly limited, and examples thereof include known dispersers such as a kneader, a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill. Further, it may be finely pulverized by mechanical grinding using frictional force. For the disperser and fine pulverization, the description of "Encyclopedia of Pigments" (Kunizo Asakura, First Edition, Asakura Shoten, 2000, 438, 310) can be referred to.

[[Photosensitive transfer material of the second embodiment]]
Hereinafter, the photosensitive transfer material of the second embodiment will be described with an example.
The photosensitive transfer material 10 shown in FIG. 2 has a temporary support 1, a transfer layer 2 including a photosensitive resin layer 3 and a refractive index adjusting layer 5, and a protective film 7 in this order.
Further, the photosensitive transfer material 10 shown in FIG. 2 has a form in which the refractive index adjusting layer 5 is arranged, but the refractive index adjusting layer 5 may not be arranged.
Hereinafter, each element constituting the photosensitive transfer material of the second embodiment will be described.
The temporary support and protective film used in the photosensitive transfer material of the second embodiment are the same as those of the temporary support and protective film in the photosensitive transfer material of the first embodiment, and the preferred embodiments are also the same.

[Photosensitive resin layer]
The photosensitive transfer material has a photosensitive resin layer.
A pattern can be formed on the transferred object by transferring the photosensitive resin layer onto the transferred object and then exposing and developing the photosensitive resin layer.
Hereinafter, the components that can be contained in the photosensitive resin layer will be described in detail.

<Binder polymer>
The photosensitive resin layer may contain a binder polymer.
Examples of the binder polymer include (meth) acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenol resin, ester resin, urethane resin, and the reaction of epoxy resin with (meth) acrylic acid. Examples thereof include the obtained epoxy acrylate resin and the acid-modified epoxy acrylate resin obtained by reacting the epoxy acrylate resin with the acid anhydride.

One of the preferred embodiments of the binder polymer is a (meth) acrylic resin in that it is excellent in alkali developability and film forming property.
In the present specification, the (meth) acrylic resin means a resin having a structural unit derived from the (meth) acrylic compound. The content of the structural unit derived from the (meth) acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, based on all the structural units of the (meth) acrylic resin. ..
The (meth) acrylic resin may be composed of only a structural unit derived from the (meth) acrylic compound, or may have a structural unit derived from a polymerizable monomer other than the (meth) acrylic compound. .. That is, the upper limit of the content of the structural unit derived from the (meth) acrylic compound is 100% by mass or less with respect to all the structural units of the (meth) acrylic resin.

Examples of the (meth) acrylic compound include (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylamide, and (meth) acrylonitrile.
Examples of the (meth) acrylic acid ester include (meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, and (meth) acrylic acid ester. ) Acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, 2,2,2-trifluoroethyl (meth) acrylate, and 2,2,3,3-tetrafluoropropyl (meth) acrylate. Meta) Acrylic acid alkyl esters are preferred.
Examples of the (meth) acrylamide include acrylamide such as diacetone acrylamide.

Examples of the (meth) acrylic acid alkyl ester include (meth) methyl acrylate, (meth) ethyl acrylate, (meth) propyl acrylate, (meth) butyl acrylate, (meth) pentyl (meth) acrylate, and (meth). Hexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, and Examples thereof include (meth) acrylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms such as dodecyl (meth) acrylic acid.
As the (meth) acrylic acid ester, a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms is preferable, and methyl (meth) acrylate or ethyl (meth) acrylate is more preferable.

The (meth) acrylic resin may have a structural unit other than the structural unit derived from the (meth) acrylic compound.
The polymerizable monomer forming the structural unit is not particularly limited as long as it is a compound other than the (meth) acrylic compound that can be copolymerized with the (meth) acrylic compound, and is, for example, styrene, vinyltoluene, and α. -Styrene compounds such as methylstyrene which may have a substituent on the α-position or aromatic ring, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid, maleic acid anhydride, monomethyl maleate, maleic acid. Examples thereof include maleic acid monoesters such as monoethyl and monoisopropyl maleic acid, fumaric acid, silicic acid, α-cyanosilicic acid, itaconic acid, and crotonic acid.
These polymerizable monomers may be used alone or in combination of two or more.

Further, the (meth) acrylic resin preferably has a structural unit having an acid group from the viewpoint of improving the alkali developability. Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group.
Among them, the (meth) acrylic resin more preferably has a structural unit having a carboxy group, and further preferably has a structural unit derived from the above-mentioned (meth) acrylic acid.

The content of the structural unit having an acid group (preferably the structural unit derived from (meth) acrylic acid) in the (meth) acrylic resin is excellent in developability, and is based on the total mass of the (meth) acrylic resin. 10% by mass or more is preferable. The upper limit is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less, in terms of excellent alkali resistance.

Further, it is more preferable that the (meth) acrylic resin has a structural unit derived from the above-mentioned (meth) acrylic acid alkyl ester.
The content of the structural unit derived from the (meth) acrylic acid alkyl ester in the (meth) acrylic resin is preferably 50% by mass to 90% by mass, preferably 60% by mass or more, based on all the structural units of the (meth) acrylic resin. 90% by mass is more preferable, and 65% by mass to 90% by mass is further preferable.

As the (meth) acrylic resin, a resin having both a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylic acid alkyl ester is preferable, and the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid are preferable. A resin composed only of structural units derived from the (meth) acrylic acid alkyl ester is more preferable.
Further, as the (meth) acrylic resin, an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate is also preferable.

Further, the (meth) acrylic resin may have at least one selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from a methacrylic acid alkyl ester because the effect in the present disclosure is more excellent. It is preferable to have both a structural unit derived from methacrylic acid and a structural unit derived from an alkyl methacrylate ester.
The total content of the constituent units derived from methacrylic acid and the constituent units derived from methacrylic acid alkyl ester in the (meth) acrylic resin is higher than that of all the constituent units of the (meth) acrylic resin because the effect in the present disclosure is more excellent. 40% by mass or more is preferable, and 60% by mass or more is more preferable. The upper limit is not particularly limited, and may be 100% by mass or less, preferably 80% by mass or less.

Further, the (meth) acrylic resin is at least one selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from methacrylic acid alkyl ester, and acrylic acid, because the effect in the present disclosure is more excellent. It is also preferable to have at least one selected from the group consisting of the structural unit derived from the acrylic acid alkyl ester and the structural unit derived from the acrylic acid alkyl ester.
From the viewpoint of the superior effect in the present disclosure, the total content of the structural unit derived from methacrylic acid and the structural unit derived from methacrylic acid alkyl ester is the structural unit derived from acrylic acid and the structural unit derived from acrylic acid alkyl ester. The mass ratio is preferably 60/40 to 80/20 with respect to the total content of the ester.

The (meth) acrylic resin preferably has an ester group at the terminal in that the photosensitive resin layer after transfer is excellent in developability.
The terminal portion of the (meth) acrylic resin is composed of a site derived from the polymerization initiator used in the synthesis. A (meth) acrylic resin having an ester group at the terminal can be synthesized by using a polymerization initiator that generates a radical having an ester group.

Further, another preferred embodiment of the binder polymer is an alkali-soluble resin.
The binder polymer is preferably, for example, a binder polymer having an acid value of 60 mgKOH / g or more from the viewpoint of developability.
Further, the binder polymer is, for example, a resin having a carboxy group having an acid value of 60 mgKOH / g or more (so-called carboxy group-containing resin) from the viewpoint that it is easily crosslinked with the crosslinked component by heating to form a strong film. More preferably, it is a (meth) acrylic resin having a carboxy group having an acid value of 60 mgKOH / g or more (so-called carboxy group-containing (meth) acrylic resin).
When the binder polymer is a resin having a carboxy group, the three-dimensional crosslink density can be increased by adding a thermally crosslinkable compound such as a blocked isocyanate compound and thermally crosslinking the binder polymer. Further, when the carboxy group of the resin having a carboxy group is dehydrated and made hydrophobic, the wet heat resistance can be improved.

The carboxy group-containing (meth) acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited as long as the above acid value conditions are satisfied, and can be appropriately selected from known (meth) acrylic resins.
For example, among the polymers described in paragraphs 0025 of JP-A-2011-095716, among the polymers described in paragraphs 0033 to 0052 of JP-A-2010-237589, a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more. , Acrylic resin containing a carboxy group having an acid value of 60 mgKOH / g or more can be preferably used.

Another preferred embodiment of the binder polymer is a styrene-acrylic copolymer. In the present specification, the styrene-acrylic copolymer refers to a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth) acrylic compound, and is a structural unit derived from the styrene compound. The total content of the structural units derived from the (meth) acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, based on all the structural units of the copolymer.
The content of the structural unit derived from the styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 5% by mass to 80% by mass, based on all the structural units of the copolymer. preferable.
The content of the structural unit derived from the (meth) acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, and 20% by mass to 95% by mass, based on all the structural units of the copolymer. Mass% is more preferred.

The binder polymer preferably has an aromatic ring structure, and more preferably has a structural unit having an aromatic ring structure, because the effect in the present disclosure is more excellent.
Examples of the monomer forming a structural unit having an aromatic ring structure include styrene compounds such as styrene, tert-butoxystyrene, methylstyrene, and α-methylstyrene, and benzyl (meth) acrylate.
Of these, styrene compounds are preferable, and styrene is more preferable.
Further, it is more preferable that the binder polymer has a structural unit (constituent unit derived from styrene) represented by the following formula (S) from the viewpoint that the effect in the present disclosure is more excellent.

When the binder polymer has a structural unit having an aromatic ring structure, the content of the structural unit having an aromatic ring structure is 5% by mass or more with respect to all the structural units of the binder polymer from the viewpoint of more excellent effect in the present disclosure. 90% by mass is preferable, 10% by mass to 70% by mass is preferable, and 20% by mass to 60% by mass is further preferable.
Further, the content of the structural unit having an aromatic ring structure in the binder polymer is preferably 5 mol% to 70 mol%, preferably 10 mol%, based on all the structural units of the binder polymer, because the effect in the present disclosure is more excellent. It is more preferably from 60 mol%, still more preferably from 20 mol% to 60 mol%.
Further, the content of the structural unit represented by the above formula (S) in the binder polymer is preferably 5 mol% to 70 mol% with respect to all the structural units of the binder polymer from the viewpoint of further excellent effects in the present disclosure. 10 mol% to 60 mol% is more preferable, 20 mol% to 60 mol% is further preferable, and 20 mol% to 50 mol% is particularly preferable.
In the present specification, when the content of the "constituent unit" is specified by the molar ratio, the above "constituent unit" shall be synonymous with the "monomer unit". Further, in the present specification, the above-mentioned "monomer unit" may be modified after polymerization by a polymer reaction or the like. The same applies to the following.

The binder polymer preferably has an aliphatic hydrocarbon ring structure because the effect in the present disclosure is more excellent. That is, the binder polymer preferably has a structural unit having an aliphatic hydrocarbon ring structure. As the structural unit having an aliphatic hydrocarbon ring structure, either a monocyclic aliphatic hydrocarbon structure or a polycyclic aliphatic hydrocarbon structure can be used. Above all, it is more preferable that the binder polymer has a ring structure in which two or more aliphatic hydrocarbon rings are fused.

Examples of the ring constituting the aliphatic hydrocarbon ring structure in the structural unit having the aliphatic hydrocarbon ring structure include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, and an isoborone ring.
Among them, a ring in which two or more aliphatic hydrocarbon rings are fused is preferable because the effect in the present disclosure is more excellent, and a tetrahydrodicyclopentadiene ring (tricyclo [5.2.1.0 ^2,6 ] decane ring) is preferable. ) Is more preferable.
Examples of the monomer forming a structural unit having an aliphatic hydrocarbon ring structure include dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.
Further, the binder polymer more preferably has a structural unit represented by the following formula (Cy), and the structural unit represented by the above formula (S) and the following formula. It is more preferable to have a structural unit represented by (Cy).

In the formula (Cy), ^{RM represents a hydrogen atom or a methyl group, and RCy} ^represents a monovalent group having an aliphatic hydrocarbon ring structure.

The RM in the formula ( ^Cy ) is preferably a methyl group.
The RCy in the formula ( ^Cy ) is preferably a monovalent group having an aliphatic hydrocarbon ring structure having 5 to 20 carbon atoms, and a fat having 6 to 16 carbon atoms, because the effect in the present disclosure is more excellent. It is more preferably a monovalent group having a group hydrocarbon ring structure, and even more preferably a monovalent group having an aliphatic hydrocarbon ring structure having 8 to 14 carbon atoms.
Further, the aliphatic hydrocarbon ring structure in RCy of the formula ( ^Cy ) has a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure, or a norbornane ring structure, because the effect in the present disclosure is more excellent. It is preferably an isoborone ring structure, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, and even more preferably a tetrahydrodicyclopentadiene ring structure.
Further, the aliphatic hydrocarbon ring structure in RCy of the formula ( ^Cy ) is preferably a ring structure in which two or more aliphatic hydrocarbon rings are fused, from the viewpoint of further excellent effect in the present disclosure. It is more preferable that the ring is a condensed ring of ~ 4 aliphatic hydrocarbon rings.
Further, RCy in the formula ( ^Cy ) is a group in which the oxygen atom of —C (= O) O— in the formula (Cy) and the aliphatic hydrocarbon ring structure are directly bonded, because the effect in the present disclosure is more excellent. That is, it is preferably an aliphatic hydrocarbon ring group, more preferably a cyclohexyl group or a dicyclopentanyl group, and even more preferably a dicyclopentanyl group.

The binder polymer may have one type of structural unit having an aliphatic hydrocarbon ring structure alone, or may have two or more types.
When the binder polymer has a structural unit having an aliphatic hydrocarbon ring structure, the content of the structural unit having an aliphatic hydrocarbon ring structure is higher than that of all the structural units of the binder polymer because the effect in the present disclosure is more excellent. 5% by mass to 90% by mass is preferable, 10% by mass to 80% by mass is more preferable, and 20% by mass to 70% by mass is further preferable.
Further, the content of the structural unit having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 5 mol% to 70 mol% with respect to all the structural units of the binder polymer from the viewpoint of further excellent effects in the present disclosure. 10 mol% to 60 mol% is more preferable, and 20 mol% to 50 mol% is further preferable.
Further, the content of the structural unit represented by the above formula (Cy) in the binder polymer is preferably 5 mol% to 70 mol% with respect to all the structural units of the binder polymer from the viewpoint of further excellent effects in the present disclosure. 10 mol% to 60 mol% is more preferable, and 20 mol% to 50 mol% is further preferable.

When the binder polymer has a structural unit having an aromatic ring structure and a structural unit having an aliphatic hydrocarbon ring structure, the total content of the structural unit having an aromatic ring structure and the structural unit having an aliphatic hydrocarbon ring structure is the present. From the viewpoint of more excellent effect in the disclosure, 10% by mass to 90% by mass is preferable, 20% by mass to 80% by mass is more preferable, and 40% by mass to 75% by mass is further preferable, based on all the constituent units of the binder polymer. ..
Further, the total content of the structural unit having an aromatic ring structure and the structural unit having an aliphatic hydrocarbon ring structure in the binder polymer is 10 with respect to all the structural units of the binder polymer because the effect in the present disclosure is more excellent. It is preferably mol% to 80 mol%, more preferably 20 mol% to 70 mol%, still more preferably 40 mol% to 60 mol%.
Further, the total contents of the structural unit represented by the above formula (S) and the structural unit represented by the above formula (Cy) in the binder polymer are all the structural units of the binder polymer from the viewpoint that the effect in the present disclosure is more excellent. On the other hand, 10 mol% to 80 mol% is preferable, 20 mol% to 70 mol% is more preferable, and 40 mol% to 60 mol% is further preferable.
Further, the molar amount nS of the structural unit represented by the above formula (S) and the molar amount nCy of the structural unit represented by the above formula (Cy) in the binder polymer are more effective in the present disclosure.
It is preferable to satisfy the relationship shown in the following formula (SCy), more preferably to satisfy the following formula (SCy-1), and further preferably to satisfy the following formula (SCy-2).
0.2 ≤ nS / (nS + nCy) ≤ 0.8 Equation (SCy)
0.30 ≤ nS / (nS + nCy) ≤ 0.75 Equation (SCy-1)
0.40 ≤ nS / (nS + nCy) ≤ 0.70 Equation (SCy-2)

The binder polymer preferably has a structural unit having an acid group because the effect in the present disclosure is more excellent.
Examples of the acid group include a carboxy group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, and a carboxy group is preferable.
As the structural unit having the acid group, the structural unit derived from (meth) acrylic acid shown below is preferable, and the structural unit derived from methacrylic acid is more preferable.

The binder polymer may have one type of structural unit having an acid group alone or two or more types.
When the binder polymer has a structural unit having an acid group, the content of the structural unit having an acid group is 5% by mass to 50% by mass with respect to all the structural units of the binder polymer because the effect in the present disclosure is more excellent. % Is preferable, 5% by mass to 40% by mass is more preferable, and 10% by mass to 30% by mass is further preferable.
Further, the content of the constituent unit having an acid group in the binder polymer is preferably 5 mol% to 70 mol%, preferably 10 mol% to 10 mol%, based on all the constituent units of the binder polymer, from the viewpoint of further excellent effect in the present disclosure. 50 mol% is more preferable, and 20 mol% to 40 mol% is further preferable.
Further, the content of the constituent unit derived from (meth) acrylic acid in the binder polymer is preferably 5 mol% to 70 mol% with respect to all the constituent units of the binder polymer from the viewpoint of further excellent effects in the present disclosure. More preferably, mol% to 50 mol%, still more preferably 20 mol% to 40 mol%.

The binder polymer preferably has a reactive group, and more preferably has a structural unit having a reactive group, because the effect in the present disclosure is more excellent.
As the reactive group, a radically polymerizable group is preferable, and an ethylenically unsaturated group is more preferable. When the binder polymer has an ethylenically unsaturated group, the binder polymer preferably has a structural unit having an ethylenically unsaturated group in the side chain.
In the present specification, the "main chain" represents a relatively longest bond chain among the molecules of the polymer compound constituting the resin, and the "side chain" refers to an atomic group branched from the main chain. show.
As the ethylenically unsaturated group, an allyl group or a (meth) acryloxy group is more preferable.
Examples of structural units having a reactive group include, but are not limited to, those shown below.

The binder polymer may have one type of structural unit having a reactive group alone or two or more types.
When the binder polymer has a structural unit having a reactive group, the content of the structural unit having a reactive group is from 5% by mass to 5% by mass with respect to all the structural units of the binder polymer from the viewpoint of better effect in the present disclosure. 70% by mass is preferable, 10% by mass to 50% by mass is more preferable, and 20% by mass to 40% by mass is further preferable.
Further, the content of the structural unit having a reactive group in the binder polymer is preferably 5 mol% to 70 mol%, preferably 10 mol%, based on all the structural units of the binder polymer, because the effect in the present disclosure is more excellent. It is more preferably from 60 mol%, still more preferably from 20 mol% to 50 mol%.

As a means for introducing a reactive group into a binder polymer, a functional group such as a hydroxy group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, and a sulfo group, an epoxy compound, and a blocked isocyanate are used. Examples thereof include a method of reacting a compound such as a compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, and a carboxylic acid anhydride.
A preferred example of a means for introducing a reactive group into a binder polymer is that a polymer having a carboxy group is synthesized by a polymerization reaction and then glycidyl (meth) acrylate is added to a part of the carboxy group of the obtained polymer by the polymer reaction. Is mentioned as a means for introducing a (meth) acryloxy group into a polymer by reacting with the polymer. By this means, a binder polymer having a (meth) acryloxy group in the side chain can be obtained.
The polymerization reaction is preferably carried out under a temperature condition of 70 ° C. to 100 ° C., and more preferably carried out under a temperature condition of 80 ° C. to 90 ° C. As the polymerization initiator used in the above polymerization reaction, an azo-based initiator is preferable, and for example, V-601 (trade name) or V-65 (trade name) manufactured by Wako Pure Chemical Industries, Ltd. is more preferable. The polymer reaction is preferably carried out under temperature conditions of 80 ° C to 110 ° C. In the above polymer reaction, it is preferable to use a catalyst such as an ammonium salt.

As the binder polymer, the polymers shown below are preferable because the effects in the present disclosure are more excellent. The content ratios (a to d) and the weight average molecular weight Mw of each structural unit shown below can be appropriately changed according to the purpose.

Further, the binder polymer may contain a polymer having a structural unit having a carboxylic acid anhydride structure (hereinafter, also referred to as “polymer X”).
The carboxylic acid anhydride structure may be either a chain carboxylic acid anhydride structure or a cyclic carboxylic acid anhydride structure, but a cyclic carboxylic acid anhydride structure is preferable.
As the ring having a cyclic carboxylic acid anhydride structure, a 5-membered ring to a 7-membered ring is preferable, a 5-membered ring or a 6-membered ring is more preferable, and a 5-membered ring is further preferable.

The structural unit having a carboxylic acid anhydride structure is a structural unit containing a divalent group obtained by removing two hydrogen atoms from the compound represented by the following formula P-1 in the main chain, or the following formula P-1. It is preferable that the monovalent group obtained by removing one hydrogen atom from the represented compound is a structural unit bonded to the main chain directly or via a divalent linking group.

In the formula P-1, ^RA1a represents a substituent, ^n1a ^RA1a may be the same or different, and ^Z1a is −C (= O) −OC (= O) −. Represents a divalent group forming a ring containing, and n ^1a represents an integer of 0 or more.

Examples of the substituent represented by ^RA1a include an alkyl group.
As Z ^1a , an alkylene group having 2 to 4 carbon atoms is preferable, an alkylene group having 2 or 3 carbon atoms is more preferable, and an alkylene group having 2 carbon atoms is further preferable.
n ^1a represents an integer of 0 or more. When Z ^1a represents an alkylene group having 2 to 4 carbon atoms, n ^1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0.
When n ^1a represents an integer of 2 or more, a plurality of ^RA1a may be the same or different. Further, although a plurality of ^RA1a may be bonded to each other to form a ring, it is preferable that the RA1a are not bonded to each other to form a ring.

As the structural unit having a carboxylic acid anhydride structure, a structural unit derived from an unsaturated carboxylic acid anhydride is preferable, a structural unit derived from an unsaturated cyclic carboxylic acid anhydride is more preferable, and an unsaturated aliphatic cyclic carboxylic acid is preferable. A structural unit derived from an acid anhydride is more preferable, a structural unit derived from maleic anhydride or an itaconic acid anhydride is particularly preferable, and a structural unit derived from maleic anhydride is most preferable.

Hereinafter, specific examples of the structural unit having a carboxylic acid anhydride structure will be given, but the structural unit having a carboxylic acid anhydride structure is not limited to these specific examples. In the following structural units, Rx represents a hydrogen atom, a methyl group, a CH ₂ OH group, or CF ₃ groups, and Me represents a methyl group.

The structural unit having a carboxylic acid anhydride structure in the polymer X may be one kind alone or two or more kinds.

The total content of the structural units having a carboxylic acid anhydride structure is preferably 0 mol% to 60 mol%, more preferably 5 mol% to 40 mol%, and 10 mol% with respect to all the structural units of the polymer X. It is more preferably ~ 35 mol%.

The photosensitive resin layer may contain only one type of polymer X, or may contain two or more types of polymer X.
When the photosensitive resin layer contains the polymer X, the content of the polymer X is 0.1% by mass to 30% by mass with respect to the total mass of the photosensitive resin layer because the effect in the present disclosure is more excellent. Is preferable, 0.2% by mass to 20% by mass is more preferable, 0.5% by mass to 20% by mass is further preferable, and 1% by mass to 20% by mass is further preferable.

The weight average molecular weight (Mw) of the binder polymer is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 10,000 to 50,000, and even more preferably 20,000, because the effect in the present disclosure is more excellent. ~ 30,000 is particularly preferable.

The acid value of the binder polymer is preferably 10 mgKOH / g to 200 mgKOH / g, more preferably 60 mgKOH / g to 200 mgKOH / g, further preferably 60 mgKOH / g to 150 mgKOH / g, and particularly preferably 60 mgKOH / g to 110 mgKOH / g.
The acid value of the binder polymer is a value measured according to the method described in JIS K0070: 1992.

The photosensitive resin layer may contain only one kind of binder polymer, or may contain two or more kinds of binder polymers.
The content of the binder polymer is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, more preferably 30% by mass, based on the total mass of the photosensitive resin layer, because the effect in the present disclosure is more excellent. More preferably, it is by mass to 70% by mass.

<Polymerizable compound>
The photosensitive resin layer preferably contains a polymerizable compound.
The polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include a radically polymerizable group and a cationically polymerizable group, and a radically polymerizable group is preferable.

The polymerizable compound preferably contains a radically polymerizable compound having an ethylenically unsaturated group (hereinafter, also simply referred to as “ethylenically unsaturated compound”).
As the ethylenically unsaturated group, a (meth) acryloxy group is preferable.
The ethylenically unsaturated compound in the present specification is a compound other than the binder polymer, and preferably has a molecular weight of less than 5,000.

As one of the preferred embodiments of the polymerizable compound, a compound represented by the following formula (M) (simply referred to as “Compound M”) can be mentioned.
^Q2 - ^R1 - ^Q1 formula (M)
In formula (M), Q ¹ and Q ² each independently represent a (meth) acryloyloxy group, and R ¹ represents a divalent linking group having a chain structure.

It is preferable that Q ^{1 and Q 2 in the formula (M) have the same group as Q 1} ^{and Q 2} ^from ^the viewpoint of ease of synthesis.
Further, Q ¹ and Q ² in the formula (M) are preferably acryloyloxy groups from the viewpoint of reactivity.
As ^R1 in the formula (M), an alkylene group, an alkyleneoxyalkylene group (-L ¹ -OL ^1- ), or a polyalkylene oxyalkylene group (-(L)" is used because the effect in the present disclosure is more excellent. ¹ -O) _p -L ^1- ) is preferable, a hydrocarbon group having 2 to 20 carbon atoms or a polyalkyleneoxyalkylene group is more preferable, an alkylene group having 4 to 20 carbon atoms is further preferable, and an alkylene group having 6 to 20 carbon atoms is more preferable. Eighteen linear alkylene groups are particularly preferred.
The hydrocarbon group may have a chain structure at least partially, and the portion other than the chain structure is not particularly limited, and is, for example, a branched chain, cyclic, or having 1 to 1 to carbon atoms. It may be any of 5 linear alkylene groups, arylene groups, ether bonds, and combinations thereof, and alkylene groups or groups in which two or more alkylene groups and one or more arylene groups are combined are preferable. , The alkylene group is more preferable, and the linear alkylene group is further preferable.
The above L ¹ independently represents an alkylene group, and an ethylene group, a propylene group, or a butylene group is preferable, and an ethylene group or a 1,2-propylene group is more preferable.
p represents an integer of 2 or more, and is preferably an integer of 2 to 10.

Further, the number of atoms of the shortest connecting chain connecting ^Q1 and ^Q2 in the compound M is preferably 3 to 50, more preferably 4 to 40, because the effect in the present disclosure is more excellent. It is preferable, 6 to 20 pieces are more preferable, and 8 pieces to 12 pieces are particularly preferable.
In the present specification, "the number of atoms in the shortest connecting chain connecting between ^Q1 and ^Q2 " means the atoms in ^R1 connected to ^Q1 to the atoms in ^R1 connected to ^Q2 . The shortest number of atoms.

Specific examples of the compound M include 1,3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate. 1,7-Heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1, 4-Cyclohexanediol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, hydrogenated bisphenol A di (meth) acrylate, hydrogenated bisphenol F di (meth) acrylate, polyethylene glycol di (meth) acrylate , Polypropylene glycol di (meth) acrylate, poly (ethylene glycol / propylene glycol) di (meth) acrylate, and polybutylene glycol di (meth) acrylate. The ester monomer can also be used as a mixture.
Among the above compounds, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and 1,10-decanediol di (meth) acrylate are more effective in the present disclosure. , And at least one compound selected from the group consisting of neopentyl glycol di (meth) acrylate, preferably 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth). ) A compound and at least one compound selected from the group consisting of 1,10-decanediol di (meth) acrylate, more preferably 1,9-nonanediol di (meth) acrylate, and 1 , 10-Decandiol di (meth) acrylate is more preferably at least one compound selected from the group consisting of acrylates.

Further, as one of the preferred embodiments of the polymerizable compound, a bifunctional or higher functional ethylenically unsaturated compound can be mentioned.
As used herein, the term "bifunctional or higher functional ethylenically unsaturated compound" means a compound having two or more ethylenically unsaturated groups in one molecule.
As the ethylenically unsaturated group in the ethylenically unsaturated compound, a (meth) acryloyl group is preferable.
As the ethylenically unsaturated compound, a (meth) acrylate compound is preferable.

The bifunctional ethylenically unsaturated compound is not particularly limited and may be appropriately selected from known compounds.
Examples of the bifunctional ethylenically unsaturated compound other than the compound M include tricyclodecanedimethanol di (meth) acrylate and tricyclodecanedimenanol di (meth) acrylate.

Commercially available products of bifunctional ethylenically unsaturated compounds include tricyclodecanedimethanol diacrylate (trade name: NK ester A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and tricyclodecanedimenanol dimethacrylate (trade name: NK ester A-DCP). Product name: NK ester DCP, manufactured by Shin Nakamura Chemical Industry Co., Ltd., 1,9-nonanediol diacrylate (trade name: NK ester A-NOD-N, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), 1,6 -Hexanediol diacrylate (trade name: NK ester A-HD-N, manufactured by Shin Nakamura Chemical Industry Co., Ltd.) can be mentioned.

The trifunctional or higher functional ethylenically unsaturated compound is not particularly limited and may be appropriately selected from known compounds.
Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, and trimethylolpropane tri (meth) acrylate. Examples thereof include ditrimethylolpropane tetra (meth) acrylate, isocyanuric acid (meth) acrylate, and (meth) acrylate compound having a glycerintri (meth) acrylate skeleton.

Here, "(tri / tetra / penta / hexa) (meth) acrylate" is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate. Yes, "(tri / tetra) (meth) acrylate" is a concept that includes tri (meth) acrylate and tetra (meth) acrylate.

Examples of the polymerizable compound include caprolactone-modified compounds of (meth) acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Industry Co., Ltd., etc.), (Meta). ) Alkylene oxide-modified compound of acrylate compound (KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Industry Co., Ltd., EBECRYL (registered trademark) manufactured by Daicel Ornex Co., Ltd. ) 135, etc.), ethoxylated glycerin triacrylate (NK ester A-GLY-9E, etc. manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) can also be mentioned.

Examples of the polymerizable compound include urethane (meth) acrylate compounds.
Examples of the urethane (meth) acrylate include urethane di (meth) acrylate, and examples thereof include propylene oxide-modified urethane di (meth) acrylate, and ethylene oxide and propylene oxide-modified urethane di (meth) acrylate.
Further, as the urethane (meth) acrylate, a urethane (meth) acrylate having trifunctionality or higher can also be mentioned. As the lower limit of the number of functional groups, 6-functionality or more is more preferable, and 8-functionality or more is further preferable. The upper limit of the number of functional groups is preferably 20 or less. Examples of trifunctional or higher functional urethane (meth) acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Industry Co., Ltd.), UA-32P (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and U-15HA (manufactured by Shin Nakamura Chemical Industry Co., Ltd.). ), UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), AH-600 (trade name) manufactured by Kyoeisha Chemical Co., Ltd., and UA-306H, UA-306T, UA-306I, UA-510H. , And UX-5000 (both manufactured by Nippon Kayaku Co., Ltd.) and the like.

One of the preferred embodiments of the polymerizable compound is an ethylenically unsaturated compound having an acid group.
Examples of the acid group include a phosphoric acid group, a sulfo group, and a carboxy group.
Among these, the carboxy group is preferable as the acid group.
As the ethylenically unsaturated compound having an acid group, a trifunctional to tetrafunctional ethylenically unsaturated compound having an acid group [pentaerythritol tri and a tetraacrylate (PETA) skeleton introduced with a carboxy group (acid value: 80 mgKOH). / G to 120 mgKOH / g)], a pentafunctional to hexafunctional ethylenically unsaturated compound having an acid group (dipentaerythritol penta and hexaacrylate (DPHA) with a carboxy group introduced into the skeleton [acid value: 25 mgKOH / g] ~ 70 mgKOH / g)] and the like.
These trifunctional or higher functional ethylenically unsaturated compounds having an acid group may be used in combination with a bifunctional ethylenically unsaturated compound having an acid group, if necessary.

As the ethylenically unsaturated compound having an acid group, at least one selected from the group consisting of a bifunctional or higher functional ethylenically unsaturated compound having a carboxy group and a carboxylic acid anhydride thereof is preferable.
When the ethylenically unsaturated compound having an acid group is at least one selected from the group consisting of a bifunctional or higher functional ethylenically unsaturated compound having a carboxy group and a carboxylic acid anhydride thereof, the developability and film strength are higher. It will increase.
The bifunctional or higher functional unsaturated compound having a carboxy group is not particularly limited and can be appropriately selected from known compounds.
Examples of the bifunctional or higher functional unsaturated compound having a carboxy group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and the like. Aronix (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.) can be mentioned.

As the ethylenically unsaturated compound having an acid group, the polymerizable compound having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942 is preferable, and the contents described in this publication are incorporated in the present specification. Will be.

Examples of the polymerizable compound include a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid, a compound obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid, and a urethane. Urethane monomers such as (meth) acrylate compounds having a bond, γ-chloro-β-hydroxypropyl-β'-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β'-(meth) acryloyloxyethyl Examples thereof include phthalic acid compounds such as -o-phthalate and β-hydroxypropyl-β'-(meth) acryloyloxyethyl-o-phthalate, and (meth) acrylic acid alkyl esters.
These may be used alone or in combination of two or more.

Examples of the compound obtained by reacting a polyvalent alcohol with an α, β-unsaturated carboxylic acid include 2,2-bis (4-((meth) acrylamide polyethoxy) phenyl) propane and 2,2-bis. Bisphenol A-based (meth) acrylate compounds such as (4-((meth) acryloxypolypropoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane , Polyethylene glycol di (meth) acrylate having 2 to 14 ethylene oxide groups, polypropylene glycol di (meth) acrylate having 2 to 14 propylene oxide groups, and 2 to 14 ethylene oxide groups. And, polyethylene polypropylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate having 2 to 14 propylene oxide groups. , Trimethylolpropane diethoxytri (meth) acrylate, trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropane tetraethoxytri (meth) acrylate, trimethylolpropane pentaethoxytri (meth) acrylate, trimethylolpropane ) Tetra acrylate, tetramethylol methanetri (meth) acrylate, tetramethylol methanetetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. Can be mentioned.
Of these, an ethylene unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable, and tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, trimethylolpropanetri (meth) acrylate, or dimethylolpropanetri (meth) acrylate, or di (Trimethylolpropane) Tetraacrylate is more preferred.

Examples of the polymerizable compound include caprolactone-modified compounds of ethylenically unsaturated compounds (for example, KAYARAD® DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin Nakamura Chemical Industry Co., Ltd., etc.). An alkylene oxide-modified compound of an ethylenically unsaturated compound (for example, KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin Nakamura Chemical Industry Co., Ltd., EBECRYL manufactured by Daicel Ornex Co., Ltd. (registered trademark). ) 135, etc.), ethoxylated glycerin triacrylate (A-GLY-9E, etc. manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and the like.

As the polymerizable compound (particularly, an ethylenically unsaturated compound), a compound containing an ester bond is preferable in that the photosensitive resin layer after transfer is excellent in developability.
The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule, but is not ethylene-free having a tetramethylolmethane structure or a trimethylolpropane structure in that the effect in the present disclosure is excellent. Saturated compounds are preferred, and tetramethylolmethanetri (meth) acrylates, trimethylolmethanetetra (meth) acrylates, trimethylolpropane tri (meth) acrylates, or di (trimethylolpropane) tetraacrylates are more preferred.
From the viewpoint of imparting reliability, the ethylenically unsaturated compound includes an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms and the above-mentioned ethylene unsaturated compound having a tetramethylol methane structure or a trimethylol propane structure. It is preferable to contain a compound.
Examples of the ethylenically unsaturated compound having an aliphatic structure having 6 or more carbon atoms include 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, and tricyclodecanedimethanoldi. Examples include (meth) acrylate.

One of the preferred embodiments of the polymerizable compound is a polymerizable compound having an aliphatic hydrocarbon ring structure (preferably a bifunctional ethylenically unsaturated compound).
As the polymerizable compound, a polymerizable compound having a ring structure in which two or more aliphatic hydrocarbon rings are condensed (preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure) is used. Preferably, a bifunctional ethylenically unsaturated compound having a ring structure in which two or more aliphatic hydrocarbon rings are fused is more preferable, and tricyclodecanedimethanol di (meth) acrylate is further preferable.
As the aliphatic hydrocarbon ring structure, a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure, or an isoborone structure is preferable because the effect in the present disclosure is more excellent.

The molecular weight of the polymerizable compound is preferably 200 to 3,000, more preferably 250 to 2,600, still more preferably 280 to 2,200, and particularly preferably 300 to 2,200.
The proportion of the content of the polymerizable compound having a molecular weight of 300 or less among the polymerizable compounds contained in the photosensitive resin layer is 30% by mass or less with respect to the content of all the polymerizable compounds contained in the photosensitive resin layer. Is preferable, 25% by mass or less is more preferable, and 20% by mass or less is further preferable.

As one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer preferably contains a bifunctional or higher functional ethylenically unsaturated compound, and more preferably contains a trifunctional or higher functional ethylenically unsaturated compound. More preferably, it contains a functional or tetrafunctional ethylenically unsaturated compound.

Further, as one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer is a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and a binder polymer having a structural unit having an aliphatic hydrocarbon ring. And are preferably included.

Further, as one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer preferably contains a compound represented by the formula (M) (compound M) and an ethylenically unsaturated compound having an acid group. , 1,9-Nonandiol diacrylate, tricyclodecanedimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group are more preferable, and 1,9-nonandiol diacrylate and More preferably, it contains a tricyclodecanedimethanol diacrylate and a succinic acid-modified form of dipentaerythritol pentaacrylate.

Further, as one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer preferably contains compound M, an ethylenically unsaturated compound having an acid group, and a thermally crosslinkable compound described later, and the compound M is preferable. It is more preferable to contain an ethylenically unsaturated compound having an acid group and a blocked isocyanate compound described later.

Further, as one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer has a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth) acrylate compound) and a trifunctional or higher functional ethylenically unsaturated compound. It preferably contains a saturated compound (preferably a trifunctional or higher functional (meth) acrylate compound).

Further, as one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer contains compound M and a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure from the viewpoint of rust prevention. Is preferable.
Further, as one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer is not ethylenically having compound M and an acid group from the viewpoints of substrate adhesion, development residue inhibitory property, and rust resistance. It is preferable to contain a saturated compound, more preferably compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and an ethylenically unsaturated compound having an acid group, and more preferably compound M, an aliphatic compound. It is more preferable to contain a bifunctional ethylenically unsaturated compound having a hydrocarbon ring structure, a trifunctional or higher functional ethylenically unsaturated compound, and an ethylenically unsaturated compound having an acid group, more preferably compound M, an aliphatic hydrocarbon ring. It is particularly preferable to contain a bifunctional ethylenically unsaturated compound having a structure, a trifunctional or higher functional ethylenically unsaturated compound, an ethylenically unsaturated compound having an acid group, and a urethane (meth) acrylate compound.
Further, as one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer is a 1,9-nonanediol from the viewpoints of substrate adhesion, development residue inhibitory property, and rust resistance. It preferably contains a diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, and preferably contains 1,9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate, and polyfunctional ethylene having a carboxylic acid group. It preferably contains a sex-unsaturated compound, further including 1,9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate, dipentaerythritol hexaacrylate, and an ethylenically unsaturated compound having a carboxylic acid group. Particularly preferably, it contains 1,9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate, an ethylenically unsaturated compound having a carboxylic acid group, and a urethane acrylate compound.

The photosensitive resin layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound.
The content of the bifunctional or higher functional ethylenically unsaturated compound in the ethylenically unsaturated compound is 60% by mass to 100% by mass with respect to the total content of all the ethylenically unsaturated compounds contained in the photosensitive resin layer. It is preferably 80% by mass to 100% by mass, more preferably 90% by mass to 100% by mass.

The polymerizable compound (particularly, the ethylenically unsaturated compound) may be used alone or in combination of two or more.
The content of the polymerizable compound (particularly, the ethylenically unsaturated compound) in the photosensitive resin layer is preferably 1% by mass to 70% by mass, preferably 5% by mass to 70% by mass, based on the total mass of the photosensitive resin layer. Is more preferable, 5% by mass to 60% by mass is further preferable, and 5% by mass to 50% by mass is particularly preferable.

<Photopolymerization initiator>
The photosensitive resin layer preferably contains a photopolymerization initiator.
The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.
Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter, also referred to as “oxym-based photopolymerization initiator”) and a photopolymerization initiator having an α-aminoalkylphenone structure (hereinafter, “α-”. Aminoalkylphenone-based photopolymerization initiator "), photopolymerization initiator having an α-hydroxyalkylphenone structure (hereinafter, also referred to as" α-hydroxyalkylphenone-based polymerization initiator "), acylphosphine oxide structure. Photopolymerization initiator (hereinafter, also referred to as “acylphosphine oxide-based photopolymerization initiator”) and photopolymerization initiator having an N-phenylglycine structure (hereinafter, “N-phenylglycine-based photopolymerization initiator”). Also referred to as "agent").

The photopolymerization initiator is selected from the group consisting of an oxime-based photopolymerization initiator, an α-aminoalkylphenone-based photopolymerization initiator, an α-hydroxyalkylphenone-based polymerization initiator, and an N-phenylglycine-based photopolymerization initiator. It is preferable to contain at least one selected from the group consisting of an oxime-based photopolymerization initiator, an α-aminoalkylphenone-based photopolymerization initiator, and an N-phenylglycine-based photopolymerization initiator. Is more preferable.

Further, as the photopolymerization initiator, for example, the polymerization initiator described in paragraphs 0031 to 0042 of JP-A-2011-95716 and paragraphs 0064-0081 of JP-A-2015-014783 may be used. ..

Commercially available photopolymerization initiators include 1- [4- (phenylthio) phenyl] -1,2-octanedione-2- (O-benzoyloxime) [trade name: IRGACURE (registered trademark) OXE-01, BASF. Manufactured by], 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] etanone-1- (O-acetyloxime) [trade name: IRGACURE (registered trademark) OXE-02 , BASF], IRGACURE (registered trademark) OXE03 (BASF), IRGACURE (registered trademark) OXE04 (BASF), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 -[4- (4-morpholinyl) phenyl] -1-butanone [trade name: Omnirad (registered trademark) 379EG, IGM Resins B. V company], 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one [trade name: Omnirad (registered trademark) 907, IGM Resins B. V company], 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one [trade name: Omnirad (registered trademark) 127 , IGM Resins B. V company], 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 [trade name: Omnirad (registered trademark) 369, IGM Resins B. V company], 2-hydroxy-2-methyl-1-phenylpropane-1-one [trade name: Omnirad (registered trademark) 1173, IGM Resins B. V company], 1-hydroxycyclohexylphenyl ketone [trade name: Omnirad (registered trademark) 184, IGM Resins B. V company], 2,2-dimethoxy-1,2-diphenylethane-1-one [trade name: Omnirad (registered trademark) 651, IGM Resins B.I. Oxime ester-based [trade name: Lunar (registered trademark) 6, manufactured by DKSH Japan Co., Ltd.], 1- [4- (phenylthio) phenyl] -3-cyclopentylpropane-1,2-dione, etc. -2- (O-benzoyloxime) (trade name: TR-PBG-305, manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), 3-Cyclohexyl-1- [9-ethyl-6- (2-furanylcarbonyl) -9H -Carbazole-3-yl] -1,2-propanedione-2- (O-acetyloxime) (trade name: TR-PBG-326, manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), 3-Cyclohexyl-1- (6) -(2- (Benzoyloxyimino) hexanoyl) -9-ethyl-9H-carbazole-3-yl) -Propane-1,2-dione-2- (O-benzoyloxime) (trade name: TR-PBG-391) , Changzhou Strong Electronics New Materials Co., Ltd.), APi-307 (1- (biphenyl-4-yl) -2-methyl-2-morpholinopropane-1-one, Shenzhen UV-ChemTech Ltd.) and the like.

The photopolymerization initiator may be used alone or in combination of two or more.
When the photosensitive resin layer contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1% by mass or more, preferably 0.5% by mass, based on the total mass of the photosensitive resin layer. The above is more preferable, and 1.0% by mass or more is further preferable. The upper limit thereof is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the photosensitive resin layer.

<Heterocyclic compound>
The photosensitive resin layer may contain a heterocyclic compound.
The heterocycle contained in the heterocyclic compound may be either a monocyclic or polycyclic complex.
Examples of the hetero atom contained in the heterocyclic compound include a nitrogen atom, an oxygen atom and a sulfur atom. 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.

Examples of the heterocyclic compound include a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazol compound, a triazine compound, a rhonin compound, a thiazole compound, a benzothiazole compound, a benzoimidazole compound, a benzoxazole compound, and a pyrimidine compound.
Among the above, the heterocyclic compound is at least one selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazol compound, a triazine compound, a rhonin compound, a thiazole compound, a benzoimidazole compound, and a benzoxazole compound. The above-mentioned compound is preferable, and at least one compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazol compound, a thiazole compound, a benzothiazole compound, a benzoimidazole compound, and a benzoxazole compound is more preferable.

A preferable specific example of the heterocyclic compound is shown below. Examples of the triazole compound and the benzotriazole compound include the following compounds.

Examples of the tetrazole compound include the following compounds.

Examples of the thiadiazole compound include the following compounds.

Examples of the triazine compound include the following compounds.

Examples of the loadonine compound include the following compounds.

Examples of the thiazole compound include the following compounds.

Examples of the benzothiazole compound include the following compounds.

Examples of the benzimidazole compound include the following compounds.

Examples of the benzoxazole compound include the following compounds.

The heterocyclic compound may be used alone or in combination of two or more.
When the photosensitive resin layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01% by mass to 20.0% by mass, preferably 0.10% by mass, based on the total mass of the photosensitive resin layer. It is more preferably ~ 10.0% by mass, further preferably 0.30% by mass to 8.0% by mass, and particularly preferably 0.50% by mass to 5.0% by mass.

<Alphatic thiol compound>
The photosensitive resin layer may contain an aliphatic thiol compound.
When the photosensitive resin layer contains an aliphatic thiol compound, the aliphatic thiol compound undergoes an en-thiol reaction with a radically polymerizable compound having an ethylenically unsaturated group, so that the film formed is cured and shrunk. It is suppressed and the stress is relieved.

As the aliphatic thiol compound, a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, a bifunctional or higher functional aliphatic thiol compound) is preferable.
Among the above, as the aliphatic thiol compound, a polyfunctional aliphatic thiol compound is more preferable from the viewpoint of adhesion of the formed pattern (particularly, adhesion after exposure).
As used herein, the term "polyfunctional aliphatic thiol compound" means an aliphatic compound having two or more thiol groups (also referred to as "mercapto groups") in the molecule.

As the polyfunctional aliphatic thiol compound, a low molecular weight compound having a molecular weight of 100 or more is preferable. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and even more preferably 150 to 1,000.

As the number of functional groups of the polyfunctional aliphatic thiol compound, for example, bifunctional to 10 functional is preferable, bifunctional to 8 functional is more preferable, and bifunctional to 6 functional is further preferable, from the viewpoint of adhesion of the formed pattern. preferable.

Examples of the polyfunctional aliphatic thiol compound include trimethylolpropanetris (3-mercaptobutylate), 1,4-bis (3-mercaptobutylyloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), and the like. 1,3,5-Tris (3-mercaptobutylyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylol ethanetris (3-mercaptobutyrate) ), Tris [(3-mercaptopropionyloxy) ethyl] isocyanurate, trimethylolpropanthris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate) Pionate), Dipentaerythritol Hexakis (3-mercaptopropionate), Ethylene glycol bisthiopropionate, 1,4-bis (3-mercaptobutylyloxy) butane, 1,2-ethanedithiol, 1, Examples thereof include 3-propanedithiol, 1,6-hexamethylenedithiol, 2,2'-(ethylenedithio) dietanthiol, meso-2,3-dimercaptosuccinic acid, and di (mercaptoethyl) ether.

Among the above, the polyfunctional aliphatic thiol compounds include trimethylolpropane tris (3-mercaptobutyrate), 1,4-bis (3-mercaptobutylyloxy) butane, and 1,3,5-tris. At least one compound selected from the group consisting of (3-mercaptobutylyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione is preferred.

Examples of the monofunctional aliphatic thiol compound include 1-octanethiol, 1-dodecanethiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, and n-. Examples thereof include octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.

The photosensitive resin layer may contain one kind of aliphatic thiol compound alone, or may contain two or more kinds of aliphatic thiol compounds.
When the photosensitive resin layer contains an aliphatic thiol compound, the content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5% by mass to 50% by mass, based on the total mass of the photosensitive resin layer. 5, 5% by mass to 30% by mass is more preferable, and 8% by mass to 20% by mass is particularly preferable.

<Thermal crosslinkable compound>
The photosensitive resin layer preferably contains a heat-crosslinkable compound from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.
As the heat-crosslinkable compound used in the photosensitive resin layer of the second embodiment, the above-mentioned heat-crosslinkable compound is preferably used in the photosensitive resin layer of the first embodiment.
The heat-crosslinkable compound may be used alone or in combination of two or more.
When the photosensitive resin layer contains a heat-crosslinkable compound, the content of the heat-crosslinkable compound is preferably 1% by mass to 50% by mass, preferably 5% by mass to 30% by mass, based on the total mass of the photosensitive resin layer. Is more preferable.

<Surfactant>
The photosensitive resin layer may contain a surfactant.
As the surfactant used in the photosensitive resin layer of the second embodiment, the above-mentioned surfactant is preferably used in the photosensitive resin layer of the first embodiment.
The surfactant may be used alone or in combination of two or more.
When the photosensitive resin layer contains a surfactant, the content of the surfactant is preferably 0.01% by mass to 3.0% by mass, preferably 0.01% by mass, based on the total mass of the photosensitive resin layer. -1.0% by mass is more preferable, and 0.05% by mass to 0.80% by mass is further preferable.

<Polymerization inhibitor>
The photosensitive resin layer may contain a polymerization inhibitor.
The polymerization inhibitor means a compound having a function of delaying or prohibiting a polymerization reaction. As the polymerization inhibitor, for example, a known compound used as a polymerization inhibitor can be used.

Examples of the polymerization inhibitor include phenothiazine compounds such as phenothiazine, bis- (1-dimethylbenzyl) phenothiazine, and 3,7-dioctylphenothiazine; bis [3- (3-tert-butyl-4-hydroxy-5-. Methylphenyl) propionic acid] [ethylene bis (oxyethylene)] 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-) Hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3) , 5-Di-t-butylanilino) -1,3,5-triazine, and hindered phenol compounds such as pentaerythritol tetrakis 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate; 4 -Nitroso compounds such as nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, and N-nitrosophenylhydroxylamine or salts thereof; methylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone. , And quinone compounds such as 4-benzoquinone; phenolic compounds such as 4-methoxyphenol, 4-methoxy-1-naphthol, and t-butylcatechol; copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, And a metal salt compound such as manganese diphenyldithiocarbamate can be mentioned.
Among them, at least one selected from the group consisting of a phenylothiazine compound, a nitroso compound or a salt thereof, and a hindered phenol compound is preferable as the polymerization inhibitor because the effect in the present disclosure is more excellent, and phenylothiazine and bis [3]. -(3-tert-Butyl-4-hydroxy-5-methylphenyl) propionic acid] [ethylenebis (oxyethylene)] 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5- Tris (3,5-di-t-butyl-4-hydroxybenzyl) and N-nitrosophenylhydroxylamine aluminum salt are more preferred.

The polymerization inhibitor may be used alone or in combination of two or more.
When the photosensitive resin layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01% by mass to 10.0% by mass, preferably 0.01% by mass, based on the total mass of the photosensitive resin layer. -5.0% by mass is more preferable, and 0.04% by mass to 3.0% by mass is further preferable.

<Hydrogen donating compound>
The photosensitive resin layer may contain a hydrogen donating compound.
The hydrogen donating compound has an action of further improving the sensitivity of the photopolymerization initiator to active light rays and suppressing the inhibition of the polymerization of the polymerizable compound by oxygen.
Examples of the hydrogen donating compound include amines and amino acid compounds.

Examples of amines include M.I. R. Sander et al., "Journal of Polymer Society", Vol. 10, pp. 3173 (1972), Japanese Patent Application Laid-Open No. 44-020189, Japanese Patent Application Laid-Open No. 51-082102, Japanese Patent Application Laid-Open No. 52-134692, Japanese Patent Application Laid-Open No. 59-138205. Examples thereof include the compounds described in Japanese Patent Application Laid-Open No. 60-0843305, Japanese Patent Application Laid-Open No. 62-018537, Japanese Patent Application Laid-Open No. 64-033104, and Research Disclosure No. 33825. More specifically, 4,4'-bis (diethylamino) benzophenone, tris (4-dimethylaminophenyl) methane (also known as leucocrystal violet), triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyl. Examples thereof include dimethylaniline and p-methylthiodimethylaniline.
Among them, at least one selected from the group consisting of 4,4'-bis (diethylamino) benzophenone and tris (4-dimethylaminophenyl) methane is preferable as the amines in that the effect in the present disclosure is more excellent. ..

Examples of the amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.
Among them, N-phenylglycine is preferable as the amino acid compound in that the effect in the present disclosure is more excellent.

Examples of the hydrogen donor compound include an organometallic compound (tributyltin acetate, etc.) described in JP-A-48-042965, a hydrogen donor described in JP-A-55-0344414, and JP-A-6. A sulfur compound (Trithian and the like) described in JP-A-308727 can also be mentioned.

The hydrogen donating compound may be used alone or in combination of two or more.
When the photosensitive resin layer contains a hydrogen donating compound, the content of the hydrogen donating compound is based on the total mass of the photosensitive resin layer in terms of improving the curing rate due to the balance between the polymerization growth rate and the chain transfer. , 0.01% by mass to 10.0% by mass, more preferably 0.01% by mass to 8.0% by mass, still more preferably 0.03% by mass to 5.0% by mass.

<Impurities, etc.>
The photosensitive resin layer may contain a predetermined amount of impurities.
The impurities in the photosensitive resin layer of the second embodiment are the same as in the preferred embodiment of the impurities described above in the photosensitive resin layer of the first embodiment.

<Residual monomer>
The photosensitive resin layer may contain a residual monomer corresponding to each structural unit of the binder polymer described above.
Regarding the residual monomer corresponding to each structural unit of the binder polymer in the photosensitive resin layer of the second embodiment, the residual monomer corresponding to each structural unit of the alkali-soluble resin described above in the photosensitive resin layer of the first embodiment. It is the same as the preferable aspect of.

<Other ingredients>
The photosensitive resin layer may contain components other than the components described above (hereinafter, also referred to as “other components”). Other components include, for example, colorants, antioxidants, and particles (eg, metal oxide particles). Further, as other components, other additives described in paragraphs 0058 to 0071 of JP-A-2000-310706 can also be mentioned.

-particle-
As the particles, metal oxide particles are preferable.
The metal in the metal oxide particles also includes metalloids such as B, Si, Ge, As, Sb, and Te.
The average primary particle diameter of the particles is preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm, for example, from the viewpoint of transparency of the cured film.
The average primary particle size of the particles is calculated by measuring the particle size of 200 arbitrary particles using an electron microscope and arithmetically averaging the measurement results. If the shape of the particle is not spherical, the longest side is the particle diameter.

When the photosensitive resin layer contains particles, it may contain only one kind of particles having different metal types and sizes, or may contain two or more kinds of particles.
The photosensitive resin layer does not contain particles, or when the photosensitive resin layer contains particles, the content of the particles is more than 0% by mass and 35% by mass or less with respect to the total mass of the photosensitive resin layer. It is preferable that the particles are not contained, or the content of the particles is more than 0% by mass and 10% by mass or less based on the total mass of the photosensitive resin layer, and the particles are not contained or the particles are contained. The amount is more preferably more than 0% by mass and 5% by mass or less with respect to the total mass of the photosensitive resin layer, and either does not contain particles or the content of particles is 0% by mass with respect to the total mass of the photosensitive resin layer. Ultra 1% by mass or less is more preferable, and it is particularly preferable that particles are not contained.

-Colorant-
The photosensitive resin layer may contain a colorant (pigment, dye, etc.), but for example, from the viewpoint of transparency, it is preferable that the photosensitive resin layer contains substantially no colorant.
When the photosensitive resin layer contains a colorant, the content of the colorant is preferably less than 1% by mass, more preferably less than 0.1% by mass, based on the total mass of the photosensitive resin layer.

-Antioxidant-
Examples of the antioxidant include 1-phenyl-3-pyrazolidone (also known as phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-. 3-Pyrazoridones such as 3-pyrazolidone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorhydroquinone; paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, and paraphenylenediamine. Be done.
Among them, 3-pyrazolidones are preferable as the antioxidant, and 1-phenyl-3-pyrazolidone is more preferable as the antioxidant in that the effect in the present disclosure is more excellent.

When the photosensitive resin layer contains an antioxidant, the content of the antioxidant is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, based on the total mass of the photosensitive resin layer. 0.01% by mass or more is more preferable. The upper limit is not particularly limited, but is preferably 1% by mass or less.

<Layer thickness of photosensitive resin layer>
The thickness of the photosensitive resin layer is not particularly limited, but is often 30 μm or less, and is preferably 20 μm or less, more preferably 15 μm or less, still more preferably 10 μm or less, and further preferably 5.0 μm in that the effect in the present disclosure is more excellent. The following are particularly preferred. As the lower limit, 0.60 μm or more is preferable, and 1.5 μm or more is more preferable, because the strength of the film obtained by curing the photosensitive resin layer is excellent.
The thickness of the photosensitive resin layer can be calculated as, for example, an average value of any five points measured by cross-sectional observation with a scanning electron microscope (SEM).

<Refractive index of photosensitive resin layer>
The refractive index of the photosensitive resin layer is preferably 1.47 to 1.56, more preferably 1.49 to 1.54.

<Color of photosensitive resin layer>
The photosensitive resin layer is preferably achromatic. Specifically, the total reflection (incident angle 8 °, light source: D-65 (2 ° field of view)) has an L ^* value of 10 to 90 in the CIE1976 (L ^* , a ^* , b ^* ) color space. The a ^* value is preferably −1.0 to 1.0, and the b ^* value is preferably −1.0 to 1.0.

The pattern (cured film of the photosensitive resin layer) obtained by curing the photosensitive resin layer is preferably achromatic.
Specifically, the total reflection (incident angle 8 °, light source: D-65 (2 ° field of view)) has a pattern L ^* value of 10 to 90 in the CIE1976 (L ^* , a ^* , b ^* ) color space. The a ^* value of the pattern is preferably −1.0 to 1.0, and the b ^* value of the pattern is preferably −1.0 to 1.0.

[Refractive index adjustment layer]
The photosensitive transfer material preferably has a refractive index adjusting layer.
As the refractive index adjusting layer, a known refractive index adjusting layer can be applied. Examples of the material contained in the refractive index adjusting layer include a binder polymer, a polymerizable compound, a metal salt, and particles.
The method for controlling the refractive index of the refractive index adjusting layer is not particularly limited, and for example, a method using a resin having a predetermined refractive index alone, a method using a resin and particles, and a composite of a metal salt and a resin are used. Is mentioned.

Examples of the binder polymer and the polymerizable compound include the binder polymer and the polymerizable compound described in the above section “Photosensitive resin layer”.

Examples of the particles include metal oxide particles and metal particles.
The type of the metal oxide particles is not particularly limited, and examples thereof include known metal oxide particles. The metal in the metal oxide particles also includes metalloids such as B, Si, Ge, As, Sb, and Te.

The average primary particle diameter of the particles is preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm, for example, from the viewpoint of transparency of the cured film.
The average primary particle size of the particles is calculated by measuring the particle size of 200 arbitrary particles using an electron microscope and arithmetically averaging the measurement results. If the shape of the particle is not spherical, the longest side is the particle diameter.

Specific examples of the metal oxide particles include zirconium oxide particles (ZrO ₂ particles), Nb ₂ O ₅ particles, titanium oxide particles (TIO ₂ particles), silicon dioxide particles (SiO ₂ particles), and a composite thereof. At least one selected from the group consisting of particles is preferable.
Among these, as the metal oxide particles, for example, at least one selected from the group consisting of zirconium oxide particles and titanium oxide particles is more preferable because the refractive index can be easily adjusted.

Commercially available metal oxide particles include fired zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT% -F04) and fired zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT% -F74). ), Fired zirconium oxide particles (CIK Nanotech Co., Ltd., product name: ZRPGM15WT% -F75), fired zirconium oxide particles (CIK Nanotech Co., Ltd., product name: ZRPGM15WT% -F76), zirconium oxide particles (Nano Youth OZ) -S30M, manufactured by Nissan Chemical Industry Co., Ltd.) and zirconium oxide particles (Nano Youth OZ-S30K, manufactured by Nissan Chemical Industry Co., Ltd.).

The particles may be used alone or in combination of two or more.
The content of the particles in the refractive index adjusting layer is preferably 1% by mass to 95% by mass, more preferably 20% by mass to 90% by mass, and 40% by mass to 85% by mass with respect to the total mass of the refractive index adjusting layer. More preferred.
When titanium oxide is used as the metal oxide particles, the content of the titanium oxide particles is preferably 1% by mass to 95% by mass, more preferably 20% by mass to 90% by mass, based on the total mass of the refractive index adjusting layer. , 40% by mass to 85% by mass is more preferable.

The refractive index of the refractive index adjusting layer is preferably higher than that of the photosensitive resin layer.
The refractive index of the refractive index adjusting layer is preferably 1.50 or more, more preferably 1.55 or more, further preferably 1.60 or more, and particularly preferably 1.65 or more. The upper limit of the refractive index of the refractive index adjusting layer is preferably 2.10 or less, more preferably 1.85 or less, further preferably 1.78 or less, and particularly preferably 1.74 or less.

The thickness of the refractive index adjusting layer is preferably 50 nm to 500 nm, more preferably 55 nm to 110 nm, and even more preferably 60 nm to 100 nm.

<Manufacturing method of photosensitive transfer material of the second embodiment>
The method for producing the photosensitive transfer material of the second embodiment is not particularly limited, and a known method can be used.
As a method for producing the photosensitive transfer material 10 shown in FIG. 2, for example, a photosensitive resin composition is applied to the surface of the temporary support 1 to form a coating film, and the coating film is further dried to form a photosensitive resin. The step of forming the layer 3 and the composition for forming the refractive index adjusting layer are applied to the surface of the photosensitive resin layer 3 to form a coating film, and the coating film is further dried to form the refractive index adjusting layer 5. Examples include steps and methods including.

The photosensitive transfer material 10 is manufactured by crimping the protective film 7 onto the refractive index adjusting layer 5 of the laminate manufactured by the above-mentioned manufacturing method.
The method for producing the photosensitive transfer material of the first embodiment temporarily includes a step of providing a protective film 7 so as to be in contact with the surface of the refractive index adjusting layer 5 opposite to the side having the temporary support 1. It is preferable to manufacture the photosensitive transfer material 10 including the support 1, the transfer layer 2 including the photosensitive resin layer 3 and the refractive index adjusting layer 5, and the protective film 7.
After manufacturing the photosensitive transfer material 10 by the above-mentioned manufacturing method, the photosensitive transfer material 10 in the form of a roll may be manufactured and stored by winding the photosensitive transfer material 10. The photosensitive transfer material in the form of a roll can be provided as it is in the bonding process with the substrate by the roll-to-roll method described later.

The method for producing the photosensitive transfer material 10 is a method in which the refractive index adjusting layer 5 is formed on the protective film 7 and then the photosensitive resin layer 3 is formed on the surface of the refractive index adjusting layer 5. You may.
Further, as a method for producing the photosensitive transfer material 10, the photosensitive resin layer 3 is formed on the temporary support 1, and the refractive index adjusting layer 5 is separately formed on the protective film 7, and the photosensitive resin layer is formed. A method may be used in which the refractive index adjusting layer 5 is bonded to the 3 and the refractive index adjusting layer 5.

The method for forming the photosensitive resin composition and the photosensitive resin layer in the second embodiment is the same as the method for forming the photosensitive resin composition and the photosensitive resin layer described above in the first embodiment, which is a preferred embodiment. Is the same.

<Composition for forming a refractive index adjusting layer and a method for forming the refractive index adjusting layer>
The composition for forming the refractive index adjusting layer preferably contains various components forming the above-mentioned refractive index adjusting layer and a solvent. In the composition for forming a refractive index adjusting layer, the preferable range of the content of each component with respect to the total solid content of the composition is the same as the preferable range of the content of each component with respect to the total mass of the refractive index adjusting layer described above. be.
The solvent is not particularly limited as long as it can dissolve or disperse the components contained in the refractive index adjusting layer, and at least one selected from the group consisting of water and a water-miscible organic solvent is preferable, with water or water. A mixed solvent with a water-miscible organic solvent is more preferable.
Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, and alcohols having 1 to 3 carbon atoms are preferable, and methanol or ethanol is more preferable.
The solvent may be used alone or in combination of two or more.
The content of the solvent is preferably 50 parts by mass to 2,500 parts by mass, more preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass to 900 parts by mass with respect to 100 parts by mass of the total solid content of the composition. The unit is more preferable.

The method for forming the refractive index adjusting layer is not particularly limited as long as it can form a layer containing the above components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.). Be done.

Further, by attaching the protective film to the refractive index adjusting layer, the photosensitive transfer material of the second embodiment can be manufactured.
The method of attaching the protective film to the refractive index adjusting layer is not particularly limited, and known methods can be mentioned.
Examples of the device for adhering the protective film to the refractive index adjusting layer include a vacuum laminator and a known laminator such as an auto-cut laminator.
It is preferable that the laminator is provided with an arbitrary heatable roller such as a rubber roller and can be pressurized and heated.

(Manufacturing method of resin pattern, manufacturing method of laminate, and etching method)
The method for producing a resin pattern according to the present disclosure is a method for producing a resin pattern for forming a resin pattern on a substrate by using the photosensitive transfer material according to the present disclosure.
The method for producing the resin pattern includes a step of peeling the protective film from the photosensitive transfer material according to the present disclosure (hereinafter, also referred to as “protective film peeling step”), and the above-mentioned photosensitive transfer material from which the protective film has been peeled off. A step of bringing the outermost layer on the side having the photosensitive resin layer to the temporary support in contact with a substrate (preferably a substrate having a conductive layer) and bonding them (hereinafter, also referred to as “bonding step”). A step of pattern-exposing the photosensitive resin layer via the temporary support (hereinafter, also referred to as “exposure step”) and a step of developing the exposed photosensitive resin layer to form a resin pattern (hereinafter, “exposed step”). It is also referred to as "development step"), and a method including the above in this order is preferable.

The method for producing a laminate according to the present disclosure is a method for producing a laminate having a resin pattern on a substrate using the photosensitive transfer material according to the present disclosure.
As a method for producing the laminate, a method including the protective film peeling step, the bonding step, the exposure step, and the developing step in this order is preferable.

The etching method according to the present disclosure is not particularly limited as long as it is a method using the photosensitive transfer material according to the present disclosure.
As an etching method according to the present disclosure, the resin pattern is arranged in a laminate in which the substrate, the conductive layer, and the resin pattern manufactured by the method for manufacturing the resin pattern according to the present disclosure are laminated in this order. A method including a step of etching the conductive layer in a region not provided is preferable.
Hereinafter, each step included in the resin pattern manufacturing method, the laminated body manufacturing method, and the etching method will be described, but unless otherwise specified, each step included in the resin pattern manufacturing method or the laminated body manufacturing method will be described. The contents of the above shall also be applied to each step included in the etching method.

<Protective film peeling process>
The method for producing the resin pattern or the method for producing the laminate preferably includes a step of peeling the protective film from the photosensitive transfer material according to the present disclosure. The method of peeling the protective film is not limited, and a known method can be applied.

<Lasting process>
It is preferable that the method for producing the resin pattern or the method for producing the laminate includes a bonding step.
In the bonding step, the substrate (or the conductive layer if the conductive layer is provided on the surface of the substrate) is brought into contact with the outermost layer on the side having the photosensitive resin layer with respect to the temporary support of the photosensitive transfer material. , It is preferable to crimp the photosensitive transfer material and the substrate. In the above aspect, in order to improve the adhesion between the outermost layer on the side having the photosensitive resin layer and the substrate with respect to the temporary support in the photosensitive transfer material, the pattern-formed photosensitive after exposure and development is improved. The resin layer can be suitably used as an etching resist when etching the conductive layer.

Further, in the bonding step, a layer other than the protective film (for example, a high refractive index layer and / or a low refractive index layer) is further formed on the surface of the photosensitive resin layer on the side where the photosensitive transfer material does not face the temporary support. In this case, the surface of the photosensitive resin layer on the side that does not have the temporary support and the substrate are bonded to each other via the layer.

The method of crimping the substrate and the photosensitive transfer material is not particularly limited, and a known transfer method or laminating method can be used.
The photosensitive transfer material is bonded to the substrate by superimposing the outermost layer on the side having the photosensitive resin layer on the temporary support of the photosensitive transfer material on the substrate, and pressurizing and heating by means such as a roll. It is preferable that this is done by applying. For bonding, a known laminator such as a laminator, a vacuum laminator, and an auto-cut laminator capable of further increasing productivity can be used.
The laminating temperature is not particularly limited, but is preferably 70 ° C to 130 ° C, for example.

It is preferable that the resin pattern manufacturing method and the etching method including the bonding step are performed by a roll-to-roll method.
Hereinafter, the roll-to-roll method will be described.
The roll-to-roll method uses a substrate that can be wound and unwound as a substrate, and winds the substrate or a structure containing the substrate before any of the steps included in the resin pattern manufacturing method or the etching method. At least one of a step of unwinding (also referred to as “unwinding step”) and a step of winding the substrate or a structure including the substrate (also referred to as “winding step”) after any of the steps. (Preferably, all steps or all steps other than the heating step) are performed while transporting the substrate or the structure including the substrate.
The unwinding method in the unwinding step and the winding method in the winding 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.

<Board>
As the substrate used in the method for producing a resin pattern according to the present disclosure, a known substrate may be used, but a substrate having a conductive layer is preferable, and it is more preferable to have a conductive layer on the surface of the substrate.
The substrate may have any layer other than the conductive layer, if necessary.
Examples of the substrate include a resin substrate, a glass substrate, and a semiconductor substrate.
Preferred embodiments of the substrate include, for example, description in paragraph 0140 of WO 2018/155193, the contents of which are incorporated herein.

Examples of the base material constituting the substrate include glass, silicon and a film.
The substrate constituting the substrate is preferably transparent. As used herein, "transparent" means that the transmittance of light having a wavelength of 400 nm to 700 nm is 80% or more.
Further, the refractive index of the substrate constituting the substrate is preferably 1.50 to 1.52.

Examples of the transparent glass substrate include tempered glass represented by Corning's gorilla glass. Further, as the transparent glass substrate, the materials used in JP-A-2010-86684, JP-A-2010-152809 and JP-A-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. Examples of such film substrates include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose and cycloolefin polymers.

As the substrate, a film substrate is preferable when it is manufactured by the roll-to-roll method. Further, when the circuit wiring for the touch panel is manufactured by the roll-to-roll method, it is preferable that the substrate is a sheet-like resin composition.

Examples of the conductive layer included in the substrate include a conductive layer used for general circuit wiring or touch panel wiring.
As the conductive layer, at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer and a conductive polymer layer is preferable from the viewpoint of conductivity and fine wire forming property. A metal layer is more preferable, and a copper layer or a silver layer is further preferable.
The substrate may have one conductive layer alone, or may have two or more conductive layers. When having two or more conductive layers, it is preferable to have conductive layers made of different materials.

Examples of the material of the conductive layer include metals and conductive metal oxides.
Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag and Au.
Examples of the conductive metal oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide) and SiO ₂ .
In addition, in this specification, "conductivity" means that the volume resistivity is less than 1 × ¹⁰⁶ Ωcm. The volume resistivity of the conductive metal oxide is preferably less than 1 × 10 ⁴ Ωcm.

When a resin pattern is produced using a substrate having a plurality of conductive layers, it is preferable that at least one of the plurality of conductive layers contains a conductive metal oxide.
As the conductive layer, an electrode pattern corresponding to the sensor of the visual recognition portion used in the capacitive touch panel or wiring of the peripheral extraction portion is preferable.
Preferred embodiments of the conductive layer include, for example, description in paragraph 0141 of WO 2018/155193, the contents of which are incorporated herein.

As the substrate having a conductive layer, a substrate having at least one of a transparent electrode and a routing wire is preferable. The above-mentioned substrate can be suitably used as a touch panel substrate.
The transparent electrode may function suitably as a touch panel electrode. The transparent electrode is preferably composed of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide), a metal mesh, and a fine metal wire such as silver nanowire.
Examples of the thin metal wire include thin wires such as silver and copper. Of these, silver conductive materials such as silver mesh and silver nanowires are preferable.

Metal is preferable as the material of the routing wiring.
Examples of the metal that is the material of the 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 routing wiring, copper, molybdenum, aluminum, or titanium is preferable, and copper is particularly preferable.

The electrode protective film for a touch panel formed by using the photosensitive transfer material according to the present disclosure directly or other electrodes for the purpose of protecting the electrodes and the like (that is, at least one of the electrodes for the touch panel and the wiring for the touch panel). It is preferably provided so as to cover the layers.

<Exposure process>
It is preferable that the method for manufacturing the resin pattern or the method for manufacturing the laminate includes a step (exposure step) of pattern-exposing the photosensitive resin layer after the above-mentioned bonding step.
Here, the "pattern exposure" refers to an exposure in a form of exposure in a pattern, that is, 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 the pattern exposure is not particularly limited and is appropriately adjusted.

The detailed arrangement and specific size of the pattern in the pattern exposure are not particularly limited. For example, at least a part (preferably) of the pattern so as to improve the display quality of a display device (for example, a touch panel) having an input device having circuit wiring manufactured by an etching method and to reduce the area occupied by the take-out wiring. The electrode pattern and / or the portion of the take-out wiring of the touch panel) preferably contains a thin wire having a width of 20 μm or less, and more preferably contains a thin wire having a width of 10 μm or less.

The light source used for exposure can be appropriately selected and used as long as it is a light source that irradiates the photosensitive resin layer with light having a wavelength that allows exposure (for example, 365 nm or 405 nm). Specific examples thereof include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps and LEDs (Light Emitting Diodes).
The exposure amount is preferably 5 mJ / cm ² to 200 mJ / cm ² , more preferably 10 mJ / cm ² to 100 mJ / cm ² .
Preferred embodiments of the light source, exposure amount and exposure method used for exposure include, for example, paragraphs 0146 to 0147 of International Publication No. 2018/155193, the contents of which are incorporated herein.

In the exposure step, the temporary support may be peeled off from the photosensitive resin layer and then the pattern exposure may be performed. Before the temporary support is peeled off, the pattern is exposed through the temporary support, and then the temporary support is peeled off. You may. When the temporary support is peeled off before exposure, the mask may be exposed in contact with the photosensitive resin layer, or may be exposed in close proximity without contact. When the temporary support is exposed without being peeled off, the mask may be exposed in contact with the temporary support, or may be exposed in close contact with the temporary support without contact. In order to prevent mask contamination due to contact between the photosensitive resin layer and the mask and to avoid the influence of foreign matter adhering to the mask on the exposure, it is preferable to perform pattern exposure without peeling the temporary support. The exposure method may be a contact exposure method in the case of contact exposure, a proximity exposure method in the case of a non-contact exposure method, a lens-based or mirror-based projection exposure method, or a direct exposure method using an exposure laser or the like. It can be selected and used. In the case of lens-based or mirror-based projection exposure, an exposure machine having an appropriate numerical aperture (NA) of the lens can be used according to the required resolving power and depth of focus. In the case of the direct exposure method, drawing may be performed directly on the photosensitive resin layer, or reduced projection exposure may be performed on the photosensitive resin layer via a lens. Further, the exposure may be performed not only in the atmosphere but also under reduced pressure or vacuum, or may be exposed by interposing a liquid such as water between the light source and the photosensitive resin layer.

<Peeling process>
The resin pattern manufacturing method, the laminated body manufacturing method, or the etching method includes a peeling step of peeling off the temporary support between the bonding step and the exposure step, or between the exposure step and the developing step. May be good.
The method for peeling the temporary support is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs 0161 to 0162 of JP2010-072589 can be used.

<Development process>
The method for producing a resin pattern or the method for producing a laminate preferably includes, after the above-mentioned exposure step, a step (development step) of developing the exposed photosensitive resin layer to form a resin pattern.
In the developing process, the photosensitive resin layer in the non-image area and other layers in the non-image area are removed. Further, in the developing step, other layers located on the photosensitive resin layer after exposure in the exposed portion may also be removed in a form of being dissolved or dispersed in the developing solution.

The exposed photosensitive resin layer can be developed by using a developing solution in the developing step.
The developing solution is not particularly limited as long as it can remove the non-image portion of the photosensitive resin layer, and for example, a known developing solution such as the developing solution described in JP-A-5-72724 can be used.
As the developing solution, an alkaline aqueous solution-based developing 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 the alkaline compound that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxy. Do, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide) can be mentioned.
As the developer, the developer described in paragraph 0194 of International Publication No. 2015/093271 is also preferably mentioned. Preferred development methods include, for example, the development method described in paragraph 0195 of International Publication No. 2015/093271.

The development method is not particularly limited, and may be any of paddle development, shower development, shower and spin development, and dip development. Shower development is a development process for removing non-image areas by spraying a developer onto the photosensitive resin layer after exposure with a shower.
After the developing step, it is preferable to spray the cleaning agent with a shower and rub with a brush to remove the developing residue.
The liquid temperature of the developing solution is not particularly limited, but is preferably 20 ° C to 40 ° C.

<Post-exposure process and post-baking process>
The method for producing a resin pattern or the method for producing a laminate includes a step of exposing the resin pattern obtained by the above developing step (post-exposure step) and / or a step of heating (post-baking step). May be good.
When both the post-exposure step and the post-baking step are included, it is preferable to carry out post-baking after post-exposure.

<Etching process>
The etching method preferably includes a step (etching step) of etching the substrate in a region where the resin pattern is not arranged.

In the etching step, the resin pattern formed from the photosensitive resin layer is used as an etching resist, and the conductive layer is etched.
As a method of etching treatment, a known method can be applied, and for example, the method described in paragraphs 0209 to 0210 of JP-A-2017-120435 and paragraph 0048-paragraph 0054 of JP-A-2010-152155. Examples thereof include a wet etching method in which the material is immersed in an etching solution, and a dry etching method such as plasma etching.

As the etching solution used for 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, and the acidic component, ferric chloride, ammonium fluoride and Examples thereof include a mixed aqueous solution with a salt selected from potassium permanganate. The acidic component may be a component in which a plurality of acidic components are combined.
The alkaline etching solution includes an aqueous solution of an alkaline component alone selected from sodium hydroxide, potassium hydroxide, ammonia, an organic amine, and a salt of an organic amine (tetramethylammonium hydroxide, etc.), and an alkaline component and a salt. Examples thereof include a mixed aqueous solution with (potassium permanganate, etc.). The alkaline component may be a component in which a plurality of alkaline components are combined.

<Removal process>
In the etching method, it is preferable to perform a step (removal step) of removing the remaining resin pattern.
The removing step is not particularly limited and can be performed as needed, but it is preferably performed after the etching step.
The method for removing the remaining resin pattern is not particularly limited, and examples thereof include a method for removing by chemical treatment, and a method for removing with a removing liquid is preferable.
As a method for removing the photosensitive resin layer, a substrate having a residual resin pattern is placed in a stirring liquid having a liquid temperature of preferably 30 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C. for 1 minute. A method of immersing for 30 minutes can be mentioned.

Examples of the removing liquid include a removing liquid in which an inorganic alkaline component or an organic alkaline component is dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof. Examples of the inorganic alkaline component include sodium hydroxide and potassium hydroxide. Examples of the organic alkali component include a primary amine compound, a secondary amine compound, a tertiary amine compound and a quaternary ammonium salt compound.
Further, the removing liquid may be used and removed by a known method such as a spray method, a shower method and a paddle method.

<Other processes>
The resin pattern manufacturing method, the laminated body manufacturing method, and the etching method may include any steps (other steps) other than the above-mentioned steps. For example, the following steps can be mentioned, but the steps are not limited to these steps.
Further, examples of the exposure step, the developing step, and other steps applicable to the etching method include the steps described in paragraphs 0035 to 0051 of JP-A-2006-23696.
Further, as other steps, for example, a step of reducing the visible light reflectance described in paragraph 0172 of International Publication No. 2019/022089, a new step on the insulating film described in paragraph 0172 of International Publication No. 2019/022089. Examples thereof include a step of forming a conductive layer, but the process is not limited to these steps.

-Step to reduce visible light reflectance-
The etching method may include a step of reducing the visible light reflectance of a part or all of the plurality of conductive layers of the substrate.
Examples of the treatment for reducing the visible light reflectance include an oxidation treatment. When the substrate has a conductive layer containing copper, the visible light reflectance of the conductive layer can be lowered by oxidizing copper to obtain copper oxide and blackening the conductive layer.
The treatment for reducing the visible light reflectance is described in paragraphs 0017 to 0025 of JP-A-2014-150118 and paragraphs 0041, 0042, 0048 and 0058 of JP-2013-206315. , The contents of these publications are incorporated herein.

-Step of forming an insulating film, step of forming a new conductive layer on the surface of the insulating film-
The etching method preferably includes a step of forming an insulating film on the surface of the circuit wiring and a step of forming a new conductive layer on the surface of the insulating film.
By the above steps, a second electrode pattern insulated from the first electrode pattern can be formed.
The step of forming the insulating film is not particularly limited, and examples thereof include a known method of forming a permanent film. Further, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having an insulating property.
The step of forming the new conductive layer on the insulating film is not particularly limited, and for example, a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.

It is also preferable that the etching method uses a substrate having a plurality of conductive layers on both surfaces of the substrate, and sequentially or simultaneously forms a circuit on the conductive layers formed on both surfaces of the substrate. With such a configuration, it is possible to form a circuit wiring for a touch panel in which a first conductive pattern is formed on one surface of a substrate and a second conductive pattern is formed on the other surface. It is also preferable to form the touch panel circuit wiring having such a configuration from both sides of the substrate by roll-to-roll.

<Use>
The resin pattern manufactured by the method for manufacturing the resin pattern according to the present disclosure, the laminate manufactured by the method for manufacturing the laminate according to the present disclosure, and the circuit wiring manufactured by the etching method according to the present disclosure are various. It can be applied to the device. Examples of the device provided with the laminated body include an input device and the like, and a touch panel is preferable, and a capacitive touch panel is more preferable. Further, the input device can be applied to a display device such as an organic electroluminescence display device and a liquid crystal display device.
When the laminate is applied to a touch panel, the formed resin pattern is preferably used as a protective film for a touch panel electrode or a touch panel wiring. That is, it is preferable that the photosensitive transfer material according to the present disclosure is used for forming an electrode protective film for a touch panel or wiring for a touch panel.

(Manufacturing method of electronic device)
The method for manufacturing the electronic device according to the present disclosure is not particularly limited as long as it is a method using the photosensitive transfer material according to the present disclosure.
The method for manufacturing the electronic device according to the present disclosure includes a step of peeling the protective film from the photosensitive transfer material according to the present disclosure, and the photosensitive transfer material from which the protective film has been peeled off. The step of bringing the outermost layer on the side having the sex resin layer into contact with the substrate having the conductive layer and adhering them, the step of pattern-exposing the photosensitive resin layer via the temporary support, and the exposure of the photosensitive resin layer. It is preferable that the manufactured electronic device has the above-mentioned resin pattern, including the steps of developing the sex resin layer to form a resin pattern in this order.
The electronic device manufactured by the method for manufacturing an electronic device according to the present disclosure preferably has the above resin pattern as a permanent film.

The specific embodiment of each step in the method of manufacturing an electronic device and the embodiment of the order in which each step is performed are as described in the above-mentioned sections of "Manufacturing method of resin pattern" and "Etching method". Yes, and the preferred embodiment is the same.
As the method for manufacturing the electronic device, a known method for manufacturing the electronic device may be referred to, except that the wiring for the electronic device is formed by the above method.
Further, the method for manufacturing an electronic device may include any process (other process) other than those described above.

The electronic device is not particularly limited, but is used in the fields of semiconductor packages, printed circuit boards, various wiring forming applications for sensor boards, touch panels, electromagnetic wave shielding materials, conductive films such as film heaters, liquid crystal sealing materials, micromachines or microelectronics. Structures are preferred.
The resin pattern is preferably used as a permanent film, for example, an interlayer insulating film, a wiring protective film, a wiring protective film having an index matching layer, or the like in the electronic device.
Among them, as the electronic device, a touch panel is particularly preferable.

3 and 4 show an example of a mask pattern used for manufacturing a touch panel.
In the pattern A shown in FIG. 3 and the pattern B shown in FIG. 4, GR is a non-image part (light-shielding part), EX is an image part (exposure part), and DL virtualizes a frame for alignment. It is shown as a target. In the method for manufacturing a touch panel, for example, by exposing the photosensitive resin layer through a mask having the pattern A shown in FIG. 3, a touch panel having a circuit wiring having the pattern A corresponding to EX can be manufactured. .. Specifically, it can be produced by the method shown in FIG. 1 of International Publication No. 2016/190405. In an example of the manufactured touch panel, the central portion (pattern portion where the qualifications are connected) of the exposed portion EX is the portion where the transparent electrode (touch panel electrode) is formed, and the peripheral portion (thin line portion) of the exposed portion EX is. This is the part where the wiring of the peripheral extraction part is formed.

According to the method for manufacturing an electronic device, an electronic device having at least wiring for an electronic device is manufactured, and preferably, for example, a touch panel having at least wiring for a touch panel is manufactured.
The touch panel preferably has a transparent substrate, electrodes, and an insulating layer or a protective layer.
Examples of the detection method on the touch panel include known methods such as a resistance film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method. Above all, the capacitance method is preferable.

The touch panel type includes a so-called in-cell type (for example, those shown in FIGS. 5, 6, 7, and 8 of JP-A-2012-51751), and a so-called on-cell type (for example, JP-A-2013-168125). The one described in FIG. 19 and those described in FIGS. 1 and 5 of JP2012-89102A, OGS (One Glass Solution) type, TOR (Touch-on-Lens) type (for example, JP-A). 2013-54727A (described in FIG. 2), various outsell types (so-called GG, G1 / G2, GFF, GF2, GF1, G1F, etc.) and other configurations (for example, Japanese Patent Application Laid-Open No. 2013-164871). The one shown in FIG. 6).
Examples of the touch panel include those described in paragraph 0229 of JP-A-2017-120435.

The embodiments according to the present disclosure will be described in more detail with reference to examples below. The materials, amounts, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the purpose of the embodiment according to the present disclosure. Therefore, the scope of the embodiments according to the present disclosure is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.

<Preparation of temporary support 1 >>
The temporary support 1 was produced by the following method.

-Preparation of Particle-Containing Layer Forming Composition 1-
Each component was mixed with the formulation shown below to obtain a particle-containing layer forming composition 1. After preparing the particle-containing layer forming composition 1, the film is filtered through a 6 μm filter (F20, manufactured by Mare Filter Systems Co., Ltd.), and subsequently, a membrane is used using a 2x6 radial flow superphobic (manufactured by Polypore Co., Ltd.). I degassed.

-Acrylic polymer (AS-563A, manufactured by Daicel FineChem Co., Ltd., solid content 27.5% by mass): 167 parts-Nonion-based surfactant (Naroacty CL95, manufactured by Sanyo Kasei Kogyo Co., Ltd., solid content 100% by mass) ): 0.7 parts ・ Anionic surfactant (Lapisol A-90, manufactured by Nichiyu Co., Ltd., diluted with water to 1% by mass of solid content): 114.4 parts ・ Carnauba wax dispersion (Cerozol 524, Chukyo) Oil and fat Co., Ltd., solid content 30% by mass): 7 parts ・ Carbodiimide compound (Carbodilite V-02-L2, manufactured by Nisshinbo Co., Ltd., diluted with water to solid content 10% by mass): 20.9 parts ・ Matting agent (Snowtex XL, manufactured by Nissan Chemical Co., Ltd., solid content 40% by mass, average particle size 50 nm): 2.8 parts, water: 690.2 parts

[Extrusion molding]
Pellets of polyethylene terephthalate (PET) using the citrate chelated organic titanium complex described in Japanese Patent No. 5575671 as a polymerization catalyst are dried to a water content of 50 ppm or less, and then put into a hopper of a uniaxial kneading extruder having a diameter of 30 mm. Then, it was melted and extruded at 280 ° C. This melt was passed through a filter (pore diameter 2 μm) and then extruded from a die onto a cooling roll at 25 ° C. to obtain an unstretched film. The extruded melt was brought into close contact with the cooling roll by using an electrostatic application method.

[Stretching, coating]
The unstretched film extruded onto a cooling roll by the above method and solidified was sequentially biaxially stretched by the following method to obtain a temporary support having a polyester film having a thickness of 16 μm and a particle-containing layer having a thickness of 40 nm.

(A) Vertical stretching An unstretched film was passed between two pairs of nip rolls having different peripheral speeds and stretched in the vertical direction (conveying direction). The preheating temperature was 75 ° C., the stretching temperature was 90 ° C., the stretching ratio was 3.4 times, and the stretching speed was 1,300% / sec.

(B) Coating The particle-containing layer forming composition 1 was coated on one side of the vertically stretched film with a bar coater so as to have a thickness of 40 nm after film formation.

(C) Transverse stretching The film subjected to the above longitudinal stretching and coating was laterally stretched under the following conditions using a tenter.
-Cross-stretching conditions-
Preheating temperature: 110 ° C
Stretching temperature: 120 ° C
Stretching ratio: 4.2 times Stretching speed: 50% / sec

[Heat fixation, heat relaxation]
Subsequently, the biaxially stretched film after the longitudinal stretching and the transverse stretching were completed was heat-fixed under the following conditions. Further, after heat fixing, the tenter width was shortened, and the heat was relaxed under the following conditions.
-Heat fixing conditions-
Heat fixing temperature: 227 ° C
Heat fixing time: 6 seconds-heat relaxation conditions-
Heat relaxation temperature: 190 ° C
Heat relaxation rate: 4%

〔Winding〕
After heat fixing and heat relaxation, both ends were trimmed, extruded (knurled) at the ends with a width of 10 mm, and then wound at a tension of 40 kg / m. The width was 1.5 m and the winding length was 6,300 m. The obtained film roll was used as a temporary support 1.
The haze of the obtained temporary support 1 was 0.2. The haze was measured as an all-light haze using a haze meter (NDH2000 manufactured by Nippon Denshoku Kogyo Co., Ltd.).
Further, the heat shrinkage rate by heating at 150 ° C. for 30 minutes is 1.0% on the MD (Machine Direction) side and on the TD (direction orthogonal to the transport direction on the film surface, Transverse Direction) side. It was 0.2%.
The film thickness of the particle-containing layer was 40 nm as measured from a cross-sectional TEM photograph. The average particle size of the particles contained in the particle-containing layer was measured by the above method using an HT-7700 type transmission electron microscope (TEM) manufactured by Hitachi High-Technologies Corporation, and found to be 50 nm.

<Preparation of temporary support 2 >>
It was manufactured in the same manner as the temporary support 1 except that the overall thickness was changed.

<Preparation of Photosensitive Resin Compositions 1 to 5>
After mixing so as to have the composition shown in Table 1 below, photosensitive resin compositions 1 to 5 (solid content concentration: 25% by mass) were prepared by adding methyl ethyl ketone.

The details of the compounds listed in Table 1 are shown below.
BPE-500: 2,2-bis (4- (methacryloxypentethoxy) phenyl) propane, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. BPE-200: 2,2-bis (4- (methacryloxydiethoxy) phenyl) Propane, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. M-270: Polypropylene glycol diacrylate, manufactured by Toa Synthetic Co., Ltd. A-TMPT: Trimethylol propantriacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. SR-454: ethoxylated ( 3) Trimethylol propantriacrylate, Sartmer SR-502: ethoxylated (9) Trimethylol propantriacrylate, Sartmer A-9300-CL1: ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate , Shin-Nakamura Chemical Industry Co., Ltd. B-CIM: Photoradical generator (photopolymerization initiator), Hampford, 2- (2-chlorophenyl) -4,5-diphenylimidazole dimer SB-PI 701: Sensitizer, 4,4'-bis (diethylamino) benzophenone, obtained from Sanyo Trading Co., Ltd. CBT-1: rust preventive, carboxybenzotriazole, TDP-G manufactured by Johoku Chemical Industry Co., Ltd .: polymerization inhibitor, phenothiazine , Kawaguchi Chemical Industry Co., Ltd. Irganox245: Hindered phenol polymerizer, BASF F-552: Fluorosurfactant, Megafuck F552, DIC Co., Ltd.

<Preparation of water-soluble resin composition>
The following components were mixed to prepare a water-soluble resin composition (composition for a water-soluble resin layer). The unit of the amount of each component is a mass part.
Ion-exchanged water: 38.12 parts Methanol (manufactured by Mitsubishi Gas Chemical Company, Inc.): 57.17 parts Clarepoval 4-88LA (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.): 3.22 parts Polyvinylpyrrolidone K-30 (Japan) Catalyst Co., Ltd.): 1.49 parts Megafuck F-444 (fluorine-based surfactant, manufactured by DIC Co., Ltd.): 0.0035 parts

<Preparation of thermoplastic resin composition>
The following components were mixed to prepare a thermoplastic resin composition.
Polymer A-2 (Polymer of benzyl methacrylate / methacrylic acid = 83/17 (mass ratio), acid value 111 mgKOH / g, glass transition temperature 75 ° C.) Solid content concentration 40.0%): 15.0 parts Dye B-1 (the following compound): 0.1 part Photoacid generator C-1 (the following compound): 0.1 part Plastic agent D-3 (NK ester A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) : 2.2 parts Polymer D-4 (8UX-015A, manufactured by Taisei Fine Chemicals Co., Ltd.): 1.1 parts Polymer D-5 (Aronix TO-2349, manufactured by Toa Synthetic Co., Ltd.): 0.5 parts Megafuck F-551 (Fluorine-based surfactant, manufactured by DIC Co., Ltd.): 0.02 part Phenothiazine: 0.03 part CBT-1 (rust preventive, carboxybenzotriazole, manufactured by Johoku Chemical Industry Co., Ltd.): 0.03 part Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.): 63.0 parts propylene glycol monomethyl ether (manufactured by Sanwa Chemical Industry Co., Ltd.): 9.0 parts propylene glycol monomethyl ether acetate (manufactured by Showa Denko Co., Ltd.) ): 9.0 copies

The dye B-1 is shown below.

The photoacid generator C-1 is shown below.

(Examples 1 to 7 and Comparative Examples 1 and 3)
<Preparation of photosensitive transfer material>
The photosensitive resin composition described in the coating layers shown in Tables 5 and 6 is applied onto the temporary support shown in Table 5 using a slit-shaped nozzle to have a coating width of 1.0 m and a layer shown in Table 6. It was applied so as to be thick and passed through a drying zone at 80 ° C. for 40 seconds to form a photosensitive resin layer. The protective film shown in Table 5 was crimped onto this to prepare a photosensitive transfer material, which was wound into a roll form.

(Examples 8 to 12 and Comparative Example 2)
<Preparation of photosensitive transfer material>
The thermoplastic resin composition shown in Table 6 is applied onto the temporary support shown in Table 5 using a slit-shaped nozzle so that the coating layer is configured as shown in Tables 5 and 6, and the coating width is 1. It was applied so as to have a layer thickness of 0.0 m and the layer thickness shown in Table 6, and passed through a drying zone at 80 ° C. for 40 seconds to form a thermoplastic resin layer. Then, the water-soluble resin composition shown in Table 6 is applied onto the thermoplastic resin layer using a slit-shaped nozzle so that the coating width is 1.0 m and the layer thickness shown in Table 6 is 80 ° C. The water-soluble resin layer was formed by passing through the drying zone of the above for 40 seconds. Further, the photosensitive resin composition shown in Table 6 is applied onto the water-soluble resin layer using a slit-shaped nozzle so that the coating width is 1.0 m and the layer thickness is as shown in Table 6, and the temperature is 80 ° C. A photosensitive resin layer was formed by passing through the drying zone for 40 seconds. The protective film shown in Table 5 was crimped onto this to prepare a photosensitive transfer material, which was wound into a roll form.

(Examples 13 to 28)
<Preparation of photosensitive resin composition>
The photosensitive resin compositions A-1 to A-10 were prepared so as to have the compositions shown in Table 2 below. The numerical values in each component column of Table 2 represent parts by mass.

Details of the compounds other than those mentioned above shown in Table 2 are shown below.
Compound B and Compound C: The following compounds

<Preparation of 36.3% by mass solid content solution of alkali-soluble resin P-1>
A 36.3% by mass solution of the polymer P-1 having the following structure (solvent: propylene glycol monomethyl ether acetate) was used. In P-1, the numerical value at the lower right of each structural unit indicates the content ratio (mol%) of each structural unit.
A 36.3% by mass solution of P-1 solid content was prepared by the polymerization step and the addition step shown below.

-Polymerization process-
Propylene glycol monomethyl ether acetate (manufactured by Sanwa Chemical Industry Co., Ltd., trade name PGM-Ac) (60 g), propylene glycol monomethyl ether (manufactured by Sanwa Chemical Industry Co., Ltd., trade name PGM) (240 g) in a 2,000 mL flask. Was introduced. The obtained liquid was heated to 90 ° C. while stirring at a stirring speed of 250 rpm (revolutions per minute).
As the preparation of the dropping liquid (1), 107.1 g of methacrylic acid (manufactured by Mitsubishi Rayon Co., Ltd., trade name Acryester M), methyl methacrylate (manufactured by Mitsubishi Gas Chemical Company, trade name MMA) (5.46 g). , And cyclohexyl methacrylate (manufactured by Mitsubishi Gas Chemical Company, Inc., trade name CHMA) (231.42 g) were mixed and diluted with PGM-Ac (60 g) to obtain a dropping liquid (1).
To prepare the dropping solution (2), dimethyl 2,2'-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd., trade name V-601) (9.637 g) was added to PGM-Ac. By dissolving with (136.56 g), a dropping liquid (2) was obtained.
The dropping liquid (1) and the dropping liquid (2) are simultaneously added dropwise to the above-mentioned 2,000 mL flask (specifically, a 2,000 mL flask containing a liquid heated to 90 ° C.) over 3 hours. did.
Next, the container of the dropping liquid (1) was washed with PGM-Ac (12 g), and the washing liquid was dropped into the 2,000 mL flask. Next, the container of the dropping liquid (2) was washed with PGM-Ac (6 g), and the washing liquid was dropped into the 2000 mL flask. During these droppings, the reaction solution in the 2,000 mL flask was kept at 90 ° C. and stirred at a stirring speed of 250 rpm. Further, as a post-reaction, the mixture was stirred at 90 ° C. for 1 hour.
V-601 (2.401 g) was added to the reaction solution after the post-reaction as the first additional addition of the initiator. Further, the container of V-601 was washed with PGM-Ac (6 g), and the washing liquid was introduced into the reaction liquid. Then, the mixture was stirred at 90 ° C. for 1 hour.
Next, V-601 (2.401 g) was added to the reaction solution as the second additional addition of the initiator. Further, the container of V-601 was washed with PGM-Ac (6 g), and the washing liquid was introduced into the reaction liquid. Then, the mixture was stirred at 90 ° C. for 1 hour.
Next, V-601 (2.401 g) was added to the reaction solution as the third additional addition of the initiator. Further, the container of V-601 was washed with PGM-Ac (6 g), and the washing liquid was introduced into the reaction liquid. Then, the mixture was stirred at 90 ° C. for 3 hours.

-Additional process-
After stirring at 90 ° C. for 3 hours, PGM-Ac (178.66 g) was introduced into the reaction solution. Next, tetraethylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (1.8 g) and hydroquinone monomethyl ether (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (0.8 g) were added to the reaction solution. Further, each container was washed with PGM-Ac (6 g), and the washing liquid was introduced into the reaction liquid. Then, the temperature of the reaction solution was raised to 100 ° C.
Next, glycidyl methacrylate (manufactured by NOF CORPORATION, trade name Blemmer G) (76.03 g) was added dropwise to the reaction solution over 1 hour. The container of Blemmer G was washed with PGM-Ac (6 g), and the washing liquid was introduced into the reaction liquid. Then, as an addition reaction, the mixture was stirred at 100 ° C. for 6 hours.
Next, the reaction solution was cooled and filtered through a mesh filter (100 mesh) for removing dust to obtain a solution of polymer D (1,158 g) (solid content concentration: 36.3% by mass). The obtained polymer P-1 had a weight average molecular weight of 27,000, a number average molecular weight of 15,000, and an acid value of 95 mgKOH / g.

P-1 (Hereinafter, the molar ratio of the constituent repeating units in the formula was 51.5: 2: 26.5: 20 in order from the constituent repeating unit on the left side).

<Preparation of 36.5% by mass solid content solution of alkali-soluble resin P-2>
82.4 g of propylene glycol monomethyl ether was placed in a flask and heated to 90 ° C. under a nitrogen stream. A solution in which 38.4 g of styrene, 30.1 g of dicyclopentanyl methacrylate and 34.0 g of methacrylic acid are dissolved in 20 g of propylene glycol monomethyl ether in this solution, and a polymerization initiator V-601 (Fuji Film Wako Pure Chemical Industries, Ltd.) )) A solution prepared by dissolving 5.4 g in 43.6 g of propylene glycol monomethyl ether acetate was simultaneously added dropwise over 3 hours. After completion of the dropping, 0.75 g of V-601 was added 3 times every 1 hour. After that, it was reacted for another 3 hours. Then, it was diluted with 58.4 g of propylene glycol monomethyl ether acetate and 11.7 g of propylene glycol monomethyl ether. The temperature of the reaction solution was raised to 100 ° C. under an air flow, and 0.53 g of tetraethylammonium bromide and 0.26 g of p-methoxyphenol were added. To this, 25.5 g of glycidyl methacrylate (NOF Corporation Blemmer GH) was added dropwise over 20 minutes. This was reacted at 100 ° C. for 7 hours to obtain a solution of the polymer P-2. The solid content concentration of the obtained solution was 36.5% by mass. The weight average molecular weight in terms of standard polystyrene in GPC was 17,000, the dispersity was 2.7, and the acid value of the polymer was 95 mgKOH / g. The amount of residual monomer measured by gas chromatography was less than 0.1% by mass with respect to the polymer solid content in any of the monomers.

P-2 (Hereinafter, the molar ratio of the constituent repeating units in the formula was 41.0: 15.2: 23.9: 19.9 in order from the left constituent repeating unit.)

<Preparation of 36.2% by mass solid content solution of alkali-soluble resin P-3>
113.5 g of propylene glycol monomethyl ether was placed in a flask and heated to 90 ° C. under a nitrogen stream. A solution in which 172 g of styrene, 4.7 g of methyl methacrylate and 112.1 g of methacrylic acid are dissolved in 30 g of propylene glycol monomethyl ether in this solution, and a polymerization initiator V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 27. A solution prepared by dissolving 0.6 g in 57.7 g of propylene glycol monomethyl ether was simultaneously added dropwise over 3 hours. After completion of the dropping, 2.5 g of V-601 was added 3 times every 1 hour. After that, it was reacted for another 3 hours. Then, it was diluted with 160.7 g of propylene glycol monomethyl ether acetate and 233.3 g of propylene glycol monomethyl ether. The temperature of the reaction solution was raised to 100 ° C. under an air flow, and 1.8 g of tetraethylammonium bromide and 0.86 g of p-methoxyphenol were added. 71.9 g of glycidyl methacrylate (Blemmer G manufactured by NOF CORPORATION) was added dropwise to this over 20 minutes. This was reacted at 100 ° C. for 7 hours to obtain a solution of resin P-3. The solid content concentration of the obtained solution was 36.2%. The weight average molecular weight in terms of standard polystyrene in GPC was 18,000, the dispersity was 2.3, and the acid value of the polymer was 124 mgKOH / g. The amount of residual monomer measured by gas chromatography was less than 0.1% by mass with respect to the polymer solid content in any of the monomers.

P-3 (Hereinafter, the molar ratio of the constituent repeating units in the formula was 55.1: 26.5: 1.6: 16.8 in order from the constituent repeating unit on the left side.)

<Preparation of 36.2% by mass solid content solution of alkali-soluble resin P-4>
In the synthesis of P-3, a 36.2% by mass solid content solution of P-4 (solvent: propylene glycol monomethyl ether acetate) was prepared by changing the type and amount of the monomer. The obtained polymer P-4 had a weight average molecular weight of 18,000, a dispersity of 2.3, and an acid value of 124 mgKOH / g.

P-4 (Hereinafter, the molar ratio of the constituent repeating units in the formula was 55.1: 24.6: 1.6: 17.0: 1.7 in order from the left constituent repeating unit.)

<Preparation of composition for forming a refractive index adjusting layer>
Next, the compositions B-1 to B-4 for forming the refractive index adjusting layer were prepared with the compositions shown in Table 3 below. The numerical value of each component in Table 3 represents "part by mass".

Polymer A in Table 3 was synthesized and prepared as follows.
1-Methylpropanol (manufactured by Tokyo Chemical Industry Co., Ltd.) (270.0 g) was introduced into a 1 L three-necked flask, and the temperature was raised to 70 ° C. under a nitrogen stream while stirring. On the other hand, allyl methacrylate (45.6 g) (manufactured by Wako Pure Chemical Industries, Ltd.) and methacrylic acid (14.4 g) (manufactured by Wako Pure Chemical Industries, Ltd.) 1-methoxypropanol (Tokyo Chemical Industry Co., Ltd.) Dissolve in (270.0 g) (manufactured by Fuji Film Co., Ltd.), and further dissolve 3.94 g of V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a dropping solution, and put it in a flask for 2.5 hours. The dropping liquid was dropped over. The reaction was carried out while maintaining the stirred state for 2.0 hours.
Then, the temperature was returned to room temperature, and the mixture was added dropwise to ion-exchanged water (2.7 L) in a stirred state, and reprecipitation was carried out to obtain a suspension. Filtration was performed by introducing a turbid solution in Nuche with a filter paper, and the filtered material was further washed with ion-exchanged water to obtain a wet powder. It was dried by blowing air at 45 ° C., and it was confirmed that the amount became constant, and polymer A was obtained as a powder in a yield of 70%.
The ratio of methacrylic acid / allyl methacrylate of the obtained polymer A was 76/24 (mass%). The weight average molecular weight Mw was 38,000.

<Preparation of coating layers 11 to 26>
Using a slit-shaped nozzle on a temporary support of a polyethylene terephthalate film (Lumirror 16QS62, manufactured by Toray Industries, Inc.) with a thickness of 16 μm, the coating amount was adjusted to the coating amount at which the film thickness after drying becomes the thickness shown in Table 4. After adjustment, any one of the photosensitive resin compositions A-1 to A-10 shown in Table 4 was applied to form a photosensitive resin layer.
After volatilizing the solvent in a drying zone at 100 ° C., among the compositions B-1 to B-4 for forming a refractive index adjusting layer shown in Table 4, the combinations shown in Table 4 are used by using a slit-shaped nozzle. Using at least one type, adjust the coating amount to an amount such that the film thickness after drying becomes the film thickness shown in Table 4, apply it on the photosensitive resin layer layer, and then dry it at a drying temperature of 80 ° C. The refractive index adjustment layer was formed. A protective film (Lumirror 16QS62, manufactured by Toray Industries, Inc.) was pressure-bonded onto the refractive index adjusting layer to prepare coating layers 11 to 26.

<Manufacturing of PET substrate with copper layer>
A copper layer having a thickness of 200 nm was prepared on a polyethylene terephthalate (PET) film having a thickness of 100 μm by a sputtering method, and a PET substrate with a copper layer was prepared.

〔evaluation〕
<Measurement of surface energy>
The surface energy (unit: mN / m) of the temporary support or the protective film is calculated by the following method.
On the measurement surface of the temporary support or protective film, the contact angles of the two liquids, pure water and methylene iodide, were measured in an atmosphere of room temperature of 23 ° C and relative humidity of 50% to 60%. Three points were measured by (Kyowa Interface Science Co., Ltd.). The average value of the measured values obtained for each liquid was taken as the contact angle of each of the two types of liquids. Using the contact angles of the two obtained liquids, the surface energy γ (= γ ^d) , which is the sum of the dispersion force γ ^d , the polarity force γ ^p , and the dispersion force and the polarity force, is obtained by the geometric mean method based on Owns-Wendt. + Gamma ^p ) was calculated.
A specific calculation method is shown. The meaning of each symbol is shown below. When γ _SL is the tension at the interface between the solid and the liquid, the mathematical formula (1) holds.
γ _SL : Surface free energy of film surface and known liquid γ _S : Surface free energy of known liquid γ _L : Surface free energy of known liquid γ _S ^d : Dispersive force component of surface free energy of film surface γ _S ^p : Polarity component of surface free energy of film surface γ _L ^d : Dispersive force component of surface free energy of known liquid γ _L ^p : Polar force component of surface free energy of known liquid γ _SL = γ _S + γ _L -2 ( γ _S ^d・ γ _L ^d ) ^1/2 -2 (γ _S ^p・ γ _L ^p ) ^1/2・・・ Equation (1)
Further, the state when the smooth solid surface and the droplet are in contact with each other at the contact angle (θ) is expressed by the following equation (Young's equation).
γ _S = γ _SL + γ _L cos θ ・・・ Equation (2)
By combining these mathematical formulas (1) and (2), the following equation is obtained.
(Γ _s ^d・ γ _L ^d ) ^1/2 + (γ _s ^p・ γ _L ^p ) ^1/2 = γ _L (1 + cos θ) / 2 ... Equation (3)
Actually, the contact angle (θ) of two kinds of liquids, pure water and methylene iodide, the surface energy γ _L of the known liquid, and each component (γ _L ^d , γ _L ^p ) are calculated in the formula (3). Substituted and solved the simultaneous equations.
As a result, the surface energy (γ _S ) of the film was calculated. The values of known liquids were as follows.
Pure water: γ _L = 72.8 mN / m, γ _L ^d = 21.8 mN / m, γ _L ^p = 51.0 mN / m
Methylene iodide: γ _L = 50.8 mN / m, γ _L ^d = 49.5 mN / m, γ _L ^p = 1.3 mN / m

<Defect evaluation>
The protective film was peeled off from the prepared photosensitive transfer material, and laminated on a PET substrate with a copper layer under laminating conditions of a laminating roll temperature of 100 ° C., a linear pressure of 0.6 MPa, and a linear velocity (laminating rate) of 4.0 m / min. The line-and-space pattern (Duty ratio 1: 1) mask and temporary support were brought into contact with each other, exposed to an ultra-high pressure mercury lamp, left at 23 ° C. for 3 hours, and then developed. Development was carried out by shower development for 40 seconds using a 1.0 mass% sodium carbonate aqueous solution at 28 ° C. A line-and-space pattern having a line width of 9 μm was formed by the above method, and the exposure amount at which the ratio of the line width to the space width was 1: 1 was determined. Then, shower etching was performed for 60 seconds using MEC Bright (MEC) to prepare a copper pattern wiring. The obtained copper pattern wiring was observed with an optical microscope. A total of 10 shots were observed, with an observation area of 0.26 mm × 0.20 mm as one shot. If there is a disconnection (open) or a connection (short circuit) between wirings even at one point in one shot, the number of defective shots in 10 shots is defined as a wiring defect and evaluated. Wiring defects in the copper pattern are based on defects in the resin pattern. It is preferably A or B.
A: The number of defective shots of the copper pattern is 0 to 1, and it is not visible or hardly visible.
B: The number of defective shots of the copper pattern is 2 to 3, and it is hardly visible.
C: The number of defective shots of the copper pattern is 4 to 5, and less than half of them are not visible.
D: The number of defective shots of the copper pattern is 6 or more, and more than half is visually recognized.

<Resolution evaluation>
The resolution was evaluated using the copper pattern wiring produced in the defect evaluation. Using a mask in which the width of the line-and-space pattern was changed, the minimum width at which the resist pattern after development could be formed was defined as the minimum resolution and evaluated. Tables 5 and 6 show the minimum resolution (μm) as the evaluation result of the resolution.

<Measurement of peeling force (adhesion evaluation)>
The protective film was peeled off from the produced photosensitive transfer material, and laminated on the PET substrate with a copper layer under laminating conditions of a laminating roll temperature of 100 ° C., a linear pressure of 0.6 MPa, and a linear velocity (laminating rate) of 1.0 m / min. Next, after attaching a tape (PINTACK manufactured by Nitto Denko Corporation) to the surface of the temporary support, a laminate having at least the temporary support and the photosensitive resin layer on a PET substrate with a copper layer is 70 mm × 10 mm. A sample was prepared by cutting into. The PET substrate side of the above sample was fixed on the reference table.
Using a tensile compression tester (SV-55, manufactured by Imada Seisakusho Co., Ltd.), pull the tape in the direction of 180 degrees at 5.5 mm / sec to obtain a photosensitive resin layer or a thermoplastic resin layer and a temporary support. The force required for peeling (peeling force) was measured.

<Measurement of Arithmetic Mean Roughness Ra>
Using a three-dimensional optical profiler (New View7300, manufactured by Zygo), the surface of the temporary support or the protective film was measured under the following conditions, and the surface profile of the film was obtained.
As the measurement / analysis software, Microscope Application of MetroPro ver8.3.2 was used. Next, the Surface Map screen was displayed with the above analysis software, and histogram data was obtained in the Surface Map screen. From the obtained histogram data, the arithmetic mean roughness was calculated, and the Ra value on the surface of the temporary support or the protective film was obtained.
When the temporary support or the protective film is attached to the photosensitive resin layer or the like, the temporary support or the protective film may be peeled off from the photosensitive resin layer, and the Ra value of the surface on the peeled side may be measured.

<Measurement of haze value>
The haze value was measured using a haze meter (NDH-2000, manufactured by Nippon Denshoku Kogyo Co., Ltd.) by a method according to JIS K 7105: 1981.

Details of the abbreviations shown in Table 5 other than those described above are as follows.
Temporary support 3: Biaxially stretched polyethylene terephthalate film, thickness 16 μm, Toray Industries, Inc. Lumirror 16QS62
Temporary support 4: Biaxially stretched polypropylene film, thickness 12 μm, Alfan E501 manufactured by Oji F-Tex Co., Ltd.
Temporary support 5: Biaxially stretched polyethylene terephthalate film, thickness 16 μm, Toray Industries, Inc. Lumirror P60
In addition, the details of the physical property values of each temporary support and the protective film used in the examples are shown below. The transport surface (outside) in Table 8 is the surface opposite to the photosensitive resin layer side of the temporary support or the protective film, and the coated surface (inside) is the photosensitive resin in the temporary support or the protective film. This is the surface on the layer side.

As shown in Tables 5 and 7, the photosensitive transfer materials of Examples 1 to 28 were compared with the photosensitive transfer materials of Comparative Examples 1 to 3, and the photosensitive resin layer was exposed via a temporary support. Even so, a resin pattern with few defects can be obtained.
Further, the photosensitive transfer materials of Examples 1 to 28 are also excellent in resolution and adhesion between the photosensitive resin layer or the thermoplastic resin layer and the temporary support.

(Example 101)
On a 100 μm thick PET substrate, ITO is formed into a film with a thickness of 150 nm by sputtering as a second conductive layer, and copper is formed into a film with a thickness of 200 nm as a conductive layer of the first layer by a vacuum vapor deposition method. This was used as a circuit forming substrate.
The photosensitive transfer material obtained in Example 10 was laminated on the copper layer (laminol temperature 120 ° C., linear pressure 0.8 MPa, linear velocity 1.0 m / min.). The laminated laminate was exposed to a contact pattern using a photomask provided with the pattern A shown in FIG. 3, which had a structure in which the conductive layer pads were connected in one direction without peeling off the temporary support. Then, the temporary support was peeled off, developed and washed with water to obtain pattern A. Next, the copper layer is etched with a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Ltd.), and then the ITO layer is etched with an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.). A substrate in which copper and ITO were both drawn in pattern A was obtained.
The remaining photosensitive resin layer (pattern A) was peeled off using a stripping solution (KP-301 manufactured by Kanto Chemical Co., Ltd.), and the photosensitive transfer material obtained in Example 10 was again laminated on the copper layer (Kanto Kagaku Co., Ltd. KP-301). Lamilol temperature 120 ° C., linear pressure 0.8 MPa, linear velocity 1.0 m / min.).
Next, the pattern was exposed using the photomask of pattern B shown in FIG. 4 in a state of alignment, and was developed and washed with water. Then, the copper layer was etched with Cu-02, and the remaining photosensitive resin layer (pattern B) was peeled off with a stripping solution (KP-301 manufactured by Kanto Chemical Co., Ltd.) to obtain a circuit wiring board. ..
When the obtained circuit board was observed with a microscope, there was no peeling or chipping, and the pattern was clean.
In the pattern A shown in FIG. 3, GR, which is a gray part, is a light-shielding part, EX is an exposed part, and DL, which is a dotted line part, virtually shows a frame for alignment.
Further, in the pattern B shown in FIG. 4, as in FIG. 3, GR, which is a gray portion, is a light-shielding portion, EX is an exposed portion, and DL, which is a dotted line portion, virtually indicates a frame for alignment alignment. It is a thing.

(Explanation of code)
1,11: Temporary support, 2,12: Transfer layer, 3,17: Photosensitive resin layer, 5: Refractive index adjustment layer, 13: Thermoplastic resin layer, 15: Water-soluble resin layer, 10,20: Photosensitive Sex transfer material, GR: light-shielding part (non-image part), EX: exposed part (image part), DL: frame for alignment alignment.

The disclosure of Japanese Patent Application No. 2020-1583839 filed on September 14, 2020 and the disclosure of Japanese Patent Application No. 2020-207962 filed on December 15, 2020 are described herein in their entirety. Incorporated into the book. All documents, patent applications, and technical standards described herein are to the same extent as specifically and individually stated that the individual documents, patent applications, and technical standards are incorporated by reference. Incorporated herein by reference.

Claims

It has a temporary support, a photosensitive resin layer, and a protective film in this order.
The surface energy of the surface of the temporary support opposite to the photosensitive resin layer side is γb (mN / m), and the surface energy of the surface of the protective film opposite to the photosensitive resin layer side is γc. A photosensitive transfer material that satisfies γb ≧ γc when (mN / m).
The photosensitive transfer material according to claim 1, wherein the temporary support has a thickness of 20 μm or less.
The photosensitive transfer material according to claim 1 or 2, wherein the thickness of the photosensitive resin layer is 10 μm or less.
The photosensitive transfer material according to any one of claims 1 to 3, further comprising another layer between the temporary support and the photosensitive resin layer.
The photosensitive transfer material according to any one of claims 1 to 4, wherein the haze value of the temporary support is less than 1.0%.
The photosensitive transfer material according to any one of claims 1 to 5, wherein the temporary support has a peeling force of 0.5 mN / mm or more.
The photosensitive transfer material according to any one of claims 1 to 6, wherein the arithmetic average roughness Ra value of the surface of the temporary support opposite to the photosensitive resin layer side is 50 nm or less. ..
The photosensitive transfer material according to any one of claims 1 to 7, wherein the arithmetic average roughness Ra value of the surface of the protective film opposite to the photosensitive resin layer side is 50 nm or less.
The photosensitive transfer material according to any one of claims 1 to 8, wherein the value of γb-γc is more than 0 mN / m and 50 mN / m or less.
The photosensitive transfer material according to any one of claims 1 to 9, wherein the value of γb-γc is 2 mN / m or more and 30 mN / m or less.
The photosensitive transfer material according to any one of claims 1 to 10, wherein the value of γb-γc is 7 mN / m or more and 20 mN / m or less.
The photosensitive transfer material according to any one of claims 1 to 11, which is a roll-shaped photosensitive transfer material.
The step of peeling the protective film from the photosensitive transfer material according to any one of claims 1 to 12.
A step of bringing the outermost layer of the photosensitive transfer material from which the protective film has been peeled off on the side having the photosensitive resin layer into contact with the substrate having the conductive layer and adhering them to the temporary support.
A step of pattern-exposing the photosensitive resin layer via the temporary support, and
A method for producing a resin pattern, which comprises a step of developing the exposed photosensitive resin layer to form a resin pattern, and the process of forming the resin pattern.
In a laminated body in which the substrate, the conductive layer, and the resin pattern produced by the method for producing a resin pattern according to claim 13 are laminated in this order, the conductivity in a region where the resin pattern is not arranged. An etching method including a step of etching a sex layer.
The step of peeling the protective film from the photosensitive transfer material according to any one of claims 1 to 12.
A step of bringing the outermost layer of the photosensitive transfer material from which the protective film has been peeled off on the side having the photosensitive resin layer into contact with the substrate having the conductive layer and adhering them to the temporary support.
A step of pattern-exposing the photosensitive resin layer via the temporary support, and
The steps of developing the exposed photosensitive resin layer to form a resin pattern are included in this order.
A method for manufacturing an electronic device in which the manufactured electronic device has the resin pattern.