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

Abstract

The present invention provides a photosensitive transfer material, a method for manufacturing a resin pattern using the photosensitive transfer material, an etching method, and a method for manufacturing an electronic device. The photosensitive transfer material sequentially comprises a temporary support, a photosensitive resin layer, and a protective film. When the surface energy of the surface of the temporary support opposite to the photosensitive resin layer is set to γb (mN / m), and the surface energy of the surface of the protective film opposite to the photosensitive resin layer is set to γc (mN / m), γb≥γc is satisfied.

Description

Technical Field

[0001] The present invention relates to a photosensitive transfer material, a method for manufacturing a resin pattern, an etching method, and a method for manufacturing an electronic device. Background Art

[0002] In a display device (such as an organic electroluminescent (EL) display device and a liquid crystal display device) having a touch panel such as an electrostatic capacitive input device, a conductive layer pattern including an electrode pattern of a sensor corresponding to a visible portion, a peripheral wiring portion, and wiring for extracting the wiring portion is provided inside the touch panel.

[0003] Generally, when forming a patterned layer, the number of steps required to obtain a desired pattern shape is small. Therefore, a method of exposing a layer of a photosensitive resin composition formed on an arbitrary substrate using a photosensitive transfer material through a mask having a desired pattern and then developing the layer is widely used.

[0004] Furthermore, as a conventional photosensitive transfer material, the photosensitive transfer material described in Japanese Patent Application Laid-Open No. 2019-128445 is known. Patent Document 1 describes a photosensitive transfer material comprising a photosensitive layer, an adhesive layer, and a temporary support on a protective film in this order, wherein the photosensitive layer contains particles, the photosensitive layer is in contact with the adhesive layer, the photosensitive layer and the adhesive layer are peelable, and the surface of the photosensitive layer after peeling has an uneven surface formed by the particles. Summary of the Invention

[0005] Technical issues to be solved by the invention

[0006] An object of one embodiment of the present invention is to provide a photosensitive transfer material capable of obtaining a resin pattern with few defects even when a photosensitive resin layer is exposed via a temporary support.

[0007] Furthermore, another embodiment of the present invention aims to provide a method for manufacturing a resin pattern, an etching method, and a method for manufacturing an electronic device using the photosensitive transfer material.

[0008] Means for solving technical problems

[0009] The present invention includes the following aspects.

[0010] <1> A photosensitive transfer material comprising, in sequence, a temporary support, a photosensitive resin layer, and a protective film, wherein, when the surface energy of the surface of the temporary support opposite to the photosensitive resin layer is set to γb (mN / m), and the surface energy of the surface of the protective film opposite to the photosensitive resin layer is set to γc (mN / m), γb ≥ γc is satisfied.

[0011] <2> The photosensitive transfer material according to <1>, wherein

[0012] The temporary support has a thickness of 20 μm or less.

[0013] <3> The photosensitive transfer material according to <1> or <2>, wherein

[0014] The photosensitive resin layer has a thickness of 10 μm or less.

[0015] <4> The photosensitive transfer material according to any one of <1> to <3>, further comprising another layer between the temporary support and the photosensitive resin layer.

[0016] <5> The photosensitive transfer material according to any one of <1> to <4>, wherein

[0017] The temporary support has a haze value of less than 1.0%.

[0018] <6> The photosensitive transfer material according to any one of <1> to <5>, wherein

[0019] The temporary support has a peeling force of 0.5 mN / mm or more.

[0020] <7> The photosensitive transfer material according to any one of <1> to <6>, wherein

[0021] The value of the arithmetic mean roughness Ra of the surface of the temporary support on the side opposite to the photosensitive resin layer side is 50 nm or less.

[0022] <8> The photosensitive transfer material according to any one of <1> to <7>, wherein

[0023] The value of the arithmetic mean roughness Ra of the surface of the protective film on the side opposite to the photosensitive resin layer side is 50 hm or less.

[0024] <9> The photosensitive transfer material according to any one of <1> to <8>, wherein

[0025] The value of γb-γc exceeds 0 mN / m and is 50 mN / m or less.

[0026] <10> The photosensitive transfer material according to any one of <1> to <9>, wherein

[0027] The value of γb-γc is 2 mN / m or more and 30 mN / m or less.

[0028] <11> The photosensitive transfer material according to any one of <1> to <10>, wherein

[0029] The value of γb-γc is 7 mN / m or more and 20 mN / m or less.

[0030] <12> The photosensitive transfer material according to any one of <1> to <11>, which is a roll-shaped photosensitive transfer material.

[0031] <13> A method for manufacturing a resin pattern, comprising:

[0032] a step of peeling the protective film from the photosensitive transfer material according to any one of <1> to <12>;

[0033] a step of bringing the outermost layer of the photosensitive transfer material from which the protective film has been peeled off, the outermost layer having the photosensitive resin layer facing the temporary support, into contact with and laminating the substrate having the conductive layer;

[0034] a step of pattern-exposing the photosensitive resin layer via the temporary support; and

[0035] A step of developing the exposed photosensitive resin layer to form a resin pattern.

[0036] <14> An etching method comprising the following steps:

[0037] In a laminated body in which the substrate, the conductive layer, and the resin pattern produced by the method for producing a resin pattern described in <13> are sequentially laminated, the conductive layer in a region where the resin pattern is not provided is subjected to etching.

[0038] <15> A method for manufacturing an electronic device, comprising:

[0039] a step of peeling the protective film from the photosensitive transfer material according to any one of <1> to <12>;

[0040] a step of bringing the outermost layer of the photosensitive transfer material from which the protective film has been peeled off, the outermost layer having the photosensitive resin layer facing the temporary support, into contact with and laminating the substrate having the conductive layer;

[0041] a step of pattern-exposing the photosensitive resin layer via the temporary support; and

[0042] a step of developing the exposed photosensitive resin layer to form a resin pattern,

[0043] The manufactured electronic device has the above-mentioned resin pattern.

[0044] Effects of the Invention

[0045] According to one embodiment of the present invention, a photosensitive transfer material can be provided that can obtain a resin pattern with few defects even when a photosensitive resin layer is exposed via a temporary support.

[0046] Furthermore, according to another embodiment of the present invention, a method for manufacturing a resin pattern, an etching method, and a method for manufacturing an electronic device using the photosensitive transfer material can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Figure 1 This is a schematic diagram showing an example of the structure of the photosensitive transfer material according to the first embodiment.

[0048] Figure 2 This is a schematic diagram showing an example of the structure of a photosensitive transfer material according to the second embodiment.

[0049] Figure 3 This is a schematic plan view showing pattern A.

[0050] Figure 4 This is a schematic plan view showing pattern B. DETAILED DESCRIPTION

[0051] Hereinafter, the content of the present invention will be described. In addition, the description will be made with reference to the drawings, but reference numerals may be omitted in some cases.

[0052] Furthermore, in this specification, a numerical range expressed using “to” means a range including the numerical values ​​described before and after “to” as the lower limit and the upper limit.

[0053] In this specification, “(meth)acrylic acid” means either or both of acrylic acid and methacrylic acid, “(meth)acrylate” means either or both of acrylate and methacrylate, and “(meth)acryloyl” means either or both of acryloyl and methacryloyl.

[0054] In this specification, when a plurality of substances corresponding to each component are present in the composition, the amount of each component in the composition refers to the total amount of the corresponding plurality of substances present in the composition unless otherwise specified.

[0055] In this specification, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes as long as the intended purpose of the process can be achieved.

[0056] In the notation of groups (atomic groups) in this specification, the notation "unsubstituted" and "unsubstituted" include groups without substitution and groups with substitution. For example, "alkyl" includes not only alkyl groups without substitution (unsubstituted alkyl groups) but also alkyl groups with substitution (substituted alkyl groups).

[0057] In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, electron beams, and other activating light (active energy rays).

[0058] Furthermore, the chemical structural formulas in this specification may be described as simplified structural formulas in which hydrogen atoms are omitted.

[0059] In this specification, "mass %" and "weight %" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning.

[0060] Furthermore, in this specification, a combination of two or more preferred aspects is a more preferred aspect.

[0061] Unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) in this specification are molecular weights calculated using polystyrene as a standard substance, using a gel permeation chromatography (GPC) analyzer using a column of TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation), using a THF (tetrahydrofuran) solvent and a differential refractometer.

[0062] In this specification, "total solids" refers to the total mass of the components after removing the solvent from the total composition. As described above, "solids" refers to the components after removing the solvent and may be solid or liquid at 25°C, for example.

[0063] (Photosensitive transfer material)

[0064] The photosensitive transfer material involved in the present invention has a temporary support body, a photosensitive resin layer and a protective film in sequence. When the surface energy of the surface of the temporary support body on the side opposite to the photosensitive resin layer side is set to γb (mN / m), and the surface energy of the surface of the protective film on the side opposite to the photosensitive resin layer side is set to γc (mN / m), γb≥γc is satisfied.

[0065] The present inventors have discovered that in a wiring formation process using a conventional photosensitive transfer material as described in Japanese Patent Gazette No. 2019-128445, when a photosensitive resin layer bonded to a substrate having a conductive layer is exposed via a temporary support, defects occur in the obtained resin pattern due to foreign matter attached to the temporary support.

[0066] As a result of detailed studies, the present inventors have found that, by adopting the above-mentioned embodiment, a resin pattern with few defects can be obtained even when the photosensitive resin layer is exposed through a temporary support.

[0067] In the photosensitive transfer material of the present invention, when the surface energy of the surface of the temporary support opposite to the photosensitive resin layer is γb (mN / m) and the surface energy of the surface of the protective film opposite to the photosensitive resin layer is γc (mN / m), γb ≥ γc. Therefore, although the detailed mechanism is unclear, it is speculated that by stacking the photosensitive transfer materials or rolling the photosensitive transfer materials into a roll, the temporary support and the protective film come into contact, and foreign matter such as dust attached to the temporary support moves toward the protective film and is removed from the temporary support. Therefore, even when the photosensitive resin layer is exposed through the temporary support, a resin pattern with few defects can be obtained.

[0068] Furthermore, "defects" in the resin pattern, as used herein, are areas of poor shape in the resin pattern. When a resin pattern with such defects is used as an etching mask to fabricate wiring, these defects can cause wiring disconnection (open circuits) or coupling between wirings (short circuits). This effect is particularly pronounced with finer patterns.

[0069] In the photosensitive transfer material involved in the present invention, when the surface energy of the surface on the side opposite to the photosensitive resin layer side in the above-mentioned temporary support body is set to γb (mN / m), and the surface energy of the surface on the side opposite to the photosensitive resin layer side in the above-mentioned protective film is set to γc (mN / m), γb≥γc is satisfied.

[0070] The method for adjusting the surface energy of the temporary support and the protective film is not particularly limited, and examples thereof include the type of resin used, the composition of additives, surface treatment, stretching treatment, and formation of a particle-containing layer described later.

[0071] In the present invention, the surface energy (unit: mN / m) of the temporary support or the protective film is calculated by the following method.

[0072] On the measurement surface of the temporary support or protective film, the contact angles of pure water and diiodomethane were measured at three points using a contact angle meter CA-A (manufactured by Kyowa Interface Science Co., Ltd.) at room temperature of 23°C and relative humidity of 50% to 60%. The average of the measured values ​​obtained for each liquid was used as the contact angle of each of the two liquids. The dispersion force γ was calculated using the geometric mean method based on the Owens-Wendt method using the contact angles of the two liquids obtained. d , polar force γ p and the surface energy γ (=γ d +γ p ).

[0073] The specific calculation method is shown in the following table. The meaning of each symbol is as follows. SL When is the tension at the interface between a solid and a liquid, the following equation (1) holds true.

[0074] γ SL : Surface free energy of film surface and known liquid

[0075] γ S : Surface free energy of the film surface

[0076] γ L : Surface free energy of known liquids

[0077] γ S d : Dispersion force component of the surface free energy of the film surface

[0078] γ S p : Polar force component of the surface free energy of the film surface

[0079] γ L d :Dispersion force component of the surface free energy of a known liquid

[0080] γ L p :Polar force component of surface free energy of known liquids

[0081] γ SL =γ S +γ L -2(γ S d γ L d ) 1 / 2 -2(γ S p γ L p ) 1 / 2...Formula (1)

[0082] The state when a smooth solid surface contacts a liquid droplet at a contact angle (θ) is expressed by the following formula (Young's formula).

[0083] γ S =γ SL +γ L cosθ……Formula (2)

[0084] Combining these equations (1) and (2) yields the following equation.

[0085] (γ s d γ L d ) 1 / 2 +(γ s p γ L p ) 1 / 2 (=γ L (1+cosθ) / 2……Formula (3)

[0086] In fact, the contact angle (θ) of pure water and diiodomethane, the surface energy γ of the known liquid L And each component (γ L d , γ L p ) into equation (3) to solve the simultaneous equations.

[0087] As a result, the surface energy (γ S ).

[0088] In the photosensitive transfer material involved in the present invention, from the perspective of the defect suppression and resolution of the resin pattern when exposed through a temporary support body (hereinafter also referred to as "defect suppression and resolution of the resin pattern"), the value of γb-γc is preferably greater than 0mN / m and less than 50mN / m, more preferably greater than 2mN / m and less than 30mN / m, and particularly preferably greater than 7mN / m and less than 20mN / m.

[0089] In the photosensitive transfer material involved in the present invention, from the viewpoint of defect suppression and resolution of the resin pattern, the value of the surface energy γb of ​​the surface on the side opposite to the photosensitive resin layer side in the above-mentioned temporary support is preferably 30mN / m to 70mN / m, more preferably 40mN / m to 65mN / m, and particularly preferably 45mN / m to 60mN / m.

[0090] In the photosensitive transfer material involved in the present invention, from the viewpoint of defect suppression and resolution of the resin pattern, the value of the surface energy γc of the surface of the protective film on the side opposite to the photosensitive resin layer side is preferably 20mN / m to 65mN / m, more preferably 25mN / m to 55mN / m, and particularly preferably 30mN / m to 45mN / m.

[0091] The photosensitive transfer material according to the present invention includes a temporary support, a photosensitive resin layer, and a protective film in this order.

[0092] Furthermore, the photosensitive transfer material according to the present invention may have other layers, for example, between the temporary support and the photosensitive resin layer, or between the photosensitive resin layer and the protective film.

[0093] From the viewpoint of further exerting the effects of the present invention, the photosensitive transfer material according to the present invention is preferably a roll-shaped photosensitive transfer material.

[0094] An example of the form of the photosensitive transfer material according to the present invention is shown below, but the present invention is not limited thereto.

[0095] (1) "Temporary support / photosensitive resin layer / refractive index adjusting layer / protective film"

[0096] (2) "Temporary support / photosensitive resin layer / protective film"

[0097] (3) "Temporary support / water-soluble resin layer / photosensitive resin layer / protective film"

[0098] (4) “Temporary support / thermoplastic resin layer / water-soluble resin layer / photosensitive resin layer / protective film”

[0099] In each of the above structures, the photosensitive resin layer is preferably a negative-type photosensitive resin layer. Furthermore, the photosensitive resin layer is preferably a colored resin layer. As described later, the photosensitive transfer material of the present invention can be used as a photosensitive transfer material for wiring protection films or as a photosensitive transfer material for etching resists.

[0100] In the case of a photosensitive transfer material for a wiring protection film, the structure of the photosensitive transfer material is preferably, for example, the structure (1) or (2) described above.

[0101] Furthermore, in the case of a photosensitive transfer material for an etching resist, the structure of the photosensitive transfer material is preferably, for example, the structures (2) to (4) described above.

[0102] In the photosensitive transfer material, when the photosensitive resin layer has a structure with other layers on the side opposite to the temporary support body, the total thickness of the other layers arranged on the side opposite to the temporary support body of the photosensitive resin layer is preferably 0.1% to 30% relative to the layer thickness of the photosensitive resin layer, and more preferably 0.1% to 20%.

[0103] The photosensitive transfer material of the present invention will be described below using a specific embodiment. The photosensitive transfer material of the first embodiment below is preferably used as a photosensitive transfer material for etching resists, and the photosensitive transfer material of the second embodiment below is preferably used as a photosensitive transfer material for wiring protection films.

[0104] [Photosensitive transfer material according to the first embodiment]

[0105] Hereinafter, the photosensitive transfer material according to the first embodiment will be described by taking an example.

[0106] Figure 1 The photosensitive transfer material 20 shown 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 in this order.

[0107] and, Figure 1 The photosensitive transfer material 20 shown in FIG. 1 is a form in which the thermoplastic resin layer 13 and the water-soluble resin layer 15 are provided. However, the thermoplastic resin layer 13 and the water-soluble resin layer 15 may not be provided.

[0108] Hereinafter, each element constituting the photosensitive transfer material according to the first embodiment will be described.

[0109] Temporary support

[0110] The photosensitive transfer material used in the present invention has a temporary support.

[0111] The temporary support is a peelable support that supports the photosensitive resin layer or the laminate including the photosensitive resin layer.

[0112] From the perspective of being able to expose the photosensitive resin layer through the temporary support when pattern-exposing the photosensitive resin layer, the temporary support is preferably light-transmissive. In this specification, "light-transmissive" means that the transmittance of light of the wavelength used in the pattern exposure is 50% or more.

[0113] From the viewpoint of improving the exposure sensitivity of the photosensitive resin layer, the temporary support preferably has a transmittance of 60% or more, more preferably 70% or more, for light of a wavelength (more preferably 365 nm) used in pattern exposure.

[0114] The transmittance of a layer of a photosensitive transfer material refers to the ratio of the intensity of the outgoing light that passes through the layer when light is incident in a direction perpendicular to the main surface of the layer (i.e., in the thickness direction) to the intensity of the incident light, and is measured using an MCPD Series manufactured by Otsuka Flectronics Co., Ltd.

[0115] Examples of the material constituting the temporary support include a glass substrate, a resin film, and paper. From the viewpoint of strength, flexibility, and light transmittance, a resin film is preferred.

[0116] Examples of the resin film include polyethylene terephthalate (PET) films, cellulose triacetate films, polystyrene films, and polycarbonate films. Among these, PET films are preferred, and biaxially stretched PET films are more preferred.

[0117] The thickness (layer thickness) of the temporary support is not particularly limited and can be selected according to the material from the viewpoints of strength as a support, flexibility required for bonding to the circuit wiring forming substrate, and light transmittance required in the initial exposure step.

[0118] 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 particularly preferably in the range of 10 μm to 16 μm from the viewpoint of ease of handling and versatility.

[0119] Furthermore, from the viewpoint of defect suppression, resolution, and linearity of the resin pattern, the thickness of the temporary support is preferably 50 μm or less, more preferably 25 μm or less, and particularly preferably 20 μm or less.

[0120] Furthermore, it is preferred that the film used as a temporary support has no deformation such as wrinkles, scratches, or defects.

[0121] From the viewpoint of pattern formation during pattern exposure across the temporary support and the transparency of the temporary support, it is preferred that the number of particles, impurities, defects, precipitates, etc. contained in the temporary support be small. The number of particles, impurities, and defects with a diameter of 1 μm or more is preferably 50 / 10 mm. 2 Less than 10 pieces / 10mm, more preferably 10 pieces / 10mm 2 Below, more preferably 3 / 10mm 2 Below, particularly preferably 0 / 10mm 2 .

[0122] From the perspective of defect suppression, resolution, and transparency of the temporary support of the resin pattern, the temporary support preferably has a low haze value. Specifically, the temporary support preferably has a haze value of 2% or less, more preferably 1.5% or less, further preferably less than 1.0%, and particularly preferably 0.5% or less.

[0123] The haze value in the present invention is measured using a haze meter (NDH-2000, manufactured by NIPPON DENSHOKU INDUSTRIES Co., LTD.) by a method in accordance with JIS K 7105:1981.

[0124] From the perspective of imparting handleability, a layer containing fine particles (lubricant layer) can be provided on the surface of the temporary support. The lubricant layer can 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 set to 0.05 μm to 0.8 μm, for example. Furthermore, the thickness of the lubricant layer can be set to 0.05 μm to 1.0 μm, for example.

[0125] From the perspective of transportability, defect suppression of the resin pattern and resolution, the arithmetic mean roughness Ra of the surface on the opposite side of the temporary support to the photosensitive resin layer side is preferably greater than the arithmetic mean roughness Ra of the surface on the photosensitive resin layer side of the temporary support.

[0126] From the perspective of transportability, defect suppression of the resin pattern and resolution, the arithmetic mean roughness Ra of the surface on the side opposite to the above-mentioned photosensitive resin layer side in the temporary support is preferably 100 nm or less, more preferably 50 nm or less, further preferably 20 nm or less, and particularly preferably 10 nm or less.

[0127] From the viewpoint of the releasability of the temporary support, the defect suppression of the resin pattern and the resolution, the arithmetic mean roughness Ra of the surface on the photosensitive resin layer side of the temporary support is preferably 100 nm or less, more preferably 50 nm or less, further preferably 20 nm or less, and particularly preferably 10 nm or less.

[0128] Furthermore, from the viewpoints of transportability, defect suppression of the resin pattern, and resolution, the value obtained by subtracting the value of the arithmetic mean roughness Ra of the surface on the photosensitive resin layer side of the temporary support from the value of the arithmetic mean roughness Ra of the surface on the side opposite to the photosensitive resin layer side of the temporary support is preferably 0 nm to 10 nm, and more preferably 0 nm to 5 nm.

[0129] The arithmetic mean roughness Ra of the surface of the temporary support or the protective film in the present invention is measured by the following method.

[0130] The surface of the temporary support or the protective film was measured using a three-dimensional optical profiler (New View 7300, manufactured by Zygo) under the following conditions to obtain the surface distribution of the thin film.

[0131] The measurement and analysis software used was the Microscope Application of MetroPro ver8.3.2. Next, the Surface Map screen was displayed using the analysis software, and histogram data was obtained from the Surface Map screen. The arithmetic mean roughness was calculated from the obtained histogram data to obtain the Ra value of the surface of the temporary support or protective film.

[0132] When a temporary support or a protective film is laminated 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.

[0133] From the perspective of the peeling inhibition of the temporary support caused by the adhesion of the upper and lower stacked stacks when the wound stack is re-conveyed using a roll-to-roll method, 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 preferably 0.5 mN / mm or more, more preferably 0.5 mN / mm to 2.0 mN / mm.

[0134] The peeling force of the temporary support in the present invention is measured as follows.

[0135] A copper layer having a thickness of 200 nm was formed on a polyethylene terephthalate (PET) film having a thickness of 100 μm by sputtering, thereby producing a PET substrate with a copper layer.

[0136] The protective film was removed from the prepared photosensitive transfer material, and the material was laminated onto the copper-layered PET substrate under lamination conditions: a laminating roll temperature of 100°C, a linear pressure of 0.6 MPa, and a linear speed (laminating speed) of 1.0 m / min. Next, an adhesive tape (NITTO DENKO CORPORATION PRINTACK) was attached to the surface of a temporary support. The laminate, comprising at least the temporary support and the photosensitive resin layer on the copper-layered PET substrate, was cut into 70 mm x 10 mm pieces to prepare a sample. The PET substrate side of the sample was secured to a sample stand.

[0137] The tape was stretched at 5.5 mm / s in a 180-degree direction using a tension-compression tester (SV-55 manufactured by IMADA-SS Corporation) to peel the photosensitive resin layer or thermoplastic resin layer from the temporary support. The peeling force (peel force) and adhesion strength were measured.

[0138] Preferred forms of temporary support bodies are described, for example, in paragraphs 0017 to 0018 of Japanese Patent Publication No. 2014-85643, paragraphs 0019 to 0026 of Japanese Patent Publication No. 2016-27363, paragraphs 0041 to 0057 of International Publication No. 2012 / 081680, paragraphs 0029 to 0040 of International Publication No. 2018 / 179370, and paragraphs 0012 to 0032 of Japanese Patent Publication No. 2019-101405, and the contents of these publications are incorporated into this specification.

[0139] 〔Protective film〕

[0140] The photosensitive transfer material has a protective film.

[0141] The photosensitive resin layer and the protective film are preferably in direct contact.

[0142] Examples of the material constituting the protective film include resin films and paper. From the viewpoint of strength and flexibility, resin films are preferred.

[0143] Examples of the resin film include polyethylene films, polypropylene films, polyethylene terephthalate films, triacetylcellulose films, polystyrene films, and polycarbonate films. Among these, polyethylene films, polypropylene films, and polyethylene terephthalate films are preferred.

[0144] 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.

[0145] From the perspective of transportability, defect suppression of the resin pattern and resolution, the arithmetic mean roughness Ra of the surface on the side opposite to the above-mentioned photosensitive resin layer in the protective film is preferably less than the arithmetic mean roughness Ra of the surface on the above-mentioned photosensitive resin layer side in the protective film, and more preferably less than the arithmetic mean roughness Ra of the surface on the above-mentioned photosensitive resin layer side in the protective film.

[0146] From the viewpoint of transportability and windability, the arithmetic mean 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, further preferably 70 nm or less, and particularly preferably 50 nm or less.

[0147] Furthermore, from the perspective of achieving even better resolution, the arithmetic mean roughness Ra of the surface of the protective film facing the photosensitive resin layer is preferably 300 nm or less, more preferably 100 nm or less, even more preferably 70 nm or less, and particularly preferably 50 nm or less. This is believed to be because when the Ra value of the protective film surface is within the above range, the uniformity of the thickness of the photosensitive resin layer and the resulting resin pattern is improved.

[0148] The lower limit of the Ra value of the surface of the protective film is not particularly limited, but is preferably 1 nm or more on both sides, more preferably 10 nm or more, and particularly preferably 20 nm or more.

[0149] Furthermore, the peeling force of the protective film is preferably smaller than the peeling force of the temporary support.

[0150] [Photosensitive resin layer]

[0151] The photosensitive transfer material according to the present invention includes a photosensitive resin layer.

[0152] The photosensitive resin layer may be a negative photosensitive resin layer or a positive photosensitive resin layer, but is preferably a negative photosensitive resin layer in which the solubility of the exposed portion in a developer is reduced by exposure and the non-exposed portion is removed by development.

[0153] The photosensitive resin layer preferably comprises an alkali-soluble resin, a polymerizable compound (preferably an ethylenically unsaturated compound) and a photopolymerization initiator. Based on the total mass of the above-mentioned photosensitive resin layer, it more preferably comprises 10% to 90% by mass of the alkali-soluble resin; 5% to 70% by mass of the ethylenically unsaturated compound; and 0.01% to 20% by mass of the photopolymerization initiator.

[0154] Hereinafter, each component will be described in order.

[0155] <Alkali-soluble resin>

[0156] The photosensitive resin layer preferably contains an alkali-soluble resin.

[0157] In this specification, the term "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.

[0158] The alkali-soluble resin is not particularly limited, and preferably, for example, a known alkali-soluble resin used for etching resists is used.

[0159] Furthermore, the alkali-soluble resin is preferably a binder polymer.

[0160] As the alkali-soluble resin, an alkali-soluble resin having an acid group is preferable.

[0161] Among them, the alkali-soluble resin is preferably the polymer A described later.

[0162] -Polymer A-

[0163] As the alkali-soluble resin, polymer A is preferably contained.

[0164] From the viewpoint of achieving better resolution by suppressing swelling of the photosensitive resin layer by the developer, the acid value of the polymer A is preferably 220 mgKOH / g or less, more preferably less than 200 mgKOH / g, and even more preferably less than 190 mgKOH / g.

[0165] The lower limit of the acid value of polymer A is not particularly limited, but is preferably 60 mgKOH / g or more, more preferably 120 mgKOH / g or more, further preferably 150 mgKOH / g or more, and particularly preferably 170 mgKOH / g or more from the viewpoint of better developability.

[0166] The acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of a sample, and in this specification, the unit is expressed as mgKOH / g. The acid value can be calculated from, for example, the average content of acid groups in the compound.

[0167] The acid value of the polymer A may be adjusted by adjusting the type of the structural unit constituting the polymer A and the content of the structural unit containing an acid group.

[0168] The weight-average molecular weight of polymer A is preferably 5,000 to 500,000. From the perspective of improving resolution and developability, the weight-average molecular weight is preferably 500,000 or less. 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, from the perspective of controlling the properties of the developed aggregates and the properties of the unexposed film such as edge melting and chipping when used as a photosensitive resin laminate, the weight-average molecular weight of polymer A is preferably 5,000 or more. The weight-average molecular weight of polymer A is more preferably 10,000 or more, further preferably 20,000 or more, and particularly preferably 30,000 or more. Edge melting refers to the ease with which the photosensitive resin layer protrudes from the end surface of the roll when the photosensitive transfer material is wound into a roll. Chipping refers to the ease with which chips fly when the unexposed film is cut with a cutter. If these shavings adhere to the upper surface of the photosensitive resin laminate, they may be transferred to the mask during the subsequent exposure process, causing defective products. The dispersity of polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and even more preferably 1.0 to 3.0. In the present invention, the molecular weight is a value measured using gel permeation chromatography. Furthermore, the dispersity is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight).

[0169] From the viewpoint of suppressing the deterioration of line width thickness or resolution when the focus position is offset during exposure, it is preferred that the photosensitive resin layer contains a monomer component having an aromatic hydrocarbon group as polymer A. In addition, as such an aromatic hydrocarbon group, for example, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted aralkyl group can be cited. The proportion of the monomer component having an aromatic hydrocarbon group in polymer A is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, particularly preferably 45% by mass or more, and most preferably 50% by mass or more, based on the total mass of all monomer components. As an upper limit, it is not particularly limited, but is preferably 95% by mass or less, more preferably 85% by mass or less. In addition, the proportion of the monomer component having an aromatic hydrocarbon group when containing a plurality of polymers A is obtained as a weight average.

[0170] As the monomer with the above-mentioned aromatic hydrocarbon group, for example, a monomer with an aralkyl group, styrene and a polymerizable styrene derivative (for example, methyl styrene, vinyl toluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.) can be mentioned. Among them, preferably a monomer with an aralkyl group or styrene. In one embodiment, when the monomer component with an aromatic hydrocarbon group in polymer A is styrene, the content ratio of the styrene monomer component is preferably 20% by mass to 50% by mass based on the total mass of all monomer components, 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.

[0171] Examples of the aralkyl group include substituted or unsubstituted phenylalkyl (excluding benzyl) and substituted or unsubstituted benzyl. Preferably, it is substituted or unsubstituted benzyl.

[0172] Examples of the monomer having a phenylalkyl group include phenylethyl (meth)acrylate and the like.

[0173] Examples of monomers having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and benzyl (meth)acrylate chloride; and vinyl monomers having a benzyl group, such as vinylbenzyl chloride and vinylbenzyl alcohol. Among these, benzyl (meth)acrylate is preferred. In one embodiment, when the monomer component having an aromatic hydrocarbon group in polymer A is benzyl (meth)acrylate, the content of the benzyl (meth)acrylate monomer component is preferably 50% to 95% by mass, more preferably 60% to 90% by mass, further preferably 70% to 90% by mass, and particularly preferably 75% to 90% by mass, based on the total mass of all monomer components.

[0174] The polymer A containing a monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing a monomer having an aromatic hydrocarbon group with at least one first monomer described below and / or at least one second monomer described below.

[0175] The polymer A not containing a monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one first monomer described below, and more preferably by copolymerizing at least one first monomer and at least one second monomer described below.

[0176] The first monomer is a monomer having a carboxyl group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. Among these, (meth)acrylic acid is preferred.

[0177] The content of the first monomer in the polymer A is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 30% by mass, based on the total mass of all monomer components.

[0178] The copolymerization ratio of the first monomer is preferably 10% to 50% by mass based on the total mass of all monomer components. From the perspective of showing good developability, controlling edge melting properties, etc., it is preferred that the copolymerization ratio be 10% by mass or more, more preferably 15% by mass or more, and further preferably 20% by mass or more. From the perspective of high resolution and hem shape of the resist pattern, and further from the perspective of chemical resistance of the resist pattern, it is preferred that the copolymerization ratio be 50% by mass or less. From these perspectives, it is more preferred that it be 35% by mass or less, further preferably 30% by mass or less, and particularly preferably 27% by mass or less.

[0179] The second monomer is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; vinyl alcohol esters such as vinyl acetate; and (meth)acrylonitrile. Among these, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate are preferred, with methyl (meth)acrylate being particularly preferred.

[0180] The content of the second monomer in the polymer A is preferably 5 to 60% by mass, more preferably 15 to 50% by mass, and even more preferably 20 to 45% by mass based on the total mass of all monomer components.

[0181] From the perspective of suppressing deterioration in line width and resolution due to focus shift during exposure, it is preferred to contain a monomer having an aralkyl group and / or styrene as a monomer. For example, a copolymer comprising methacrylic acid, benzyl methacrylate, and styrene, or a copolymer comprising methacrylic acid, methyl methacrylate, benzyl methacrylate, and styrene is preferred.

[0182] In one embodiment, polymer A preferably comprises 25% to 40% by mass of a monomer component having an aromatic hydrocarbon group, 20% to 35% by mass of a first monomer component, and 30% to 45% by mass of a second monomer component. Furthermore, in another embodiment, polymer A preferably comprises 70% to 90% by mass of a monomer component having an aromatic hydrocarbon group and 10% to 25% by mass of the first monomer component.

[0183] Polymer A may have a branched structure or an alicyclic structure on the side chain. Furthermore, Polymer A may have a linear structure on the side chain. By using a monomer containing a group having a branched structure on the side chain or a monomer containing a group having an alicyclic structure on the side chain, a branched structure or an alicyclic structure can be introduced into the side chain of Polymer A. The group having an alicyclic structure may be monocyclic or polycyclic.

[0184] Specific examples of monomers containing a group having a branched structure on a side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, isoamyl (meth)acrylate, t-amyl (meth)acrylate, sec-isoamyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, t-octyl (meth)acrylate, etc. Among these, isopropyl (meth)acrylate, isobutyl (meth)acrylate, or t-butyl methacrylate is preferred, and isopropyl methacrylate or t-butyl methacrylate is more preferred.

[0185] Examples of the monomer containing a group having an alicyclic structure in a side chain include monomers having a monocyclic aliphatic hydrocarbon group and monomers having a polycyclic aliphatic hydrocarbon group, and examples include (meth)acrylates having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. More specific examples include (bicyclo[2.2.1]heptyl-2-(meth)acrylate, 1-adamantyl(meth)acrylate, 2-adamantyl(meth)acrylate, 3-methyl-1-adamantyl(meth)acrylate, 3,5-dimethyl-1-adamantyl(meth)acrylate, 3-ethyladamantyl(meth)acrylate, 3-methyl-5-ethyl-1-adamantyl(meth)acrylate, 3,5,8-triethyl-1-adamantyl(meth)acrylate, 3,5-dimethyl-8-ethyl-1-adamantyl(meth)acrylate, 2-methyl-2-adamantyl(meth)acrylate, and 2-ethyl-2-adamantyl(meth)acrylate.

[0015] Examples of the present invention include methyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, octahydro-4,7-methanoindene-5-yl (meth)acrylate, octahydro-4,7-methanoindene-1-ylmethyl (meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl (meth)acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fenchyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, and cyclohexyl (meth)acrylate. Among these (meth)acrylates, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fenchyl (meth)acrylate, 1-menthol (meth)acrylate, or tricyclodecane (meth)acrylate is preferred, and cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate is particularly preferred.

[0186] Polymer A may be used alone or in combination of two or more. When two or more polymers are used in combination, it is preferred to use a mixture of two polymers A containing monomer components having aromatic hydrocarbon groups, or to use a mixture of a polymer A containing monomer components having aromatic hydrocarbon groups and a polymer A not containing monomer components having aromatic hydrocarbon groups. In the latter case, the proportion of the polymer A containing monomer components having aromatic hydrocarbon groups used relative to the total amount of polymer A is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, and more preferably 90% by mass or more.

[0187] Polymer A is preferably synthesized by adding an appropriate amount of a free radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to a solution of one or more of the monomers described above diluted with a solvent such as acetone, methyl ethyl ketone, or isopropyl alcohol, followed by heating and stirring. Synthesis may also be performed while a portion of the mixture is dropwise added to the reaction solution. Alternatively, after the reaction is complete, a solvent is further added to adjust the desired concentration. In addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may also be used as the synthesis apparatus.

[0188] The glass transition temperature Tg of polymer A is preferably 30°C or higher and 135°C or lower. By using a polymer A having a Tg of 135°C or lower in the photosensitive resin layer, it is possible to suppress the deterioration of line width or resolution when the focus position shifts during exposure. From this viewpoint, the Tg of polymer A is more preferably 130°C or lower, further preferably 120°C or lower, and particularly preferably 110°C or lower. Furthermore, from the viewpoint of improving edge melting resistance, it is preferred to use a polymer A having a Tg of 30°C or higher. From this viewpoint, the Tg of 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.

[0189] The photosensitive resin layer may contain a resin other than the alkali-soluble resin.

[0190] Examples of resins other than alkali-soluble resins include acrylic resins, styrene-acrylic acid copolymers (wherein the styrene content is 40% by mass or less), polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycol.

[0191] The alkali-soluble resin may be used alone or in combination of two or more.

[0192] The ratio of the alkali-soluble resin to the total mass of the photosensitive resin layer is preferably in the range of 10% to 90% by mass, more preferably 30% to 70% by mass, and even more preferably 40% to 60% by mass. From the perspective of controlling the development time, the ratio of the alkali-soluble resin to the photosensitive resin layer is preferably set to 90% by mass or less. On the other hand, from the perspective of improving edge melting resistance, the ratio of the alkali-soluble resin to the photosensitive resin layer is preferably set to 10% by mass or more.

[0193] <Polymerizable compounds>

[0194] The photosensitive resin layer preferably contains a polymerizable compound. In this specification, the "polymerizable compound" refers to a compound different from the alkali-soluble resin that is polymerized by the action of a polymerization initiator described below.

[0195] The polymerizable group possessed by the polymerizable compound is not particularly limited as long as it is a group that participates in the polymerization reaction. Examples thereof include groups having ethylenically unsaturated groups such as vinyl, acryloyl, methacryloyl, styryl and maleimide groups; and groups having cationic polymerizable groups such as epoxy and oxetane groups.

[0196] As the polymerizable group, a group having an ethylenically unsaturated group is preferred, and an acryloyl group or a methacryloyl group is more preferred.

[0197] Furthermore, as the polymerizable compound, it is preferred that an ethylenically unsaturated compound be included, and it is more preferred that a (meth)acrylate compound be included.

[0198] The ethylenically unsaturated compound is a compound having one or more ethylenically unsaturated groups.

[0199] The photosensitive resin layer preferably contains a bifunctional or higher-functional ethylenically unsaturated compound as the ethylenically unsaturated compound.

[0200] Here, the bifunctional or higher-functional ethylenically unsaturated compound refers to a compound having two or more ethylenically unsaturated groups in one molecule.

[0201] As the ethylenically unsaturated group, a (meth)acryloyl group is more preferred.

[0202] As the ethylenically unsaturated compound, a (meth)acrylate compound is preferred.

[0203] From the viewpoint of further improving the photosensitivity of the photosensitive resin layer, the ethylenically unsaturated compound preferably contains a compound having two or more ethylenically unsaturated groups in one molecule (polyfunctional ethylenically unsaturated compound).

[0204] Furthermore, from the viewpoint of achieving better resolution and releasability, 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 even more preferably 2 or less.

[0205] From the viewpoint of achieving a better balance between the photosensitivity, resolution, and releasability of the photosensitive resin layer, the photosensitive resin layer preferably contains a bifunctional or trifunctional ethylenically unsaturated compound having two or three ethylenically unsaturated groups in one molecule, and more preferably contains a bifunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule.

[0206] From the viewpoint of excellent releasability, the content of the bifunctional ethylenically unsaturated compound in the photosensitive resin layer is preferably 60% by mass or more, more preferably more than 70% by mass, and further preferably 90% by mass or more relative to the content of the ethylenically unsaturated compound. The upper limit is not particularly limited and may be 100% by mass. That is, all of the ethylenically unsaturated compounds contained in the photosensitive resin layer may be bifunctional ethylenically unsaturated compounds.

[0207] Furthermore, as the ethylenically unsaturated compound, a (meth)acrylate compound containing a (meth)acryloyl group as a polymerizable group is preferred.

[0208] -Ethylenically unsaturated compound B1-

[0209] The photosensitive resin layer preferably contains an ethylenically unsaturated compound B1 having an aromatic ring and 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.

[0210] In the photosensitive resin layer, from the perspective of achieving better resolution, the mass ratio of the content of the ethylenically unsaturated compound B1 relative to the content of the ethylenically unsaturated compound is preferably 40% by mass or greater, more preferably 50% by mass or greater, further preferably 55% by mass or greater, and particularly preferably 60% by mass or greater. The upper limit is not particularly limited, but from the perspective of releasability, it is preferably 99% by mass or less, more preferably 95% by mass or less, further preferably 90% by mass or less, and particularly preferably 85% by mass or less.

[0211] Examples of the aromatic ring possessed by the ethylenically unsaturated compound B1 include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, and an anthracene ring, aromatic heterocyclic rings such as a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring, and a pyridine ring, and condensed rings thereof. An aromatic hydrocarbon ring is preferred, and a benzene ring is more preferred. The aromatic rings may have substituents.

[0212] The ethylenically unsaturated compound B1 may have only one aromatic ring, or may have two or more aromatic rings.

[0213] From the viewpoint of improving the resolution by suppressing the swelling of the photosensitive resin layer caused by the developer, the ethylenically unsaturated compound B1 preferably has a bisphenol structure.

[0214] Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), a bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and a bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane). The bisphenol A structure is preferred.

[0215] Examples of the ethylenically unsaturated compound B1 having a bisphenol structure include compounds having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure.

[0216] The two polymerizable groups may be bonded directly to each terminal of the bisphenol structure or through one or more alkyleneoxy groups. The alkyleneoxy groups added to the terminals of the bisphenol structure are preferably ethyleneoxy or propyleneoxy, with ethyleneoxy being more preferred. The number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16, and more preferably 6 to 14, per molecule.

[0217] 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 the publication are incorporated into the present specification.

[0218] As the ethylenically unsaturated compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferred, and 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane is more preferred.

[0219] Examples of 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloyloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloyloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxydodecethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), and 2,2-bis(4-(methacryloyloxypentadecethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.). Co., Ltd.), 2,2-bis(4-(methacryloyloxydiethoxy)phenyl)propane (BPE-200, Shin-Nakamura Chemical Co., Ltd.), and ethoxylated (10) bisphenol A diacrylate (NK ESTER A-BPE-10, Shin-Nakamura Chemical Co., Ltd.).

[0220] As the ethylenically unsaturated compound B1, a compound represented by the following formula (Bis) can be used.

[0221] [Chemical Formula 1]

[0222]

[0223] In formula (Bis), R1 and R2 each independently represent a hydrogen atom or a methyl group, A is C2H4, B is C3H6, n1 and n3 each independently represent an integer from 1 to 39, and n1+n3 each represent an integer from 2 to 40, n2 and n4 each independently represent an integer from 0 to 29, and n2+n4 each represent an integer from 0 to 30, and the arrangement of the repeating units of -(AO)- and -(BO)- may be random or block. In the case of a block, either -(AO)- or -(BO)- may be on the bisphenol structure side.

[0224] In one embodiment, n1+n2+n3+n4 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. Furthermore, n2+n4 is preferably an integer of 0 to 10, more preferably an integer of 0 to 4, even more preferably an integer of 0 to 2, and particularly preferably 0.

[0225] The ethylenically unsaturated compound B1 may be used alone or in combination of two or more.

[0226] From the perspective of achieving better resolution, the content of the ethylenically unsaturated compound B1 in the photosensitive resin layer is preferably 10% by mass or more, and more preferably 20% by mass or more, relative to the total mass of the photosensitive resin layer. The upper limit is not particularly limited, but from the perspective of transferability and edge melting (a phenomenon in which components in the photosensitive resin layer ooze out from the ends of the photosensitive transfer material), it is preferably 70% by mass or less, and more preferably 60% by mass or less.

[0227] The photosensitive resin layer may contain an ethylenically unsaturated compound other than the above-mentioned ethylenically unsaturated compound B1.

[0228] The ethylenically unsaturated compounds other than the ethylenically unsaturated compound B1 are not particularly limited and can be appropriately selected from known compounds. Examples include compounds having one ethylenically unsaturated group per molecule (monofunctional ethylenically unsaturated compounds), bifunctional ethylenically unsaturated compounds without an aromatic ring, and trifunctional or higher ethylenically unsaturated compounds.

[0229] Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl butanediol, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate.

[0230] 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.

[0231] Examples of the alkylene glycol di(meth)acrylate include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate.

[0232] 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.

[0233] Examples of urethane di(meth)acrylates include propylene oxide-modified urethane di(meth)acrylates and ethylene oxide- and propylene oxide-modified urethane di(meth)acrylates. Examples of commercially available products include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0234] Examples of trifunctional or higher-functional ethylenically unsaturated compounds include dipentaerythritol (tri / tetra / penta / hexa) (meth)acrylate, pentaerythritol (tri / tetra) (meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerol tri(meth)acrylate, and alkylene oxide-modified products thereof.

[0235] Here, “(tri / tetra / penta / hexa) (meth) acrylate” is a concept including tri(meth) acrylate, tetra(meth) acrylate, penta(meth) acrylate and hexa(meth) acrylate, and “(tri / tetra) (meth) acrylate” is a concept including 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 more preferably contains the above-mentioned ethylenically unsaturated compound B1 and two or more trifunctional or higher ethylenically unsaturated compounds. In this case, the mass ratio of the ethylenically unsaturated compound B1 to the trifunctional or higher ethylenically unsaturated compound is preferably (total mass of the ethylenically unsaturated compound B1): (total mass of the trifunctional or higher ethylenically unsaturated compounds) = 1:1 to 5:1, more preferably 1.2:1 to 4:1, and even more preferably 1.5:1 to 3:1.

[0236] Furthermore, in one embodiment, the photosensitive resin layer preferably contains the above-mentioned ethylenically unsaturated compound B1 and two or more trifunctional ethylenically unsaturated compounds.

[0237] Examples of the alkylene oxide-modified trifunctional or higher ethylenically unsaturated compound include caprolactone-modified (meth)acrylate compounds (e.g., KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd. and A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd.), alkylene oxide-modified (meth)acrylate compounds (e.g., KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd. and ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd. and EBECRYL (registered trademark) 135 manufactured by Daicel-Allnex Ltd.), ethoxylated glyceryl triacrylate (e.g., A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.), ARONIX (registered trademark) TO-2349 (TOAGOSEI Co., Ltd.), ARONIX M-520 (manufactured by Toagosei Co., Ltd.), and ARONIX M-510 (manufactured by Toagosei Co., Ltd.).

[0238] Furthermore, as ethylenically unsaturated compounds other than the ethylenically unsaturated compound B1, ethylenically unsaturated compounds having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942 can be used.

[0239] From the viewpoint of resolution and linearity, the ratio Mm / Mb of the content Mm of the ethylenically unsaturated compound to the content Mb of the alkali-soluble resin in the photosensitive resin layer is preferably 1.0 or less, more preferably 0.9 or less, and particularly preferably 0.5 or more and 0.9 or less.

[0240] Furthermore, from the viewpoint of curability and resolution, the ethylenically unsaturated compound in the photosensitive resin layer preferably contains a (meth)acrylic compound.

[0241] Furthermore, from the viewpoints of curability, resolution, and linearity, it is more preferred that the ethylenically unsaturated compound in the photosensitive resin layer include a (meth)acrylic compound, and the content of the acrylic compound is 60% by mass or less relative to the total mass of the (meth)acrylic compound contained in the photosensitive resin layer.

[0242] The molecular weight (weight average molecular weight (Mw) when having a distribution) of the ethylenically unsaturated compound including the ethylenically unsaturated compound B1 is preferably 200 to 3,000, more preferably 280 to 2,200, and further preferably 300 to 2,200.

[0243] The polymerizable compound (especially an ethylenically unsaturated compound) may be used alone or in combination of two or more.

[0244] The content of the polymerizable compound (especially the ethylenically unsaturated compound) in the photosensitive resin layer is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and even more preferably 20 to 50% by mass relative to the total mass of the photosensitive resin layer.

[0245] <Photopolymerization initiator>

[0246] The photosensitive resin layer preferably contains a photopolymerization initiator.

[0247] The photopolymerization initiator is a compound that initiates polymerization of an ethylenically unsaturated compound upon receiving activating light such as ultraviolet light, visible light, and X-rays. The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.

[0248] Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferred.

[0249] Examples of the photoradical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α-aminoalkylphenone structure, a photopolymerization initiator having an α-hydroxyalkylphenone structure, a photopolymerization initiator having an acylphosphine oxide structure, a photopolymerization initiator having an N-phenylglycine structure, and a bisimidazole compound.

[0250] As the photoradical polymerization initiator, for example, polymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-95716 and paragraphs 0064 to 0081 of JP-A-2015-14783 can be used.

[0251] Examples of the photoradical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisil (p,p'-dimethoxybenzyl), TAZ-110 (trade name: manufactured by Midori Kagaku Co., Ltd.), benzophenone, TAZ-111 (trade name: manufactured by Midori Kagaku Co., Ltd.), Irgacure OXE01, OXE02, OXE03, and OXE04 (manufactured by BASF), Omnirad 651 and 369 (trade name: manufactured by IGM Resins BV), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0252] 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-carbazol-3-yl]ethanone-1-(O-acetoxime) (trade name: IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]-1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins BV), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 5000), and 1-[4-(4-methylthiophenyl)methyl]-1-[4-(4-morpholino)phenyl]-1-butanone. 907, manufactured by IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (trade name: Omnirad 127, manufactured by IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1-one (trade name: Omnirad 369, manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, manufactured by IGM Resins BV), 1-hydroxycyclohexyl phenyl ketone (trade name: Omnirad 184, manufactured by IGM Resins BV), 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: Omnirad 651, manufactured by IGM Resins BV) BV), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, manufactured by IGM Resins BV), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, manufactured by IGM Resins BV), an oxime ester-based photopolymerization initiator (trade name: Lunar 6, manufactured by DKSH Japan KK), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (trade name: B-CIM, manufactured by Hampford), and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.).

[0253] A photocationic polymerization initiator (photoacid generator) is a compound that generates acid in response to active light. Preferred photocationic polymerization initiators are compounds that generate acid in response to active light with a wavelength of 300 nm or longer, preferably 300-450 nm, but their chemical structure is not limited. Furthermore, photocationic polymerization initiators that are not directly sensitive to active light with a wavelength of 300 nm or longer can also be used in combination with a sensitizer, as long as they generate acid in response to active light with a wavelength of 300 nm or longer when used in combination with a sensitizer.

[0254] As the photocationic polymerization initiator, one that generates an acid with a pKa of 4 or less is preferred, one that generates an acid with a pKa of 3 or less is more preferred, and one that generates an acid with a pKa of 2 or less is particularly preferred. The lower limit of the pKa is not particularly limited, but is preferably -10.0 or greater, for example.

[0255] Examples of the photocationic polymerization initiator include ionic photocationic polymerization initiators and nonionic photocationic polymerization initiators.

[0256] Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.

[0257] As the ionic photocationic polymerization initiator, those described in paragraphs 0114 to 0133 of JP-A-2014-85643 can be used.

[0258] Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Trichloromethyl-s-triazines, diazomethane compounds, and imide sulfonate compounds may be those described in paragraphs 0083 to 0088 of Japanese Patent Application Publication No. 2011-221494. Furthermore, oxime sulfonate compounds may be those described in paragraphs 0084 to 0088 of International Publication No. 2018 / 179640.

[0259] The photosensitive resin layer may contain one type of photopolymerization initiator alone, or may contain two or more types.

[0260] 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, and even more preferably 1.0% by mass or more, relative to the total mass of the photosensitive resin layer. The upper limit is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the photosensitive resin layer.

[0261] Pigment

[0262] From the perspective of visibility of the exposed and non-exposed areas, pattern visibility after development, and resolution, the photosensitive resin layer preferably contains a pigment, more preferably a pigment having a maximum absorption wavelength of 450 nm or greater within the wavelength range of 400 nm to 780 nm during color development and whose maximum absorption wavelength changes due to acid, base, or free radicals (also referred to as "pigment N"). Although the detailed mechanism is not yet clear, the inclusion of pigment N improves adhesion to adjacent layers (e.g., a temporary support and other adjacent layers), resulting in better resolution.

[0263] In this specification, the phrase "a pigment's maximum absorption wavelength changes due to acid, alkali, or free radicals" refers to any of the following: a pigment in a coloring state is decolorized by acid, alkali, or free radicals; a pigment in a decolorized state is colorized by acid, alkali, or free radicals; and a pigment in a coloring state is changed to a coloring state of another hue.

[0264] Specifically, pigment N can be a compound that develops color by exposure and changes from a bleached state, or a compound that decolorizes by exposure and changes from a bleached state. In this case, it can be a pigment that generates acid, alkali or free radicals in the photosensitive resin layer by exposure and plays a role and develops or decolorizes the state, or it can be a pigment that develops or decolorizes the state by acid, alkali or free radicals and changes the state (such as pH) in the photosensitive resin layer. Furthermore, it can also be a pigment that directly receives acid, alkali or free radicals as stimulation and changes the state of color development or decolorization without exposure.

[0265] Among them, from the viewpoint of visibility and resolution of the exposed and non-exposed areas, 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.

[0266] From the viewpoint of visibility and resolution of the exposed and non-exposed areas, the photosensitive resin layer preferably contains, as the dye N, both a dye that changes the maximum absorption wavelength by radicals and a photoradical polymerization initiator.

[0267] Furthermore, 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 acid, alkali, or radicals.

[0268] As an example of the color development mechanism of the dye N in the present invention, a radical-reactive dye, an acid-reactive dye or an alkali-reactive dye (e.g., a colorless dye) is added to a photosensitive resin layer to develop color by the radicals, acid or base generated by the photoradical polymerization initiator, photocationic polymerization initiator (photoacid generator) or photobase generator after exposure.

[0269] From the viewpoint of visibility of the exposed and non-exposed areas, the maximum absorption wavelength of the dye N in the wavelength range of 400 nm to 780 nm during color development is preferably 550 nm or longer, more preferably 550 nm to 700 nm, and even more preferably 550 nm to 650 nm.

[0270] Furthermore, the pigment N may have only one maximum absorption wavelength within the wavelength range of 400 nm to 780 nm when developing color, or may have two or more. In the case where the pigment N has two or more maximum absorption wavelengths within the wavelength range of 400 nm to 780 nm when developing color, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or longer.

[0271] The maximum absorption wavelength of pigment N was obtained by measuring the transmission spectrum of a solution containing pigment N (liquid temperature 25°C) in the range of 400 nm to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) in an atmospheric environment, and detecting the wavelength at which the light intensity is minimized (maximum absorption wavelength).

[0272] Examples of dyes that develop or fade color by exposure include colorless compounds.

[0273] Examples of dyes that are decolorized by exposure include colorless compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes.

[0274] The dye N is preferably a colorless compound from the viewpoint of visibility of the exposed portion and the non-exposed portion.

[0275] Examples of colorless compounds include colorless compounds having a triarylmethane skeleton (triarylmethane-based pigments), colorless compounds having a spiropyran skeleton (spiropyran-based pigments), colorless compounds having a fluoran skeleton (fluoran-based pigments), colorless compounds having a diarylmethane skeleton (diarylmethane-based pigments), colorless compounds having a rhodamine lactam skeleton (rhodamine lactam-based pigments), colorless compounds having an indolylphthalide skeleton (indolylphthalide-based pigments), and colorless compounds having a colorless aurantium skeleton (colorless aurantium dyes).

[0276] Among them, triarylmethane-based dyes or fluoran-based dyes are preferred, and colorless compounds having a triphenylmethane skeleton (triphenylmethane-based dyes) or fluoran-based dyes are more preferred.

[0277] From the perspective of visibility of the exposed and non-exposed portions, the colorless compound preferably has a lactone ring, a sultine ring, or a sultone ring. Thus, by reacting the lactone ring, sultine ring, or sultone ring of the colorless compound with a free radical generated by a photoradical polymerization initiator or an acid generated by a photocationic polymerization initiator, the colorless compound can be changed to a closed-ring state to decolorize or to an open-ring state to develop color. The colorless compound preferably has a lactone ring, sultine ring, or sultone ring, and a compound that develops color by free radicals or acid ring-opening the lactone ring, sultine ring, or sultone ring is more preferably a compound that has a lactone ring and develops color by free radicals or acid ring-opening the lactone ring.

[0278] Examples of the pigment N include the following dyes and colorless compounds.

[0279] Specific examples of the dye in the pigment N include brilliant green, ethyl violet, methyl green, crystal violet, Viscin red, methyl violet 2B, quinolizine red, rose bengal, formyl yellow, thimorph, xylenol blue, methyl orange, p-methyl red, Congo red, benzopurine 4B, α-naphthyl red, naphthalene blue 2B, naphthalene blue A, methyl violet, malachite green, hydroquinone, Victoria Pure Blue-alkylnaphthalenesulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Pink #312 (manufactured by ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Red 5B (manufactured by ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Scarlet #308 (manufactured by ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Red OG (manufactured by ORIENT CHEMICAL INDUSTRIES CO., LTD.), and the like. Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Industries Co., Ltd.), Oil Green #502 (manufactured by Orient Chemical Industries Co., Ltd.), Spiron Red BEH Special (manufactured by Hodogaya Chemical Co., Ltd.), m-cresol violet, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, golden ammonia, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0280] Specific examples of the colorless compound in the dye N include p,p',p"-hexamethyltriaminotriphenylmethane (colorless crystal violet), Pergascript Blue SRB (manufactured by Novartis International AG), crystal violet lactone, malachite green lactone, benzoyl leuco-methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluoran, 2-anilino-3-methyl-6-(N-ethyl-p-formyldiamino)fluoran, 3,6-dimethoxyfluoran, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluoran, 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilino Fluoran, 3-(N,N-diethylamino)-6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-phenylfluoran, 3-(N,N-diethylamino)-6-methyl-7-chlorofluoran, 3-(N,N-diethylamino)-6-methoxy-7-aminofluoran, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluoran, 3-(N,N-diethylamino)-7-chlorofluoran, 3-(N,N-diethylamino)-7-phenylfluoran, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluoran, 3-(N,N-dibutylamino)-6-methyl-7-phenylfluoran, 3-hydropyridyl-6-methyl-7-anilinofluoran, 3-pyrrolidinyl-6-methyl-7-anilinofluoran, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-n-butylamino)-6-methyl-7-anilinofluoran, butyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthan-3-one.

[0281] From the viewpoint of visibility of the exposed and non-exposed areas, and pattern visibility and resolution after development, the dye N is preferably a dye that changes the maximum absorption wavelength by radicals, and more preferably a dye that develops color by radicals.

[0282] As the pigment N, leuco crystal violet, crystal violet lactone, brilliant green or Victoria pure blue-alkylnaphthalene sulfonate is preferred.

[0283] The pigment may be used alone or in combination of two or more.

[0284] From the viewpoint of visibility of the exposed and non-exposed areas, and visibility and resolution of the pattern after development, the content of the pigment is preferably 0.1% by mass or more, more preferably 0.1% by mass to 10% by mass, further preferably 0.1% by mass to 5% by mass, and particularly preferably 0.1% by mass to 1% by mass, relative to the total mass of the photosensitive resin layer.

[0285] Furthermore, from the viewpoint of visibility of the exposed and non-exposed portions, and visibility and resolution of the pattern after development, the content of the pigment N is preferably 0.1% by mass or more, more preferably 0.1% by mass to 10% by mass, further preferably 0.1% by mass to 5% by mass, and particularly preferably 0.1% by mass to 1% by mass, relative to the total mass of the photosensitive resin layer.

[0286] The content of the dye N refers to the content of the dye when all the dyes N contained in the photosensitive resin layer are in a colored state. Hereinafter, a method for quantifying the content of the dye N will be described using a dye that develops color by radicals as an example.

[0287] Two solutions were prepared, each containing 0.001 g or 0.01 g of the pigment dissolved in 100 mL of methyl ethyl ketone. Irgacure OXE01 (trade name, BASF Japan Ltd.), a photoradical polymerization initiator, was added to each solution and irradiated with 365 nm light to generate free radicals, causing all the pigments to develop color. The absorbance of each solution was then measured at 25°C using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) under atmospheric conditions to create a calibration curve.

[0288] Next, the absorbance of the solution containing the photosensitive resin layer was measured using the same method as above, except that 3g of the photosensitive resin layer was dissolved in methyl ethyl ketone instead of the pigment. The pigment content in the photosensitive resin layer was calculated using a calibration curve based on the absorbance of the solution containing the obtained photosensitive resin layer.

[0289] Thermally cross-linkable compounds

[0290] From the perspective of the strength of the obtained cured film and the adhesiveness of the obtained uncured film, the photosensitive resin layer preferably contains a thermally crosslinkable compound. In addition, in this specification, the thermally crosslinkable compound having an ethylenically unsaturated group described later is not treated as a polymerizable compound, but as a thermally crosslinkable compound.

[0291] Examples of the heat-crosslinkable compound include methylol compounds and blocked isocyanate compounds, of which blocked isocyanate compounds are preferred from the viewpoint of the strength of the resulting cured film and the adhesiveness of the resulting uncured film.

[0292] The blocked isocyanate compound reacts with a hydroxyl group and a carboxyl group. Therefore, when, for example, a resin and / or a polymerizable compound has at least one of a hydroxyl group and a carboxyl group, the hydrophilicity of the film formed decreases, thereby tending to enhance the function of the film formed by curing the photosensitive resin layer as a protective film.

[0293] The blocked isocyanate compound refers to a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) by a blocking agent.

[0294] 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.

[0295] The dissociation temperature of the blocked isocyanate refers to "the temperature of an endothermic peak accompanying the deprotection reaction of the blocked isocyanate when measured by DSC (Differential Scanning Calorimetry) analysis using a differential scanning calorimeter."

[0296] 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.

[0297] Examples of the end-capping agent having a dissociation temperature of 100°C to 160°C include active methylene compounds [malonic acid diesters (such as dimethyl malonate, diethyl malonate, di-n-butyl malonate, and di-2-ethylhexyl malonate)] and oxime compounds (formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime, which have a structure represented by -C(=N-OH)- in the molecule).

[0298] Among these, as a blocking agent having a dissociation temperature of 100° C. to 160° C., for example, an oxime compound is preferably contained from the viewpoint of storage stability.

[0299] For example, from the viewpoints of improving the brittleness of the film and enhancing the adhesion to the transfer target, the blocked isocyanate compound preferably has an isocyanurate structure.

[0300] The blocked isocyanate compound having an isocyanurate structure is obtained by, for example, isocyanurating hexamethylene diisocyanate to protect it.

[0301] Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure using an oxime compound as a blocking agent are preferred from the viewpoint that the dissociation temperature can be more easily set within a preferred range and development residue can be easily reduced compared to compounds not having an oxime structure.

[0302] The blocked isocyanate compound may have a polymerizable group.

[0303] The polymerizable group is not particularly limited, and a known polymerizable group can be used. A radical polymerizable group is preferred.

[0304] Examples of the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloyloxy group, a (meth)acrylamide group, and a styryl group, and groups having an epoxy group such as a glycidyl group.

[0305] Among these, as the polymerizable group, an ethylenically unsaturated group is preferred, a (meth)acryloyloxy group is more preferred, and an acryloyloxy group is further preferred.

[0306] As the blocked isocyanate compound, a commercially available product can be used.

[0307] Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (all manufactured by SHOWA DENKO KK), and blocked Duranate series (for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation).

[0308] Furthermore, as the blocked isocyanate compound, compounds having the following structures can also be used.

[0309] [Chemical Formula 2]

[0310]

[0311] The heat-crosslinkable compound may be used alone or in combination of two or more.

[0312] When the photosensitive resin layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass, based on the total mass of the photosensitive resin layer.

[0313] <Other ingredients>

[0314] The photosensitive resin layer may contain components other than the above-mentioned alkali-soluble resin, ethylenically unsaturated compound, photopolymerization initiator, pigment, and thermally crosslinkable compound.

[0315] -Surfactants-

[0316] From the viewpoint of thickness uniformity, the photosensitive resin layer preferably contains a surfactant.

[0317] Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants, and nonionic surfactants are preferred.

[0318] Examples of the surfactant include those described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Patent Application Laid-Open No. 2009-237362.

[0319] As the surfactant, a fluorine-based surfactant or a silicone-based surfactant is preferable.

[0320] Examples of commercially available fluorochemical surfactants include Megaface (trade name) 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 (the above is DIC Corporation), Fluorad (trade name) FC430, FC431, FC171 (all manufactured by Sumitomo 3M Limited), 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 Inc.), P olyFox (trade name) PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA Solutions Inc.), Ftergent (trade name), 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F (all manufactured by Neos Corporation), U-120E (Uni-chem Co., Ltd.), etc.

[0321] Furthermore, fluorine-based surfactants preferably include acrylic compounds having a molecular structure containing a functional group containing a fluorine atom, and in which the fluorine-containing functional group is partially cleaved upon application of heat, thereby volatilizing the fluorine atom. Examples of such fluorine-based surfactants include the Megaface (trade name) DS series manufactured by DIC Corporation (Chemical Industry Daily (February 22, 2016), Nikkei Industry News (February 23, 2016)), for example, Megaface (trade name) DS-21.

[0322] Furthermore, as the fluorine-based surfactant, a polymer of a fluorine-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound is also preferably used.

[0323] Fluorine-based surfactants can also use end-capped polymers. Fluorine-based surfactants can also preferably use fluorine-containing polymers containing structural units derived from (meth)acrylate compounds having fluorine atoms and structural units derived from (meth)acrylate compounds having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy and propyleneoxy groups).

[0324] Fluorine-based surfactants that can be used are fluorine-containing polymers having an ethylenically unsaturated group in a side chain, and examples thereof include Megaface (trade name) RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0325] Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, Pluronic (trade name) L10, L31, L61, L62, 10R5, 17R2, 25R2 (all manufactured by BASF), Tetronic (trade name) 304, 701, 704, 901, 904, 150R1, HYDROPALAT WE 3323 (all manufactured by BASF), Solsperse (trade name) 20000 (all manufactured by The Lubrizol Corporation), NCW-101, NCW-1001, NCW-1002 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN (trade name) D-1105, D-6112, D-6112-W, D-6315 (all manufactured by Takemoto Oil & Fat Co., Ltd.), OLFINE E1010, Surfynol 104, 400, 440 (all manufactured by Nissin Chemical Co., Ltd.), etc.

[0326] From the viewpoint of improving environmental suitability, the fluorine-based surfactant is preferably a surfactant derived from an alternative material to a compound having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS).

[0327] Examples of the silicone surfactant include linear polymers composed of siloxane bonds and modified siloxane polymers having organic groups introduced into side chains or terminals.

[0328] Specific examples of silicone surfactants include EXP.S-309-2, EXP.S-315, EXP.S-503-2, and EXP.S-505-2 (all manufactured by DIC Corporation), DOWSIL (trade name) 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.) and X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002, KP-101, KP-103, KP-104, KP-1 05. KP-106, KP-109, KP-109, KP-112, KP-120, KP-121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-3 22. KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, KP-652 (the above are Shin-Etsu Chemical Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials Inc.), BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, BYK323 (all manufactured by BYK Chemie), etc.

[0329] The photosensitive resin layer may contain one type of surfactant alone, or two or more types thereof.

[0330] 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, relative to the total mass of the photosensitive resin layer.

[0331] -additive-

[0332] The photosensitive resin layer may contain known additives in addition to the above-mentioned components as needed.

[0333] Examples of additives include polymerization inhibitors, sensitizers, plasticizers, heterocyclic compounds, benzotriazoles, carboxybenzotriazoles, pyridines (isonicotinamide, etc.), purine bases (adenine, etc.), and solvents. The photosensitive resin layer may contain one of each additive alone or two or more.

[0334] The photosensitive resin layer may contain a polymerization inhibitor, and a radical polymerization inhibitor is preferred.

[0335] Examples of polymerization inhibitors include the thermal polymerization inhibitors described in paragraph 0018 of Japanese Patent No. 4502784. Among these, phenothiazine, phenoxazine, or 4-methoxyphenol are preferred. Other polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxylamine aluminum salt, and diphenylnitrosoamine. To minimize the sensitivity of the photosensitive resin composition, nitrosophenylhydroxylamine aluminum salt is preferably used as the polymerization inhibitor.

[0336] Examples of the benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.

[0337] Examples of the carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminovinylcarboxybenzotriazole. Examples of the carboxybenzotriazoles include commercially available products such as CBT-1 (trade name, manufactured by JOHOKU CHEMICAL CO., LTD.).

[0338] The total content of the polymerization inhibitor, benzotriazoles, and carboxybenzotriazoles is preferably 0.01% to 3% by mass, more preferably 0.05% to 1% by mass, relative to the total mass of the photosensitive resin layer. From the perspective of imparting storage stability to the photosensitive resin composition, the above content is preferably 0.01% by mass or greater. On the other hand, from the perspective of maintaining sensitivity and suppressing dye discoloration, the above content is preferably 3% by mass or less.

[0339] The photosensitive resin layer may contain a sensitizer.

[0340] 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, triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

[0341] The photosensitive resin layer may contain one type of sensitizer alone, or two or more types.

[0342] When the photosensitive resin layer contains a sensitizer, the content of the sensitizer can be appropriately selected depending on the purpose. From the viewpoint of improving the sensitivity to the light source and improving the curing speed based on the balance between the polymerization rate and the chain transfer, the content of the sensitizer is preferably 0.01% by mass to 5% by mass, and more preferably 0.05% by mass to 1% by mass, relative to the total mass of the photosensitive resin layer.

[0343] The photosensitive resin layer may contain at least one selected from a plasticizer and a heterocyclic compound.

[0344] Examples of the plasticizer and heterocyclic compound include compounds described in paragraphs 0097 to 0103 and 0111 to 0118 of International Publication No. 2018 / 179640.

[0345] The photosensitive resin layer may contain a solvent. When the photosensitive resin layer is formed from a photosensitive resin composition containing a solvent, the solvent may remain in the photosensitive resin layer.

[0346] In addition, the photosensitive resin layer may also contain known additives such as metal oxide particles, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic precipitation inhibitors.

[0347] Additives contained in the photosensitive resin layer are described in paragraphs 0165 to 0184 of Japanese Patent Application Laid-Open No. 2014-85643, the contents of which are incorporated into this specification.

[0348] <Impurities, etc.>

[0349] The photosensitive resin layer may contain a predetermined amount of impurities.

[0350] Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof. Among them, halide ions, sodium ions, and potassium ions are easily incorporated as impurities, and therefore are preferably set to the following contents.

[0351] The impurity content in the photosensitive resin layer is preferably 80 ppm or less, more preferably 10 ppm or less, and further preferably 2 ppm or less, based on mass. The impurity content can be 1 ppb or more, or even 0.1 ppm or more, based on mass.

[0352] Methods for keeping the impurity content within the above range include selecting raw materials with low impurity content as raw materials for the composition, preventing impurities from entering during the preparation of the photosensitive resin layer, and removing them by washing.

[0353] Impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, and ion chromatography.

[0354] The photosensitive resin layer preferably contains a low content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane. The content of these compounds relative to the total mass of the photosensitive resin layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less, based on mass.

[0355] The lower limit can be set to 10 ppb or greater, or even 100 ppb or greater, based on mass relative to the total mass of the photosensitive resin layer. The content of these compounds can be suppressed using the same methods as for the aforementioned metal impurities. Furthermore, their quantification can be performed using known measurement methods.

[0356] From the viewpoint of improving reliability and lamination properties, the water content in the photosensitive resin layer is preferably 0.01% by mass to 1.0% by mass, and more preferably 0.05% by mass to 0.5% by mass.

[0357] <Residual monomer>

[0358] The photosensitive resin layer may contain residual monomers corresponding to the respective structural units of the alkali-soluble resin.

[0359] From the perspective of patterning properties and reliability, the residual monomer content is preferably 5,000 ppm by mass or less, more preferably 2,000 ppm by mass or less, and even more preferably 500 ppm by mass or less, relative to the total mass of the alkali-soluble resin. The lower limit is not particularly limited, but is preferably 1 ppm by mass or more, and more preferably 10 ppm by mass or more.

[0360] From the perspective of patterning properties and reliability, the residual monomer content of each structural unit of the alkali-soluble resin is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, and even more preferably 100 mass ppm or less, relative to the total mass of the photosensitive resin layer. The lower limit is not particularly limited, but is preferably 0.1 mass ppm or more, and more preferably 1 mass ppm or more.

[0361] The residual monomer content of monomers when synthesizing an alkali-soluble resin by polymer reaction is also preferably within the above range. For example, when synthesizing an alkali-soluble resin by reacting glycidyl acrylate with a carboxylic acid side chain, the glycidyl acrylate content is preferably within the above range.

[0362] The amount of residual monomers can be measured by known methods such as liquid chromatography and gas chromatography.

[0363] <Physical properties, etc.>

[0364] 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, even more preferably 0.5 μm to 15 μm, particularly preferably 0.5 μm to 10 μm, and most preferably 0.5 μm to 8 μm. This improves the developability of the photosensitive resin layer and thus enhances resolution.

[0365] Furthermore, in one embodiment, the thickness is preferably 0.5 μm to 5 μm, more preferably 0.5 μm to 4 μm, and even more preferably 0.5 μm to 3 μm.

[0366] Furthermore, from the viewpoint of resolution, the thickness of the photosensitive resin layer is preferably 10 μm or less, and more preferably 8 μm or less.

[0367] The thickness of each layer of the photosensitive transfer material is measured by observing a cross section perpendicular to the main surface of the photosensitive transfer material using a scanning electron microscope (SEM), measuring the thickness of each layer at 10 or more points on the obtained observation image, and calculating the average value.

[0368] Furthermore, from the perspective of achieving better adhesion, the transmittance of the photosensitive resin layer for light at a wavelength of 365 nm is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more. The upper limit is not particularly limited, but is preferably 99.9% or less.

[0369] <Formation method>

[0370] The method for forming the photosensitive resin layer is not particularly limited as long as it is a method that can form a layer containing the above-mentioned components.

[0371] As a method for forming the photosensitive resin layer, for example, there can be mentioned a method of preparing a photosensitive resin composition containing an alkali-soluble resin, an ethylenically unsaturated compound, a photopolymerization initiator, and a solvent, applying the photosensitive resin composition to a surface of a temporary support, etc., and drying the coating of the photosensitive resin composition.

[0372] Examples of the photosensitive resin composition used for forming the photosensitive resin layer include compositions containing an alkali-soluble resin, an ethylenically unsaturated compound, a photopolymerization initiator, the optional components described above, and a solvent.

[0373] The photosensitive resin composition preferably contains a solvent in order to adjust the viscosity of the photosensitive resin composition and facilitate formation of a photosensitive resin layer.

[0374] -Solvents-

[0375] The solvent contained in the photosensitive resin composition is not particularly limited as long as it can dissolve or disperse the alkali-soluble resin, the ethylenically unsaturated compound, the photopolymerization initiator, and the above-mentioned optional components, and a known solvent can be used.

[0376] Examples of the solvent include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol, ethanol, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aprotic polar solvents (N,N-dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents, amide solvents, lactone solvents, and mixed solvents containing two or more of these.

[0377] When producing a photosensitive transfer material comprising a temporary support, a thermoplastic resin layer, a water-soluble resin layer, a photosensitive resin layer, and a protective film, the photosensitive resin composition preferably contains at least one solvent selected from an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. More preferably, the photosensitive resin composition comprises a mixed solvent comprising at least one solvent selected from an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent and at least one solvent selected from a ketone solvent and a cyclic ether solvent. Even more preferably, the photosensitive resin composition comprises at least one solvent selected from an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent, and a cyclic ether solvent.

[0378] 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.

[0379] 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.

[0380] As the solvent, the solvents described in paragraphs 0092 to 0094 of International Publication No. 2018 / 179640 and the solvents described in paragraph 0014 of Japanese Patent Application Laid-Open No. 2018-177889 can be used, and these contents are incorporated into this specification.

[0381] The photosensitive resin composition may contain one type of solvent alone, or may contain two or more types.

[0382] The content of the solvent when applying the photosensitive resin composition is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content in the photosensitive resin composition.

[0383] The method for preparing the photosensitive resin composition is not particularly limited. For example, a method of preparing the photosensitive resin composition by preliminarily preparing a solution in which each component is dissolved in the above-mentioned solvent and mixing the solution at a predetermined ratio can be mentioned.

[0384] Before forming the photosensitive resin layer, the photosensitive resin composition is preferably filtered using a filter having a pore size of 0.2 μm to 30 μm.

[0385] The method for applying the photosensitive resin composition is not particularly limited, and the composition may be applied by a known method. Examples of the coating method include slit coating, spin coating, curtain coating, and inkjet coating.

[0386] The photosensitive resin layer can be formed by applying a photosensitive resin composition on a protective film to be described later and drying the composition.

[0387] Furthermore, from the viewpoints of resolution and releasability of the temporary support, the photosensitive transfer material in the present invention preferably has another layer between the temporary support and the photosensitive resin layer.

[0388] Preferred examples of the other layer include a thermoplastic resin layer and a water-soluble resin layer.

[0389] Among them, it is preferable to have a thermoplastic resin layer and a water-soluble resin layer as the other layers.

[0390] [Thermoplastic resin layer]

[0391] The photosensitive transfer material of the present invention may include a thermoplastic resin layer. The photosensitive transfer material preferably includes a thermoplastic resin layer between the temporary support and the photosensitive resin layer. This is because the thermoplastic resin layer between the temporary support and the photosensitive resin layer improves the photosensitive transfer material's ability to conform to the adherend and suppresses the introduction of air bubbles between the adherend and the photosensitive transfer material, resulting in improved interlayer adhesion.

[0392] The thermoplastic resin layer preferably contains an alkali-soluble resin as the thermoplastic resin.

[0393] Examples of the alkali-soluble resin include acrylic resins, polystyrene resins, styrene-acrylic acid copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycol.

[0394] From the perspective of developability and adhesion to the layer adjacent to the thermoplastic resin layer, the alkali-soluble resin is preferably an acrylic resin. Here, "acrylic resin" refers to a resin having at least one selected from the group consisting of a structural unit derived from (meth)acrylic acid, a structural unit derived from a (meth)acrylate, and a structural unit derived from a (meth)acrylic amide.

[0395] In the acrylic resin, the total content of the structural units derived from (meth)acrylic acid, the structural units derived from (meth)acrylate, and the structural units derived from (meth)acrylic acid amide is preferably 50% by mass or more relative to the total mass of the acrylic resin. In the acrylic resin, the total content of the structural units derived from (meth)acrylic acid and the structural units derived from (meth)acrylate is preferably 30% by mass to 100% by mass, and more preferably 50% by mass to 100% by mass relative to the total mass of the acrylic resin.

[0396] Furthermore, the alkali-soluble resin is preferably a polymer having an acid group. Examples of the acid group include a carboxyl group, a sulfo group, a phosphoric acid group, and a phosphonic acid group, with a carboxyl group being preferred.

[0397] From the perspective of developability, the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or greater, and more preferably a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or greater. There is no upper limit on the acid value. The acid value of the alkali-soluble resin is preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less.

[0398] As the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more, there is no limitation and it can be appropriately selected from known resins for use. As the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more, for example, the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more in the polymer described in paragraph 0025 of Japanese Patent Application Laid-Open No. 2011-95716, the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more in the polymer described in paragraphs 0033 to 0052 of Japanese Patent Application Laid-Open No. 2010-237589, and the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more in the binder polymer described in paragraphs 0053 to 0068 of Japanese Patent Application Laid-Open No. 2016-224162 can be cited.

[0399] The content of the structural unit having a carboxyl group in the carboxyl group-containing acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and particularly preferably 12 to 30% by mass, based on the total mass of the carboxyl group-containing acrylic resin.

[0400] From the viewpoint of developability and adhesion of a layer adjacent to the thermoplastic resin layer, the alkali-soluble resin is particularly preferably an acrylic resin having a structural unit derived from (meth)acrylic acid.

[0401] 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 ethylenically unsaturated groups, condensation-polymerizing groups (e.g., hydroxyl groups and carboxyl groups), and addition-polymerizing reactive groups (e.g., epoxy groups and (blocked) isocyanate groups).

[0402] 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.

[0403] The thermoplastic resin layer may contain one kind of alkali-soluble resin alone or two or more kinds of alkali-soluble resins.

[0404] From the viewpoint of developability and adhesion to the layer adjacent to the thermoplastic resin layer, the content of the alkali-soluble resin is preferably 10% by mass to 99% by mass, more preferably 20% by mass to 90% by mass, further preferably 40% by mass to 80% by mass, and particularly preferably 50% by mass to 70% by mass, relative to the total mass of the thermoplastic resin layer.

[0405] The thermoplastic resin layer preferably includes a pigment (hereinafter sometimes referred to as "pigment B") having a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 nm to 780 nm when developing color and a maximum absorption wavelength that changes due to acid, base, or free radicals. Preferred embodiments of pigment B are the same as those of pigment N described above, except for the aspects described below.

[0406] From the viewpoint of visibility of the exposed area, visibility of the non-exposed area, and resolution, the dye B is preferably a dye whose maximum absorption wavelength changes with acid or radicals, and more preferably a dye whose maximum absorption wavelength changes with acid.

[0407] From the viewpoint of visibility of the exposed portion, visibility of the non-exposed portion, and resolution, the thermoplastic resin layer preferably contains, as the dye B, a dye whose maximum absorption wavelength changes due to acid, and a compound that generates acid due to light as described later.

[0408] The thermoplastic resin layer may contain the pigment B alone or in combination of two or more.

[0409] From the viewpoint of visibility of the exposed portion and the non-exposed portion, the content of the pigment B is preferably 0.2% by mass or more, more preferably 0.2% by mass 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, relative to the total mass of the thermoplastic resin layer.

[0410] Here, the content ratio of pigment B refers to the content ratio of the pigment when all the pigment B contained in the thermoplastic resin layer is in a coloring state. Below, the quantitative method of the content ratio of pigment B is described by taking the pigment that develops color by free radicals as an example. Prepare two solutions by dissolving the pigment (0.001g) and dissolving the pigment (0.01g) in methyl ethyl ketone (100mL). After adding IRGACURE OXE-01 (BASF) as a photoradical polymerization initiator to each solution obtained, irradiate 365nm light to generate free radicals, which turn all the pigments into a coloring state. Then, using a spectrophotometer (UV3100, Shimadzu Corporation) under atmospheric environment, the absorbance of each solution at a liquid temperature of 25°C is measured to create a calibration curve. Then, instead of the pigment, the thermoplastic resin layer (0.1g) is dissolved in methyl ethyl ketone. Except for this, the absorbance of the solution that makes all the pigments develop color is measured by the same method as above. The amount of the pigment contained in the thermoplastic resin layer is calculated from the absorbance of the solution containing the obtained thermoplastic resin layer according to the calibration curve.

[0411] The thermoplastic resin layer may contain a compound that generates an acid, base, or free radical by light (hereinafter sometimes referred to as "compound C"). Compound C is preferably a compound that generates an acid, base, or free radical by receiving active light (e.g., ultraviolet light and visible light). Examples of compound C include known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators). Compound C is preferably a photoacid generator.

[0412] From the viewpoint of resolution, the thermoplastic resin layer preferably contains a photoacid generator. Examples of the photoacid generator include the photocationic polymerization initiator contained in the negative photosensitive resin layer, and preferred embodiments are the same except for the aspects described below.

[0413] From the viewpoint of sensitivity and resolution, the photoacid generator is preferably at least one selected from an onium salt compound and an oxime sulfonate compound. From the viewpoint of sensitivity, resolution, and adhesion, an oxime sulfonate compound is more preferred.

[0414] Furthermore, the photoacid generator preferably has the following structure.

[0415] [Chemical Formula 3]

[0416]

[0417] The thermoplastic resin layer may contain a photobase generator. Examples of the photobase generator include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamine, O-carbamoyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)-1-benzyl-1-diamine. Methylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaminecobalt(III) tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2,6-dimethyl-3,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine and 2,6-dimethyl-3,5-diacetyl-4-(2,4-dinitrophenyl)-1,4-dihydropyridine.

[0418] The thermoplastic resin layer may contain a photoradical polymerization initiator. Examples of the photoradical polymerization initiator include the photoradical polymerization initiator contained in the negative photosensitive resin layer, and preferred embodiments are also the same.

[0419] The thermoplastic resin layer may contain one type of compound C alone or two or more types of compound C.

[0420] From the viewpoint of visibility of the exposed portion, visibility of the non-exposed portion, and resolution, the content of the compound C is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, relative to the total mass of the thermoplastic resin layer.

[0421] 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.

[0422] The molecular weight of the plasticizer (the molecular weight of an oligomer or polymer is referred to as the weight average molecular weight (Mw). The same shall apply to this paragraph hereinafter) is preferably smaller than the molecular weight of the alkali-soluble resin. The molecular weight of the plasticizer is preferably 200 to 2,000.

[0423] The plasticizer is not limited as long as it is a compound that is compatible with the alkali-soluble resin and exhibits plasticity. From the perspective of imparting plasticity, the plasticizer is preferably a compound having an alkyleneoxy group in the molecule, more preferably a polyalkylene glycol compound. The alkyleneoxy group contained in the plasticizer preferably has a polyethoxy structure or a polypropyleneoxy structure.

[0424] From the viewpoints of resolution and storage stability, the plasticizer preferably contains a (meth)acrylate compound. From the viewpoints of compatibility, resolution, and adhesion to 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.

[0425] Examples of the (meth)acrylate compound used as a plasticizer include those listed above for the ethylenically unsaturated compounds. In a photosensitive transfer material, when a thermoplastic resin layer and a negative photosensitive resin layer are disposed in direct contact, it is preferred that the thermoplastic resin layer and the negative photosensitive resin layer each contain the same (meth)acrylate compound. This is because when the thermoplastic resin layer and the negative photosensitive resin layer each contain the same (meth)acrylate compound, diffusion of components between the layers is suppressed, thereby improving storage stability.

[0426] When the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, the (meth)acrylate compound is preferably not polymerized in the exposed portion after exposure from the viewpoint of adhesion of the layer adjacent to the thermoplastic resin layer.

[0427] In one embodiment, the (meth)acrylate compound used as a plasticizer is preferably a (meth)acrylate compound having two or more (meth)acryloyl groups in one molecule from the viewpoints of resolution, adhesion to a layer adjacent to the thermoplastic resin layer, and developability.

[0428] In one embodiment, the (meth)acrylate compound used as the plasticizer is preferably a (meth)acrylate compound or a urethane (meth)acrylate compound having an acid group.

[0429] The thermoplastic resin layer may contain one type of plasticizer alone or two or more types of plasticizers.

[0430] From the viewpoints of resolution, adhesion to the layer adjacent to the thermoplastic resin layer, and developability, the content of the plasticizer is preferably 1% by mass to 70% by mass, more preferably 10% by mass to 60% by mass, and particularly preferably 20% by mass to 50% by mass, relative to the total mass of the thermoplastic resin layer.

[0431] From the viewpoint of thickness uniformity, the thermoplastic resin layer preferably contains a surfactant. Examples of the surfactant include the surfactants that can be contained in the negative photosensitive resin layer, and preferred embodiments are also the same.

[0432] The thermoplastic resin layer may contain one type of surfactant alone or two or more types of surfactants.

[0433] 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, relative to the total mass of the thermoplastic photosensitive resin layer.

[0434] The thermoplastic resin layer may contain a sensitizer. Examples of the sensitizer include the sensitizers that may be contained in the negative photosensitive resin layer.

[0435] The thermoplastic resin layer may contain one type of sensitizer alone or two or more types of sensitizers.

[0436] From the viewpoint of improving sensitivity to light sources and visibility of exposed and non-exposed areas, the content of the sensitizer is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass, relative to the total mass of the thermoplastic resin layer.

[0437] The thermoplastic resin layer may contain known additives in addition to the above-mentioned components as needed.

[0438] The thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese Patent Application Laid-Open No. 2014-85643, the contents of which are incorporated herein by reference.

[0439] The thickness of the thermoplastic resin layer is not limited. From the perspective of adhesion of adjacent layers to the thermoplastic resin layer, the average thickness of the thermoplastic resin layer is preferably 1 μm or greater, more preferably 2 μm or greater. There is no upper limit to the average thickness of the thermoplastic resin layer. From the perspective of developability and resolution, 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.

[0440] The method for forming the thermoplastic resin layer is not limited as long as it is a method that can form a layer containing the above-mentioned components. As a method for forming the thermoplastic resin layer, for example, a method of applying a thermoplastic resin composition on the surface of a temporary support and drying the coating of the thermoplastic resin composition can be cited.

[0441] Examples of the thermoplastic resin composition include compositions containing the above-mentioned components. The thermoplastic resin composition preferably contains a solvent in order to adjust the viscosity of the thermoplastic resin composition and facilitate formation of the thermoplastic resin layer.

[0442] The solvent contained in the thermoplastic resin composition is not limited as long as it can dissolve or disperse the components contained in the thermoplastic resin layer. Examples of the solvent include the solvents that can be contained in the above-mentioned photosensitive resin composition, and the preferred embodiments are the same.

[0443] The thermoplastic resin composition may contain one type of solvent alone or two or more types of solvents.

[0444] The content of the solvent in the thermoplastic resin composition is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content in the thermoplastic resin composition.

[0445] The preparation of the thermoplastic resin composition and the formation of the thermoplastic resin layer can be carried out according to the above-mentioned methods for preparing the photosensitive resin composition and forming the photosensitive resin layer. For example, a solution of each component contained in the thermoplastic resin layer dissolved in the above-mentioned solvent is prepared in advance, and the resulting solutions are mixed in predetermined proportions to prepare the thermoplastic resin composition. The resulting thermoplastic resin composition is then applied to the surface of a temporary support, and the coating of the thermoplastic resin composition is dried to form the thermoplastic resin layer. Alternatively, the thermoplastic resin layer can be formed on the surface of the photosensitive resin layer after the photosensitive resin layer is formed on the protective film.

[0446] [Water-soluble resin layer]

[0447] The photosensitive transfer material preferably has a water-soluble resin layer between the thermoplastic resin layer and the photosensitive resin layer. The water-soluble resin layer can suppress mixing of components during formation and storage of multiple layers.

[0448] The water-soluble resin layer is preferably a water-soluble layer from the viewpoint of developability and suppression of mixing of components during coating of multiple layers and storage after coating. In the present invention, "water-soluble" means a solubility of 0.1 g or more in 100 g of water at a pH of 7.0 at a liquid temperature of 22°C.

[0449] As the water-soluble resin layer, for example, there can be mentioned an oxygen barrier layer having an oxygen barrier function described as a "separation layer" in Japanese Patent Application Laid-Open No. 5-72724. By using the water-soluble resin layer as an oxygen barrier layer, the sensitivity during exposure is improved, and the time load of the exposure machine is reduced, resulting in improved productivity. The oxygen barrier layer used as the water-soluble resin layer can be appropriately selected from known layers. The oxygen barrier layer used as the water-soluble resin layer is preferably an oxygen barrier layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (a 1% by mass aqueous solution of sodium carbonate at 22°C).

[0450] The water-soluble resin layer preferably contains a resin. Examples of the resin contained in the water-soluble resin layer include polyvinyl alcohol resins, polyvinyl pyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof. The resin contained in the water-soluble resin layer is preferably a water-soluble resin.

[0451] From the viewpoint of suppressing mixing of components between multiple layers, the resin contained in the water-soluble resin layer is preferably a resin different from either the polymer A contained in the negative photosensitive resin layer or the thermoplastic resin (alkali-soluble resin) contained in the thermoplastic resin layer.

[0452] From the viewpoint of oxygen barrier properties and suppression of mixing of components during multi-layer coating and storage after coating, the water-soluble resin layer preferably contains polyvinyl alcohol, and more preferably contains polyvinyl alcohol and polyvinyl pyrrolidone.

[0453] The water-soluble resin layer may contain one type of resin alone or two or more types of resins.

[0454] From the viewpoint of oxygen barrier properties and mixing of components during coating of multiple layers and storage after coating, the content ratio of the resin in the water-soluble resin layer is preferably 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 particularly preferably 90% by mass to 100% by mass, relative to the total mass of the water-soluble resin layer.

[0455] Furthermore, the water-soluble resin layer may contain additives as needed. Examples of the additives include surfactants.

[0456] 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 this range, mixing of components during the formation and storage of multiple layers can be suppressed without reducing oxygen barrier properties, and the increase in the time required to remove the water-soluble resin layer during development can be suppressed.

[0457] The method for forming the water-soluble resin layer is not limited as long as it can form a layer containing the above-mentioned components. Examples of the method for forming the water-soluble resin layer include a method in which a water-soluble resin layer composition is applied to the surface of a thermoplastic resin layer or a negative photosensitive resin layer, and then the coating film of the water-soluble resin layer composition is dried.

[0458] Examples of the composition for the water-soluble resin layer include compositions comprising a resin and any additives. To adjust the viscosity of the composition for the water-soluble resin layer and facilitate formation of the water-soluble resin layer, the composition for the water-soluble resin layer preferably contains a solvent. The solvent is not limited as long as it can dissolve or disperse the resin. The solvent is preferably at least one selected from water and a water-miscible organic solvent, more preferably water or a mixed solvent of water and a water-miscible organic solvent.

[0459] Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerol. The water-miscible organic solvent is preferably an alcohol having 1 to 3 carbon atoms, more preferably methanol or ethanol.

[0460] The photosensitive transfer material may include layers other than the above-mentioned layers (hereinafter also referred to as "other layers"). Examples of the other layers include contrast enhancement layers.

[0461] The contrast enhancement layer is described in paragraph 0134 of International Publication No. 2018 / 179640. Furthermore, other layers are described in paragraphs 0194 to 0196 of Japanese Patent Application Laid-Open No. 2014-85643. The contents of these publications are incorporated into this specification.

[0462] 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 using the method for measuring the thickness of each layer described above.

[0463] From the viewpoint of further exerting the effects of the present invention, the total thickness of each layer in the photosensitive transfer material excluding the temporary support and the protective film is preferably 20 μm or less, more preferably 10 μm or less, further preferably 8 μm or less, and particularly preferably 2 μm or more and 8 μm or less.

[0464] From the viewpoint of further exerting the effects of the present invention, the total thickness of the photosensitive resin layer, water-soluble resin layer and thermoplastic resin layer in the photosensitive transfer material is preferably 20 μm or less, more preferably 10 μm or less, further preferably 8 μm or less, and particularly preferably 2 μm or more and 8 μm or less.

[0465] [Method for producing photosensitive transfer material]

[0466] The method for producing the photosensitive transfer material according to the present invention is not particularly limited, and a known production method, for example, a known method for forming each layer, can be used.

[0467] Below, for reference Figure 1 , while explaining the method for producing the photosensitive transfer material of the present invention. However, the photosensitive transfer material of the present invention is not limited to the photosensitive transfer material having Figure 1 Materials of the structure shown.

[0468] Figure 1 This 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 invention. Figure 1The photosensitive transfer material 20 shown has a structure in which 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 stacked in this order.

[0469] As a method for producing the above-mentioned photosensitive transfer material 20, for example, there can be cited a method including the following steps: a step of applying a thermoplastic resin composition on the surface of a temporary support 11 and then drying the coating of the thermoplastic resin composition to form a thermoplastic resin layer 13; a step of applying a water-soluble resin layer composition on the surface of the thermoplastic resin layer 13 and then drying the coating of the water-soluble resin layer composition to form a water-soluble resin layer 15; and a step of applying a photosensitive resin composition containing a binder polymer and an ethylenically unsaturated compound on the surface of the water-soluble resin layer 15 and then drying the coating of the photosensitive resin composition to form a photosensitive resin layer 16.

[0470] In the above-described production method, it is preferred to use a thermoplastic resin composition containing at least one solvent selected from an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, a water-soluble resin layer composition containing at least one solvent selected from water and a water-miscible organic solvent, and a photosensitive resin composition containing a binder polymer, an ethylenically unsaturated compound, and at least one solvent selected from an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. This can suppress mixing of components contained in the thermoplastic resin layer 13 with components contained in the water-soluble resin layer 15 during the period of coating the water-soluble resin layer composition on the surface of the thermoplastic resin layer 13 and / or storage of the laminate having a coating film of the water-soluble resin layer composition. Furthermore, mixing of components contained in the water-soluble resin layer 15 with components contained in the photosensitive resin layer 16 can be suppressed during the period of coating the water-soluble resin layer 15 and / or storage of the laminate having a coating film of the photosensitive resin composition.

[0471] The protective film 19 is brought into pressure contact with the photosensitive resin layer 17 of the laminated body produced by the above-described production method, thereby producing the photosensitive transfer material 20 .

[0472] As a method for manufacturing a photosensitive transfer material used in the present invention, it is preferred to manufacture a photosensitive transfer material 20 including 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, by including a step of providing a protective film 19 in contact with the second surface of the photosensitive resin layer 17.

[0473] After the photosensitive transfer material 20 is manufactured by the above-described manufacturing method, a roll-shaped photosensitive transfer material can be produced and stored by winding the photosensitive transfer material 20. The roll-shaped photosensitive transfer material can be provided as is to the substrate lamination step in the roll-to-roll method described later.

[0474] The photosensitive transfer material of the present invention can be appropriately used for various applications required for precision microfabrication based on photolithography. After the photosensitive resin layer is patterned, the photosensitive resin layer can be etched as a coating, or electroforming with electroplating as the main method can be performed. In addition, the cured film obtained by patterning can be used as a permanent film, for example, as an interlayer insulating film, a wiring protection film, a wiring protection film with a refractive index matching layer, etc. In addition, the photosensitive transfer material of the present invention can be appropriately used for various wiring formation applications of semiconductor packages, printed circuit boards, sensor substrates, touch panels, electromagnetic shielding materials, conductive films such as thin film heaters, liquid crystal sealing materials, the formation of structures in the fields of microcomputers or microelectronics, etc.

[0475] Furthermore, in the photosensitive transfer material of the first embodiment, a preferred embodiment is also one in which the photosensitive resin layer is a colored resin layer containing a pigment.

[0476] In addition to the uses mentioned above, the colored resin layer is suitable for forming colored pixels or black matrices in color filters used in liquid crystal displays (LCDs) and solid-state imaging devices such as CCDs (charge-coupled devices) and CMOSs ​​(complementary metal oxide semiconductors).

[0477] The configuration other than the pigment in the colored resin layer is the same as the above configuration.

[0478] Pigments

[0479] The photosensitive resin layer may be a colored resin layer containing a pigment.

[0480] In recent years, electronic devices have liquid crystal display windows that are sometimes equipped with cover glass (cover glass) to protect the liquid crystal display window. The cover glass has a black frame-shaped light-shielding layer formed on the periphery of the back side of a transparent glass substrate. To form this light-shielding layer, a colored resin layer can be used.

[0481] The pigment can be appropriately selected according to the desired hue and can be selected from black pigments, white pigments, and color pigments other than black and white. In particular, when forming a black pattern, a black pigment is preferably selected as the pigment.

[0482] As black pigment, as long as in the scope of the effect in the present invention, then can suitably select known black pigment (organic pigment or inorganic pigment etc.).Wherein, from the viewpoint of optical density, as black pigment, for example, can preferably enumerate carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide and graphite etc., especially preferred carbon black.As carbon black, from the viewpoint of surface resistance, preferably at least a portion of surface is coated with resin carbon black.

[0483] From the viewpoint of dispersion stability, the particle size of the black pigment is preferably 0.001 μm to 0.1 μm, and more preferably 0.01 μm to 0.08 μm in terms of number average particle size.

[0484] Here, the particle size refers to the diameter of a circle obtained by calculating the area of ​​the pigment particles from a photographic image of the pigment particles taken with an electron microscope and taking into account a circle with the same area as the area of ​​the pigment particles. The number average particle size is the average value obtained by calculating the above particle size for any 100 particles and averaging the 100 particle sizes thus calculated.

[0485] As pigments other than black pigments, white pigments described in paragraphs 0015 and 0114 of Japanese Patent Application Laid-Open No. 2005-007765 can be used. Specifically, among white pigments, inorganic pigments are preferably titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate, more preferably titanium oxide or zinc oxide, and even more preferably titanium oxide. As inorganic pigments, rutile or anatase titanium oxide is more preferably used, and rutile titanium oxide is particularly preferred.

[0486] Furthermore, the surface of titanium oxide may be treated with silica, alumina, titania, zirconia, or an organic substance, or may be treated with two or more of these treatments. This can suppress the catalytic activity of titanium oxide and improve its heat resistance and matte properties.

[0487] From the viewpoint of reducing the thickness of the photosensitive resin layer after heating, the surface treatment of the titanium oxide is preferably at least one of an alumina treatment and a zirconia treatment, and particularly preferably both an alumina treatment and a zirconia treatment.

[0488] Furthermore, when the photosensitive resin layer is a colored resin layer, it is also preferred that the photosensitive resin layer further contain a color pigment in addition to the black pigment and the white pigment from the viewpoint of transferability. When a color pigment is contained, the particle size of the color pigment is preferably 0.1 μm or less, and more preferably 0.08 μm or less, from the viewpoint of better dispersibility.

[0489] Examples of color pigments include Victoria Pure Blue BO (Color Index (CI) 42595), auramine (CI 41000), Fat Black HB (CI 26150), Monolight Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hostaperm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11), Pastel Pink B Supura (CI Pigment Red 81), Monastral Fast Blue (CI Pigment Red 146), and Permanent Yellow HR (CI Pigment Yellow 83). Blue) (CI Pigment Blue 15), Monolight Fast Black B (CI Pigment Black 1) and carbon, CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red 215, CI Pigment Green 7, CI Pigment Blue 15:1, CI Pigment Blue 15:4, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64 and CI Pigment Violet 23. Among them, CI Pigment Red 177 is preferred.

[0490] When the photosensitive resin layer contains a pigment, the content of the pigment is preferably greater than 3% by mass and less than 40% by mass, more preferably greater than 3% by mass and less than 35% by mass, further preferably greater than 5% by mass and less than 35% by mass, and particularly preferably greater than 10% by mass and less than 35% by mass, relative to the total mass of the photosensitive resin layer.

[0491] When the photosensitive resin layer contains pigments other than the black pigment (white pigment and color pigment), the content of the pigments other than the black pigment is preferably 30% by mass or less, more preferably 1% by mass to 20% by mass, and further preferably 3% by mass to 15% by mass relative to the black pigment.

[0492] When the photosensitive resin layer contains a black pigment and is formed from a photosensitive resin composition, the black pigment (preferably carbon black) is preferably introduced into the photosensitive resin composition in the form of a pigment dispersion.

[0493] The dispersion can be prepared by adding a mixture obtained by pre-mixing black pigment and pigment dispersant to an organic solvent (or vehicle) and dispersing it using a disperser. The pigment dispersant can be selected according to the pigment and solvent, for example, a commercially available dispersant can be used. In addition, the vehicle refers to the medium part that disperses the pigment when preparing the pigment dispersion. It is liquid and contains a binder component that maintains the black pigment in a dispersed state and a solvent component (organic solvent) that dissolves and dilutes the binder component.

[0494] As a dispersion machine, there is no particular limitation, for example, known dispersion machines such as a kneader, a roller mill, an attritor, a super mill, a dissolver, a homomixer and a sand mill can be enumerated. In addition, the dispersion machine can be finely pulverized by mechanical grinding and friction. About dispersion machine and fine pulverization, reference can be made to the record of " Pigment Dictionary " (written by Kunizo Asakura, first edition, Asakura Bookstore, 2000, 438 pages, 310 pages).

[0495] [Photosensitive transfer material according to the second embodiment]

[0496] Hereinafter, the photosensitive transfer material according to the second embodiment will be described by taking an example.

[0497] Figure 2 The photosensitive transfer material 10 shown includes 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.

[0498] and, Figure 2 The photosensitive transfer material 10 shown in FIG. 1 is in an embodiment in which the refractive index adjusting layer 5 is provided, but the refractive index adjusting layer 5 may not be provided.

[0499] Hereinafter, each element constituting the photosensitive transfer material according to the second embodiment will be described.

[0500] The temporary support and protective film used for the photosensitive transfer material of the second embodiment are the same as those of the photosensitive transfer material of the first embodiment, and the preferred embodiments are also the same.

[0501] [Photosensitive resin layer]

[0502] The photosensitive transfer material has a photosensitive resin layer.

[0503] After the photosensitive resin layer is transferred onto the transfer target, exposure and development are performed, whereby a pattern can be formed on the transfer target.

[0504] Hereinafter, components that may be contained in the photosensitive resin layer will be described in detail.

[0505] <Binder polymer>

[0506] The photosensitive resin layer may contain a binder polymer.

[0507] Examples of the binder polymer include (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkanol resins, phenolic resins, ester resins, urethane resins, epoxy acrylate resins obtained by reacting epoxy resins with (meth)acrylic acid, and acid-modified epoxy acrylate resins obtained by reacting epoxy acrylate resins with acid anhydrides.

[0508] As one of the preferred aspects of the binder polymer, a (meth)acrylic resin can be mentioned from the viewpoint of excellent alkali developability and thin film formability.

[0509] In this specification, a (meth)acrylic resin refers to a resin having structural units derived from a (meth)acrylic compound. The content of the structural units derived from the (meth)acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, relative to all structural units in the (meth)acrylic resin.

[0510] The (meth)acrylic resin may be composed solely of structural units derived from a (meth)acrylic compound, or may contain structural units derived from a polymerizable monomer other than a (meth)acrylic compound. Specifically, the upper limit of the content of structural units derived from a (meth)acrylic compound is 100% by mass or less relative to all structural units in the (meth)acrylic resin.

[0511] Examples of the (meth)acrylic acid compound include (meth)acrylic acid, (meth)acrylate, (meth)acrylic acid ester, (meth)acrylamide, and (meth)acrylonitrile.

[0512] Examples of the (meth)acrylate include alkyl (meth)acrylates, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, benzyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, with alkyl (meth)acrylate being preferred.

[0513] Examples of (meth)acrylamide include acrylamides such as diacetone acrylamide.

[0514] Examples of the alkyl (meth)acrylate include alkyl (meth)acrylates having an alkyl group having 1 to 12 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, and dodecyl (meth)acrylate.

[0515] As the (meth)acrylate, an alkyl (meth)acrylate having an alkyl group having 1 to 4 carbon atoms is preferable, and methyl (meth)acrylate or ethyl (meth)acrylate is more preferable.

[0516] The (meth)acrylic resin may have a structural unit other than the structural unit derived from the (meth)acrylic compound.

[0517] The polymerizable monomer forming the above-mentioned structural unit is not particularly limited as long as it is a compound other than a (meth)acrylic acid compound copolymerizable with the (meth)acrylic acid compound. Examples thereof include styrene compounds which may have a substituent at the α position or on the aromatic ring, such as styrene, vinyltoluene, and α-methylstyrene; vinyl alcohol esters such as acrylonitrile and vinyl n-butyl ether; maleic acid, maleic anhydride, maleic acid monoesters such as monomethyl maleate, monoethyl maleate, and monoisopropyl maleate; fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, and crotonic acid.

[0518] These polymerizable monomers may be used alone or in combination of two or more.

[0519] Furthermore, from the viewpoint of further improving alkali developability, the (meth)acrylic resin preferably contains a structural unit having an acid group. Examples of the acid group include a carboxyl group, a sulfone group, a phosphoric acid group, and a phosphonic acid group.

[0520] Among these, the (meth)acrylic resin more preferably contains a structural unit having a carboxyl group, and further preferably contains a structural unit derived from the above-mentioned (meth)acrylic acid.

[0521] From the perspective of excellent developability, the content of structural units having an acid group (preferably structural units derived from (meth)acrylic acid) in the (meth)acrylic resin is preferably 10% by mass or more relative to the total mass of the (meth)acrylic resin. The upper limit is not particularly limited, but from the perspective of excellent alkali resistance, it is preferably 50% by mass or less, and more preferably 40% by mass or less.

[0522] Furthermore, the (meth)acrylic resin more preferably has a structural unit derived from the above-mentioned alkyl (meth)acrylate.

[0523] The content of the structural unit derived from the alkyl (meth)acrylate in the (meth)acrylic resin is preferably 50 to 90% by mass, more preferably 60 to 90% by mass, and further preferably 65 to 90% by mass, based on all the structural units of the (meth)acrylic resin.

[0524] The (meth)acrylic resin preferably contains both a structural unit derived from (meth)acrylic acid and a structural unit derived from an alkyl (meth)acrylate. More preferably, the (meth)acrylic resin contains only a structural unit derived from (meth)acrylic acid and a structural unit derived from an alkyl (meth)acrylate.

[0525] Furthermore, 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 preferred.

[0526] Furthermore, from the viewpoint of achieving more excellent effects in the present invention, the (meth)acrylic resin preferably has at least one selected from the group consisting of structural units derived from methacrylic acid and structural units derived from alkyl methacrylates, and preferably has both structural units derived from methacrylic acid and structural units derived from alkyl methacrylates.

[0527] From the perspective of achieving even better effects of the present invention, the total content of structural units derived from methacrylic acid and structural units derived from alkyl methacrylate in the (meth)acrylic resin is preferably 40% by mass or more, and more preferably 60% by mass or more, relative to all structural units in the (meth)acrylic resin. The upper limit is not particularly limited and may be 100% by mass or less, and preferably 80% by mass or less.

[0528] Furthermore, from the viewpoint of achieving more excellent effects in the present invention, the (meth)acrylic resin also preferably has at least one selected from the group consisting of structural units derived from methacrylic acid and structural units derived from methacrylic acid alkyl esters, and at least one selected from the group consisting of structural units derived from acrylic acid and structural units derived from acrylate alkyl esters.

[0529] From the viewpoint of further improving the effects of the present invention, the total content of the structural units derived from methacrylic acid and the structural units derived from alkyl methacrylate is preferably 60 / 40 to 80 / 20 in terms of mass ratio relative to the total content of the structural units derived from acrylic acid and the structural units derived from alkyl acrylate.

[0530] The (meth)acrylic resin preferably has an ester group at the terminal from the viewpoint of excellent developability of the photosensitive resin layer after transfer.

[0531] The terminal portion of the (meth)acrylic resin is composed of a site derived from the polymerization initiator used for 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.

[0532] Furthermore, another preferred embodiment of the binder polymer includes an alkali-soluble resin.

[0533] For example, from the viewpoint of developability, the binder polymer preferably has an acid value of 60 mgKOH / g or more.

[0534] Furthermore, from the viewpoint of easily forming a strong film by thermal cross-linking with the cross-linking component by heating, the binder polymer is more preferably, for example, a resin having a carboxyl group (so-called carboxyl group-containing resin) having an acid value of 60 mgKOH / g or more, and further preferably a (meth) acrylic resin having a carboxyl group (so-called carboxyl group-containing (meth) acrylic resin) having an acid value of 60 mgKOH / g or more.

[0535] If the binder polymer is a resin having carboxyl groups, the three-dimensional crosslinking density can be increased by thermal crosslinking, for example, by adding a thermally crosslinkable compound such as a blocked isocyanate compound. Furthermore, if the carboxyl groups of the resin having carboxyl groups are dehydrated and hydrophobized, wet heat resistance can be improved.

[0536] The carboxyl group-containing (meth)acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited as long as the above-mentioned acid value conditions are satisfied, and can be appropriately selected from known (meth)acrylic resins.

[0537] For example, carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or higher among the polymers described in paragraph 0025 of JP-A-2011-095716 and carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or higher among the polymers described in paragraphs 0033 to 0052 of JP-A-2010-237589 can be preferably used.

[0538] Another preferred embodiment of the binder polymer is a styrene-acrylic acid copolymer. In this specification, a styrene-acrylic acid copolymer refers to a resin having structural units derived from a styrene compound and structural units derived from a (meth)acrylic acid compound, wherein the total content of the structural units derived from the styrene compound and the structural units derived from the (meth)acrylic acid compound is preferably 30% by mass or more, and more preferably 50% by mass or more, relative to the total structural units of the copolymer.

[0539] 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 even more preferably 5% by mass to 80% by mass, based on all the structural units of the copolymer.

[0540] The content of the structural unit derived from the (meth)acrylic acid compound is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 20% to 95% by mass, based on all the structural units of the copolymer.

[0541] From the viewpoint of achieving more excellent effects in the present invention, the binder polymer preferably has an aromatic ring structure, and more preferably contains a structural unit having an aromatic ring structure.

[0542] Examples of the monomer forming the structural unit having an aromatic ring structure include styrene compounds such as styrene, t-butoxystyrene, methylstyrene, and α-methylstyrene, and benzyl (meth)acrylate.

[0543] Among them, styrene compounds are preferred, and styrene is more preferred.

[0544] Furthermore, from the viewpoint of achieving more excellent effects in the present invention, the binder polymer more preferably has a structural unit represented by the following formula (S) (structural unit derived from styrene).

[0545] [Chemical Formula 4]

[0546]

[0547] When the binder polymer contains a structural unit having an aromatic ring structure, from the viewpoint of achieving a more excellent effect in the present invention, the content of the structural unit having an aromatic ring structure is preferably 5% by mass to 90% by mass relative to all the structural units of the binder polymer, more preferably 10% by mass to 70% by mass, and further preferably 20% by mass to 60% by mass.

[0548] Furthermore, from the viewpoint of achieving better effects in the present invention, the content of the structural units having an aromatic ring structure in the binder polymer is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, and further preferably 20 mol% to 60 mol%, relative to all structural units of the binder polymer.

[0549] In addition, from the viewpoint of achieving a better effect in the present invention, the content of the structural unit represented by the above formula (S) in the binder polymer is preferably 5 mol% to 70 mol% relative to all the structural units of the binder polymer, more preferably 10 mol% to 60 mol%, further preferably 20 mol% to 60 mol%, and particularly preferably 20 mol% to 50 mol%.

[0550] In this specification, when the content of a "structural unit" is specified by molar ratio, the "structural unit" and the "monomer unit" have the same meaning. Furthermore, in this specification, the "monomer unit" may be modified after polymerization through a polymer reaction or the like. This also applies hereinafter.

[0551] From the perspective of achieving even better effects in the present invention, the binder polymer preferably has an aliphatic hydrocarbon ring structure. That is, the binder polymer preferably contains 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. Among these, the binder polymer more preferably has a ring structure comprising two or more condensed aliphatic hydrocarbon rings.

[0552] Examples of the ring constituting the aliphatic hydrocarbon ring structure in the structural unit having an aliphatic hydrocarbon ring structure include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, and an isoborane ring.

[0553] Among them, from the viewpoint of more excellent effects in the present invention, a ring in which two or more aliphatic hydrocarbon rings are condensed is preferred, and a tetrahydrodicyclopentadiene ring (tricyclo[5.2.1.0 2，6 ]decane ring).

[0554] Examples of the monomer that forms the structural unit having an aliphatic hydrocarbon ring structure include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate.

[0555] Furthermore, from the viewpoint of achieving more excellent effects in the present invention, the binder polymer more preferably has a structural unit represented by the following formula (Cy), and more preferably has a structural unit represented by the above formula (S) and a structural unit represented by the following formula (Cy).

[0556] [Chemical Formula 5]

[0557]

[0558] R in formula (Cy) M represents a hydrogen atom or a methyl group, R Cy It represents a monovalent group having an aliphatic hydrocarbon ring structure.

[0559] R in formula (Cy) M Preferred is methyl.

[0560] From the viewpoint of further improving the effects of the present invention, R in formula (Cy) CyIt is preferably a monovalent group having an aliphatic hydrocarbon ring structure having 5 to 20 carbon atoms, more preferably a monovalent group having an aliphatic hydrocarbon ring structure having 6 to 16 carbon atoms, and still more preferably a monovalent group having an aliphatic hydrocarbon ring structure having 8 to 14 carbon atoms.

[0561] Furthermore, from the viewpoint of further improving the effects of the present invention, R Cy The aliphatic hydrocarbon ring structure in is preferably a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure or an isoborane ring structure, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, further preferably a tetrahydrodicyclopentadiene ring structure.

[0562] Furthermore, from the viewpoint of further improving the effects of the present invention, R Cy The aliphatic hydrocarbon ring structure in is preferably a ring structure in which two or more aliphatic hydrocarbon rings are condensed, and more preferably a ring in which 2 to 4 aliphatic hydrocarbon rings are condensed.

[0563] Furthermore, from the viewpoint of further improving the effects of the present invention, R in formula (Cy) Cy The group in which the oxygen atom of -C(=O)O- in formula (Cy) is directly bonded to the aliphatic hydrocarbon ring structure, that is, an aliphatic hydrocarbon ring group is preferred, a cyclohexyl group or a dicyclopentyl group is more preferred, and a dicyclopentyl group is further preferred.

[0564] The binder polymer may contain one type of structural unit having an aliphatic hydrocarbon ring structure alone, or may contain two or more types.

[0565] When the binder polymer contains a structural unit having an aliphatic hydrocarbon ring structure, from the viewpoint of achieving a more excellent effect in the present invention, the content of the structural unit having an aliphatic hydrocarbon ring structure is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 80% by mass, and even more preferably 20% by mass to 70% by mass relative to all the structural units of the binder polymer.

[0566] Furthermore, from the viewpoint of achieving better effects in the present invention, the content of the structural unit having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 5 mol% to 70 mol% relative to all the structural units of the binder polymer, more preferably 10 mol% to 60 mol%, and further preferably 20 mol% to 50 mol%.

[0567] In addition, from the viewpoint of achieving better effects in the present invention, the content of the structural unit represented by the above formula (Cy) in the binder polymer is preferably 5 mol% to 70 mol% relative to all structural units of the binder polymer, more preferably 10 mol% to 60 mol%, and further preferably 20 mol% to 50 mol%.

[0568] In the case where the binder polymer has structural units having an aromatic ring structure and structural units having an aliphatic hydrocarbon ring structure, from the viewpoint of achieving a more excellent effect in the present invention, the total content of the structural units having an aromatic ring structure and the structural units having an aliphatic hydrocarbon ring structure relative to all the structural units of the binder polymer is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and even more preferably 40% by mass to 75% by mass.

[0569] Furthermore, from the viewpoint of achieving a more excellent effect in the present invention, the total content of structural units having an aromatic ring structure and structural units having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 10 mol% to 80 mol% relative to all structural units of the binder polymer, more preferably 20 mol% to 70 mol%, and even more preferably 40 mol% to 60 mol%.

[0570] In addition, from the viewpoint of achieving a better effect in the present invention, the total content of the structural unit represented by the above formula (S) and the structural unit represented by the above formula (Cy) in the binder polymer is preferably 10 mol% to 80 mol%, more preferably 20 mol% to 70 mol%, and further preferably 40 mol% to 60 mol% relative to all the structural units of the binder polymer.

[0571] Furthermore, from the viewpoint of achieving better effects in the present invention, 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 preferably satisfy the relationship represented by the following formula (SCy), more preferably satisfy the following formula (SOy-1), and further preferably satisfy the following formula (SCy-2).

[0572] 0.2≤nS / (nS+nCy)≤0.8 Formula (SCy)

[0573] 0.30≤nS / (nS+nCy)≤0.75 Formula (SCy-1)

[0574] 0.40≤nS / (nS+nCy)≤0.70 Formula (SCy-2)

[0575] From the viewpoint of achieving more excellent effects in the present invention, the binder polymer preferably contains a structural unit having an acid group.

[0576] Examples of the acid group include a carboxyl group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, and a carboxyl group is preferred.

[0577] As the structural unit having the acid group, a structural unit derived from (meth)acrylic acid as shown below is preferred, and a structural unit derived from methacrylic acid is more preferred.

[0578] [Chemical Formula 6]

[0579]

[0580] The binder polymer may contain a single type of structural unit having an acid group, or may contain two or more types.

[0581] When the binder polymer contains a structural unit having an acid group, from the viewpoint of achieving a more excellent effect in the present invention, the content of the structural unit having an acid group is preferably 5% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and even more preferably 10% by mass to 30% by mass relative to all the structural units of the binder polymer.

[0582] Furthermore, from the viewpoint of achieving better effects in the present invention, the content of the structural unit having an acid group in the binder polymer is preferably 5 mol% to 70 mol% relative to all the structural units of the binder polymer, more preferably 10 mol% to 50 mol%, and further preferably 20 mol% to 40 mol%.

[0583] Furthermore, from the viewpoint of further improving the effects of the present invention, the content of the structural units derived from (meth)acrylic acid in the binder polymer is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 50 mol%, and even more preferably 20 mol% to 40 mol%, relative to all the structural units of the binder polymer.

[0584] From the viewpoint of achieving more excellent effects in the present invention, the binder polymer preferably has a reactive group, and more preferably contains a structural unit having a reactive group.

[0585] As the reactive group, a free radical polymerizable group is preferred, and an ethylenically unsaturated group is more preferred. When the binder polymer has an ethylenically unsaturated group, the binder polymer preferably contains a structural unit having an ethylenically unsaturated group in a side chain.

[0586] In this specification, a "main chain" refers to the relatively longest bond chain in the molecule of a polymer compound constituting a resin, and a "side chain" refers to an atomic group branching from the main chain.

[0587] As the ethylenically unsaturated group, an allyl group or a (meth)acryloyloxy group is more preferable.

[0588] Examples of the structural unit having a reactive group include the following structural units, but the present invention is not limited to these.

[0589] [Chemical Formula 7]

[0590]

[0591] The binder polymer may contain a single type of structural unit having a reactive group, or may contain two or more types.

[0592] When the binder polymer contains a structural unit having a reactive group, from the viewpoint of achieving a more excellent effect in the present invention, the content of the structural unit having a reactive group is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 50% by mass, and even more preferably 20% by mass to 40% by mass relative to all the structural units of the binder polymer.

[0593] Furthermore, from the viewpoint of achieving better effects in the present invention, the content of the structural unit having a reactive group in the binder polymer is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, and further preferably 20 mol% to 50 mol%, relative to all structural units of the binder polymer.

[0594] Examples of methods for introducing reactive groups into binder polymers include reacting compounds such as epoxy compounds, blocked isocyanate compounds, isocyanate compounds, vinyl sulfone compounds, aldehyde compounds, methylol compounds, and carboxylic anhydride with functional groups such as hydroxyl groups, carboxyl groups, primary amino groups, secondary amino groups, acetoacetyl groups, and sulfonic groups.

[0595] A preferred example of a method for introducing reactive groups into a binder polymer is a method in which a polymer having carboxyl groups is synthesized by polymerization, and then glycidyl (meth)acrylate is reacted with a portion of the carboxyl groups of the resulting polymer by a polymer reaction to introduce (meth)acryloyloxy groups into the polymer. This method can produce a binder polymer having (meth)acryloyloxy groups on its side chains.

[0596] The polymerization reaction is preferably carried out at a temperature of 70°C to 100°C, more preferably at a temperature of 80°C to 90°C. The polymerization initiator used in the polymerization reaction is preferably an azo initiator, and more preferably V-601 (trade name) or V-65 (trade name) manufactured by FUJIFILM Wako Pure Chemical Corporation. The polymer reaction is preferably carried out at a temperature of 80°C to 110°C. In the polymer reaction, a catalyst such as an ammonium salt is preferably used.

[0597] From the viewpoint of achieving more excellent effects in the present invention, the following polymers are preferred as binder polymers: The content ratios (a to d) and weight average molecular weight Mw of the following structural units can be appropriately changed depending on the intended purpose.

[0598] [Chemical Formula 8]

[0599]

[0600] [Chemical Formula 9]

[0601]

[0602] Furthermore, the binder polymer may include a polymer containing a structural unit having a carboxylic acid anhydride structure (hereinafter also referred to as "polymer X").

[0603] The carboxylic acid anhydride structure may be either a chain carboxylic acid anhydride structure or a cyclic carboxylic acid anhydride structure, but is preferably a cyclic carboxylic acid anhydride structure.

[0604] The ring of the cyclic carboxylic acid anhydride structure is preferably a 5- to 7-membered ring, more preferably a 5- or 6-membered ring, and still more preferably a 5-membered ring.

[0605] The structural unit having a carboxylic acid anhydride structure is preferably a structural unit containing a divalent group formed by removing two hydrogen atoms from a compound represented by the following formula P-1 in the main chain, or a structural unit in which a monovalent group formed by removing one hydrogen atom from a compound represented by the following formula P-1 is bonded to the main chain directly or via a divalent linking group.

[0606] [Chemical Formula 10]

[0607]

[0608] In formula P-1, R A1a represents a substituent, n 1a R A1a Can be the same or different, Z 1a represents a divalent group forming a ring containing -C(=O)-OC(=O)-, n 1a Indicates an integer greater than 0.

[0609] As R A1a Examples of the substituent represented by include an alkyl group.

[0610] As Z 1a , preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and further preferably an alkylene group having 2 carbon atoms.

[0611] n 1a Indicates an integer greater than 0. 1a In the case of an alkylene group having 2 to 4 carbon atoms, n 1a It is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0.

[0612] In n 1aWhen an integer greater than 2 is represented, there are multiple R A1a Can be the same or different. Also, there are multiple R A1a They may bond to each other to form a ring, but preferably bond to each other without forming a ring.

[0613] The structural unit having a carboxylic acid anhydride structure is preferably a structural unit derived from an unsaturated carboxylic acid anhydride, more preferably a structural unit derived from an unsaturated cyclic carboxylic acid anhydride, further preferably a structural unit derived from an unsaturated aliphatic cyclic carboxylic acid anhydride, particularly preferably a structural unit derived from maleic anhydride or itaconic anhydride, and most preferably a structural unit derived from maleic anhydride.

[0614] Specific examples of the structural unit having a carboxylic acid anhydride structure are given below, 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 CH2OH group or a CF3 group, and Me represents a methyl group.

[0615] [Chemical Formula 11]

[0616]

[0617] [Chemical Formula 12]

[0618]

[0619] The structural unit having a carboxylic acid anhydride structure in the polymer X may be of a single type or of two or more types.

[0620] The total content of the structural units having a carboxylic anhydride structure is preferably 0 mol% to 60 mol% based on all structural units of the polymer X, more preferably 5 mol% to 40 mol%, further preferably 10 mol% to 35 mol%.

[0621] The photosensitive resin layer may contain only one type of polymer X, or may contain two or more types.

[0622] When the photosensitive resin layer contains a polymer X, from the viewpoint of achieving more excellent effects in the present invention, the content of the polymer X is preferably 0.1% by mass to 30% by mass, more preferably 0.2% by mass to 20% by mass, further preferably 0.5% by mass to 20% by mass, and even more preferably 1% by mass to 20% by mass, relative to the total mass of the photosensitive resin layer.

[0623] From the viewpoint of achieving more excellent effects in the present invention, the weight average molecular weight (Mw) of the binder polymer is preferably 5,000 or more, more preferably 10,000 or more, further preferably 10,000 to 50,000, and particularly preferably 20,000 to 30,000.

[0624] 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.

[0625] The acid value of the binder polymer is a value measured according to the method described in JIS K0070:1992.

[0626] The photosensitive resin layer may contain only one type of binder polymer, or may contain two or more types.

[0627] From the viewpoint of achieving more excellent effects of the present invention, the content of the binder polymer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass relative to the total mass of the photosensitive resin layer.

[0628] <Polymerizable compounds>

[0629] The photosensitive resin layer preferably contains a polymerizable compound.

[0630] The polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include radical polymerizable groups and cation polymerizable groups, with radical polymerizable groups being preferred.

[0631] The polymerizable compound preferably contains a radical polymerizable compound having an ethylenically unsaturated group (hereinafter, also simply referred to as an "ethylenically unsaturated compound").

[0632] As the ethylenically unsaturated group, a (meth)acryloyloxy group is preferred.

[0633] In addition, the ethylenically unsaturated compound in this specification is a compound other than the above-mentioned binder polymer, and preferably has a molecular weight of less than 5,000.

[0634] One preferred embodiment of the polymerizable compound includes a compound represented by the following formula (M) (also simply referred to as "compound M").

[0635] Q 2 -R 1 -Q 1 Formula (M)

[0636] Q in formula (M) 1 and Q 2 Each independently represents a (meth)acryloyloxy group, R 1 It represents a divalent linking group having a chain structure.

[0637] Q in formula (M)1 and Q 2 From the perspective of ease of synthesis, Q 1 and Q 2 The same groups are preferred.

[0638] Furthermore, from the viewpoint of reactivity, Q in formula (M) 1 and Q 2 Preferred is an acryloyloxy group.

[0639] As R in formula (M) 1 From the viewpoint of the better effect of the present invention, alkylene, alkyleneoxyalkylene (-L 1 -OL 1 -) or polyalkyleneoxyalkylene (-(L 1 -O) P -L 1 -), more preferably a hydrocarbon group or polyalkyleneoxyalkylene group having 2 to 20 carbon atoms, further preferably an alkylene group having 4 to 20 carbon atoms, and particularly preferably a linear alkylene group having 6 to 18 carbon atoms.

[0640] The above-mentioned hydrocarbon group only needs to have a chain structure in at least a part. There is no particular limitation on the part other than the above-mentioned chain structure. For example, it can be any one of a branched, cyclic or linear alkylene group having 1 to 5 carbon atoms, an arylene group, an ether bond, and a combination thereof. Preferably, it is an alkylene group or a group composed of two or more alkylene groups and one or more arylene groups. More preferably, it is an alkylene group, and even more preferably, a linear alkylene group.

[0641] In addition, the above L 1 Each independently represents an alkylene group, preferably an ethylene group, a propylene group or a butylene group, more preferably an ethylene group or a 1,2-propylene group.

[0642] p represents an integer of 2 or greater, and is preferably an integer of 2-10.

[0643] Furthermore, from the viewpoint of further improving the effect of the present invention, the linker Q in the compound M 1 With Q 2 The number of atoms in the shortest connecting chain between the atoms is preferably 3 to 50, more preferably 4 to 40, further preferably 6 to 20, and particularly preferably 8 to 12.

[0644] In this manual, "Connecting Q 1 With Q 2 The number of atoms in the shortest chain between 1 R 1 Atoms in Q 2 R 1The shortest number of atoms connected to the atoms in the string.

[0645] Specific examples of compound M include 1,3-butanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-pentanediol 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, tricyclodecane dimethanol 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. These ester monomers may also be used as a mixture.

[0646] Among the above compounds, from the viewpoint of more excellent effects in the present invention, at least one compound selected from 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate is preferred. At least one compound selected from 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate is more preferred. At least one compound selected from 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate is even more preferred.

[0647] Furthermore, as one of the preferred aspects of the polymerizable compound, there is mentioned a bifunctional or higher functional ethylenically unsaturated compound.

[0648] In this specification, a "bifunctional or higher-functional ethylenically unsaturated compound" refers to a compound having two or more ethylenically unsaturated groups in one molecule.

[0649] As the ethylenically unsaturated group in the ethylenically unsaturated compound, a (meth)acryloyl group is preferred.

[0650] As the ethylenically unsaturated compound, a (meth)acrylate compound is preferred.

[0651] The bifunctional ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds.

[0652] Examples of the bifunctional ethylenically unsaturated compound other than the compound M include tricyclodecane dimethanol di(meth)acrylate and tricyclodecane dimethanol di(meth)acrylate.

[0653] Examples of commercially available bifunctional ethylenically unsaturated compounds include tricyclodecane dimethanol diacrylate (trade name: NK ESTER A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (trade name: NK ESTER DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (trade name: NK ESTER A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), and 1,6-hexanediol diacrylate (trade name: NK ESTER A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0654] The trifunctional or higher-functional ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds.

[0655] Examples of trifunctional or higher-functional ethylenically unsaturated compounds include dipentaerythritol (tri / tetra / penta / hexa) (meth)acrylate, pentaerythritol (tri / tetra) (meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerol tri(meth)acrylate skeleton.

[0656] Here, “(tri / tetra / penta / hexa) (meth)acrylate” is a concept including tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and “(tri / tetra) (meth)acrylate” is a concept including tri(meth)acrylate and tetra(meth)acrylate.

[0657] Examples of the polymerizable compound include caprolactone-modified compounds of (meth)acrylate compounds (such as KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd. and A-930(-1CL) manufactured by Shin-Nakamura Chemical Co., Ltd.), alkylene oxide-modified compounds of (meth)acrylate compounds (such as KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd. and ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd. and EBECRYL (registered trademark) 135 manufactured by DAICEL-ALLNEX LTD.), and ethoxylated glyceryl triacrylate (such as NK ESTER A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0658] Examples of the polymerizable compound include urethane (meth)acrylate compounds.

[0659] Examples of the urethane (meth)acrylate include urethane di(meth)acrylates, such as propylene oxide-modified urethane di(meth)acrylate and ethylene oxide- and propylene oxide-modified urethane di(meth)acrylate.

[0660] Furthermore, examples of urethane (meth)acrylates include trifunctional or higher urethane (meth)acrylates. The lower limit of the number of functional groups is more preferably hexafunctional or higher, and even more preferably octafunctional or higher. The upper limit of the number of functional groups is preferably 20 or lower. Examples of trifunctional or higher-functional urethane (meth)acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), AH-600 (trade name) manufactured by Kyoeisha Chemical Co., Ltd., and UA-306H, UA-306T, UA-306I, UA-510H, and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).

[0661] One preferred embodiment of the polymerizable compound is an ethylenically unsaturated compound having an acid group.

[0662] Examples of the acid group include a phosphoric acid group, a sulfonic acid group, and a carboxyl group.

[0663] Among these, as the acid group, a carboxyl group is preferred.

[0664] Examples of the ethylenically unsaturated compound having an acid group include trifunctional to tetrafunctional ethylenically unsaturated compounds having an acid group [ethylenically unsaturated compounds having a carboxyl group introduced into the skeleton of pentaerythritol tri- and tetraacrylate (PETA) (acid value: 80 mgKOH / g to 120 mgKOH / g)], and pentafunctional to hexafunctional ethylenically unsaturated compounds having an acid group [ethylenically unsaturated compounds having a carboxyl group introduced into the skeleton of dipentaerythritol penta- and hexaacrylate (DPHA) [acid value: 25 mgKOH / g to 70 mgKOH / g)].

[0665] 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, as needed.

[0666] As the ethylenically unsaturated compound having an acid group, at least one selected from bifunctional or higher-functional ethylenically unsaturated compounds having a carboxyl group and carboxylic anhydrides thereof is preferred.

[0667] When the ethylenically unsaturated compound having an acid group is at least one selected from bifunctional or higher-functional ethylenically unsaturated compounds having a carboxyl group and carboxylic anhydrides thereof, the developability and film strength are further improved.

[0668] The bifunctional or higher functional ethylenically unsaturated compound having a carboxyl group is not particularly limited and can be appropriately selected from known compounds.

[0669] Examples of bifunctional or higher-functional ethylenically unsaturated compounds having a carboxyl group include ARONIX (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), ARONIX (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and ARONIX (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.).

[0670] 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 preferred, and the contents described in the publication are incorporated into the present specification.

[0671] Examples of the polymerizable compound include compounds obtained by reacting an α,β-unsaturated carboxylic acid with a polyol, compounds obtained by reacting an α,β-unsaturated carboxylic acid with a glycidyl group-containing compound, urethane monomers such as (meth)acrylate compounds having a urethane bond, phthalic acid compounds such as γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl phthalate, and β-hydroxypropyl-β'-(meth)acryloyloxyethyl phthalate, and alkyl (meth)acrylates.

[0672] These can be used alone or in combination of two or more.

[0673] Examples of the compound obtained by reacting an α,β-unsaturated carboxylic acid with a polyol include bisphenol A (meth)acrylate compounds such as 2,2-bis(4-((meth)acryloyloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxypolypropoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloyloxypolyethoxypolypropoxy)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 polyethylene polypropylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups and 2 to 14 propylene oxide groups. trimethylolpropane tri(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy tri(meth)acrylate, trimethylolpropane diethoxy tri(meth)acrylate, trimethylolpropane triethoxy tri(meth)acrylate, trimethylolpropane tetraethoxy tri(meth)acrylate, trimethylolpropane pentaethoxy tri(meth)acrylate, di(trimethylolpropane) tetraacrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0674] Among them, ethylenically unsaturated compounds having a tetramethylolmethane structure or a trimethylolpropane structure are preferred, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane)tetraacrylate is more preferred.

[0675] Examples of the polymerizable compound include caprolactone-modified compounds of ethylenically unsaturated compounds (e.g., KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide-modified compounds of ethylenically unsaturated compounds (e.g., KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by DAICEL-ALLNEX Ltd., etc.), and ethoxylated glyceryl triacrylate (e.g., A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0676] As the polymerizable compound (particularly an ethylenically unsaturated compound), from the viewpoint of excellent developability of the photosensitive resin layer after transfer, it is preferred that the polymerizable compound contain an ester bond.

[0677] The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule. However, from the viewpoint of excellent effects in the present invention, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferred, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane)tetraacrylate is more preferred.

[0678] From the viewpoint of imparting reliability, the ethylenically unsaturated compound preferably includes an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms and an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure.

[0679] 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 tricyclodecane dimethanol di(meth)acrylate.

[0680] One preferred embodiment of the polymerizable compound is a polymerizable compound having an aliphatic hydrocarbon ring structure (preferably a bifunctional ethylenically unsaturated compound).

[0681] As the above-mentioned polymerizable compound, a polymerizable compound having a ring structure in which two or more aliphatic hydrocarbon rings are condensed (preferably a structure selected from a tricyclodecane structure and a tricyclodecene structure) is preferred, a bifunctional ethylenically unsaturated compound having a ring structure in which two or more aliphatic hydrocarbon rings are condensed is more preferred, and tricyclodecane dimethanol di(meth)acrylate is further preferred.

[0682] As the aliphatic hydrocarbon ring structure, from the viewpoint of more excellent effects in the present invention, a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure, or an isoborane structure is preferred.

[0683] The molecular weight of the polymerizable compound is preferably 200 to 3,000, more preferably 250 to 2,600, further preferably 280 to 2,200, and particularly preferably 300 to 2,200.

[0684] The proportion of the polymerizable compound having a molecular weight of 300 or less in the photosensitive resin layer is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less relative to the total content of the polymerizable compounds in the photosensitive resin layer.

[0685] As one preferred embodiment of the photosensitive resin layer, the photosensitive resin layer preferably contains a difunctional or higher-functional ethylenically unsaturated compound, more preferably a trifunctional or higher-functional ethylenically unsaturated compound, and even more preferably a trifunctional or tetrafunctional ethylenically unsaturated compound.

[0686] Furthermore, as one preferred embodiment of the photosensitive resin layer, the photosensitive resin layer preferably contains a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and a binder polymer containing a structural unit having an aliphatic hydrocarbon ring.

[0687] Furthermore, as one of the preferred forms of the photosensitive resin layer, the photosensitive resin layer preferably comprises a compound represented by formula (M) (compound M) and an ethylenically unsaturated compound having an acid group, more preferably comprises 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate and a multifunctional ethylenically unsaturated compound having a carboxylic acid group, and further preferably comprises 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate and a succinic acid modified form of dipentaerythritol pentaacrylate.

[0688] Furthermore, as one of the preferred aspects 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 below, and more preferably contains compound M, an ethylenically unsaturated compound having an acid group, and a blocked isocyanate compound described below.

[0689] Furthermore, as one preferred embodiment of the photosensitive resin layer, the photosensitive resin layer preferably contains a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth)acrylate compound) and a trifunctional or higher functional ethylenically unsaturated compound (preferably a trifunctional or higher functional (meth)acrylate compound).

[0690] Furthermore, as one of the preferred aspects of the photosensitive resin layer, the photosensitive resin layer preferably contains the compound M and a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure from the viewpoint of rust prevention.

[0691] Furthermore, as one of the preferred aspects of the photosensitive resin layer, from the viewpoints of substrate adhesion, development residue inhibition and rust resistance, the photosensitive resin layer preferably comprises compound M and an ethylenically unsaturated compound having an acid group, more preferably comprises compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and an ethylenically unsaturated compound having an acid group, further preferably comprises compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a trifunctional or higher ethylenically unsaturated compound and an ethylenically unsaturated compound having an acid group, and particularly preferably comprises compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a trifunctional or higher ethylenically unsaturated compound, an ethylenically unsaturated compound having an acid group and a carbamate (meth)acrylate compound.

[0692] Furthermore, as one of the preferred aspects of the photosensitive resin layer, from the viewpoints of substrate adhesion, development residue suppression and rust resistance, the photosensitive resin layer preferably comprises 1,9-nonanediol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, more preferably comprises 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, further preferably comprises 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, dipentaerythritol hexaacrylate and an ethylenically unsaturated compound having a carboxylic acid group, and particularly preferably comprises 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, an ethylenically unsaturated compound having a carboxylic acid group and a urethane acrylate compound.

[0693] The photosensitive resin layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound.

[0694] The content of the difunctional or higher functional ethylenically unsaturated compound in the ethylenically unsaturated compound is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and further preferably 90 to 100% by mass relative to the total content of all ethylenically unsaturated compounds contained in the photosensitive resin layer.

[0695] The polymerizable compound (especially an ethylenically unsaturated compound) may be used alone or in combination of two or more.

[0696] The content of the polymerizable compound (especially the ethylenically unsaturated compound) in the photosensitive resin layer is preferably 1% by mass to 70% by mass, more preferably 5% by mass to 70% by mass, further preferably 5% by mass to 60% by mass, and particularly preferably 5% by mass to 50% by mass, relative to the total mass of the photosensitive resin layer.

[0697] <Photopolymerization initiator>

[0698] The photosensitive resin layer preferably contains a photopolymerization initiator.

[0699] There are no particular restrictions on the photopolymerization initiator, and a known photopolymerization initiator can be used.

[0700] Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter also referred to as an “oxime-based photopolymerization initiator”), a photopolymerization initiator having an α-aminoalkylphenone structure (hereinafter also referred to as an “α-aminoalkylphenone-based photopolymerization initiator”), a photopolymerization initiator having an α-hydroxyalkylphenone structure (hereinafter also referred to as an “α-hydroxyalkylphenone-based photopolymerization initiator”), a photopolymerization initiator having an acylphosphine oxide structure (hereinafter also referred to as an “acylphosphine oxide-based photopolymerization initiator”), and a photopolymerization initiator having an N-phenylglycine structure (hereinafter also referred to as an “N-phenylglycine-based photopolymerization initiator”).

[0701] The photopolymerization initiator preferably includes at least one selected from oxime-based photopolymerization initiators, α-aminoalkylphenone-based photopolymerization initiators, α-hydroxyalkylphenone-based photopolymerization initiators, and N-phenylglycine-based photopolymerization initiators, and more preferably includes at least one selected from oxime-based photopolymerization initiators, α-aminoalkylphenone-based photopolymerization initiators, and N-phenylglycine-based photopolymerization initiators.

[0702] Furthermore, as the photopolymerization initiator, for example, polymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-95716 and paragraphs 0064 to 0081 of JP-A-2015-014783 can be used.

[0703] Examples of commercially available photopolymerization 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-carbazol-3-yl]ethanone-1-(O-acetoxime) [trade name: IRGACURE (registered trademark) OXE-02, manufactured by BASF], IRGACURE (registered trademark) OXE03 (manufactured by BASF), IRGACURE (registered trademark) OXE04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, IGM Resins BV], 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one [Trade name: Omnirad (registered trademark) 907, manufactured by IGM Resins BV], 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one [Trade name: Omnirad (registered trademark) 127, manufactured by IGM Resins BV], 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone [Trade name: Omnirad (registered trademark) 369, manufactured by IGM Resins BV], 2-hydroxy-2-methyl-1-phenylpropan-1-one [Trade name: Omnirad (registered trademark) 1173, manufactured by IGM Resins BV], 1-hydroxycyclohexylphenyl ketone [Trade name: Omnirad (registered trademark) 184, IGM Resins BV], 2,2-dimethoxy-1,2-diphenylethane-1-one [trade name: Omnirad (registered trademark) 651, manufactured by IGM Resins BV], oxime esters [trade name: Lunar (registered trademark) 6, manufactured by DKSH MANAGEMENT LTD.], 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-305, manufactured by Changzhuo Trony New Electric Materials Co., Ltd.), 3-cyclohexyl-1-[9-ethyl-6-(2-furylcarbonyl)-9H-carbazol-3-yl]-1,2-propanedione-2-(O-acetyloxime) (trade name: TR-PBG-326, manufactured by Changzhuo Trony New Electric Materials Co., Ltd. MATERIALS C0.,LTD.(manufactured by Shenzhen UV-ChemTech Ltd.), 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)octanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, manufactured by Changzhuo Trony New Electric Materials Co., Ltd.), and APi-307 (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropane-1-one, manufactured by Shenzhen UV-ChemTech Ltd.).

[0704] The photopolymerization initiator may be used alone or in combination of two or more.

[0705] When the photosensitive resin layer contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, relative to the total mass of the photosensitive resin layer. Furthermore, the upper limit thereof is preferably 10% by mass or less, and more preferably 5% by mass or less, relative to the total mass of the photosensitive resin layer.

[0706] <Heterocyclic compounds>

[0707] The photosensitive resin layer may contain a heterocyclic compound.

[0708] The heterocyclic ring of the heterocyclic compound may be either a monocyclic ring or a polycyclic ring.

[0709] Examples of the heteroatom possessed by 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 a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably has a nitrogen atom.

[0710] Examples of the heterocyclic compound include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, and pyrimidine compounds.

[0711] Among the above, the heterocyclic compound is preferably at least one compound selected from triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzimidazole compounds and benzoxazole compounds, and more preferably at least one compound selected from triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds and benzoxazole compounds.

[0712] Preferred specific examples of the heterocyclic compound are shown below. As the triazole compound and the benzotriazole compound, the following compounds can be exemplified.

[0713] [Chemical Formula 13]

[0714]

[0715] [Chemical Formula 14]

[0716]

[0717] Examples of the tetrazole compound include the following compounds.

[0718] [Chemical Formula 15]

[0719]

[0720] [Chemical Formula 16]

[0721]

[0722] Examples of the thiadiazole compound include the following compounds.

[0723] [Chemical Formula 17]

[0724]

[0725] Examples of the triazine compound include the following compounds.

[0726] [Chemical Formula 18]

[0727]

[0728] Examples of the rhodanine compound include the following compounds.

[0729] [Chemical Formula 19]

[0730]

[0731] Examples of the thiazole compound include the following compounds.

[0732] [Chemical Formula 20]

[0733]

[0734] Examples of the benzothiazole compound include the following compounds.

[0735] [Chemical Formula 21]

[0736]

[0737] Examples of the benzimidazole compound include the following compounds.

[0738] [Chemical Formula 22]

[0739]

[0740] [Chemical Formula 23]

[0741]

[0742] Examples of the benzoxazole compound include the following compounds.

[0743] [Chemical Formula 24]

[0744]

[0745] The heterocyclic compound may be used alone or in combination of two or more.

[0746] 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, more preferably 0.10% by mass to 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, relative to the total mass of the photosensitive resin layer.

[0747] <Aliphatic thiol compounds>

[0748] The photosensitive resin layer may contain an aliphatic thiol compound.

[0749] When the photosensitive resin layer contains an aliphatic thiol compound, the aliphatic thiol compound and the radical polymerizable compound having an ethylenically unsaturated group undergo an ene-thiol reaction, whereby the curing shrinkage of the formed film is suppressed and stress is relaxed.

[0750] The aliphatic thiol compound is preferably a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (ie, a bifunctional or higher-functional aliphatic thiol compound).

[0751] Among the above, as the aliphatic thiol compound, from the viewpoint of the adhesion of the formed pattern (particularly the adhesion after exposure), a polyfunctional aliphatic thiol compound is more preferred.

[0752] In this specification, the "polyfunctional aliphatic thiol compound" refers to an aliphatic compound having two or more thiol groups (also referred to as "mercapto groups") in the molecule.

[0753] The polyfunctional aliphatic thiol compound is preferably a low molecular weight compound having a molecular weight of not less than 100. 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.

[0754] The number of functional groups of the polyfunctional aliphatic thiol compound is preferably difunctional to decafunctional, more preferably difunctional to octafunctional, and even more preferably difunctional to hexafunctional, from the viewpoint of adhesion of the formed pattern.

[0755] Examples of the polyfunctional aliphatic thiol compound include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolethane tris(3-mercaptobutyrate), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, trimethylolpropane tris(3-mercaptobutyrate), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, and trimethylolpropane tris(3-mercaptobutyrate). (3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), ethylene glycol bisthiopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2'-(ethylenedithio)diethanethiol, meso-2,3-dimercaptosuccinic acid and bis(mercaptoethyl) ether.

[0756] Among the above, the polyfunctional aliphatic thiol compound is preferably at least one compound selected from trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0757] Examples of the monofunctional aliphatic thiol compound include 1-octanethiol, 1-dodecanethiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.

[0758] The photosensitive resin layer may contain a single aliphatic thiol compound, or may contain two or more aliphatic thiol compounds.

[0759] 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, further preferably 5% by mass to 30% by mass, and particularly preferably 8% by mass to 20% by mass, relative to the total mass of the photosensitive resin layer.

[0760] Thermally cross-linkable compounds

[0761] The photosensitive resin layer preferably contains a thermally crosslinkable compound from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.

[0762] As the thermally crosslinkable compound used in the photosensitive resin layer of the second embodiment, the thermally crosslinkable compound described above in the photosensitive resin layer of the first embodiment can be preferably used.

[0763] The heat-crosslinkable compound may be used alone or in combination of two or more.

[0764] When the photosensitive resin layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass, based on the total mass of the photosensitive resin layer.

[0765] Surfactants

[0766] The photosensitive resin layer may contain a surfactant.

[0767] As the surfactant used in the photosensitive resin layer of the second embodiment, the surfactant described above in the photosensitive resin layer of the first embodiment can be preferably used.

[0768] The surfactant may be used alone or in combination of two or more.

[0769] When the photosensitive resin layer contains a surfactant, the content of the surfactant is preferably 0.01 to 3.0 mass %, more preferably 0.01 to 1.0 mass %, and further preferably 0.05 to 0.80 mass % relative to the total mass of the photosensitive resin layer.

[0770] <Polymerization inhibitor>

[0771] The photosensitive resin layer may contain a polymerization inhibitor.

[0772] The term "polymerization inhibitor" refers to a compound that has the function of delaying or preventing a polymerization reaction. For example, a known compound used as a polymerization inhibitor can be used as the polymerization inhibitor.

[0773] 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)propionate][ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl), 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl), and 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine. and hindered phenol compounds such as pentaerythritol tetrakis 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate; nitroso compounds or their salts such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine and N-nitrosophenylhydroxylamine; quinone compounds such as methylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone and 4-benzoquinone; phenol compounds such as 4-methoxyphenol, 4-methoxy-1-naphthol and tert-butylcatechol; metal salt compounds such as copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate and manganese diphenyldithiocarbamate.

[0774] Among them, from the viewpoint of more excellent effects in the present invention, the polymerization inhibitor is preferably at least one selected from phenothiazine compounds, nitroso compounds or salts thereof, and hindered phenol compounds, and more preferably phenothiazine, 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-tert-butyl-4-hydroxybenzyl) and N-nitrosophenylhydroxylamine aluminum salt.

[0775] The polymerization inhibitors may be used alone or in combination of two or more.

[0776] When the photosensitive resin layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 10.0% by mass, more preferably 0.01 to 5.0% by mass, and further preferably 0.04 to 3.0% by mass, relative to the total mass of the photosensitive resin layer.

[0777] <Hydrogen-donating compounds>

[0778] The photosensitive resin layer may contain a hydrogen-donating compound.

[0779] The hydrogen-donating compound has the functions of further increasing the sensitivity of the photopolymerization initiator to active light and suppressing the polymerization inhibition of the polymerizable compound caused by oxygen.

[0780] Examples of the hydrogen-donating compound include amines and amino acid compounds.

[0781] Examples of the amines include compounds described in "Journal of Polymer Society" by MR Sander et al., Vol. 10, p. 3173 (1972), Japanese Patent Publication 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, Japanese Patent Application Laid-Open No. 60-084305, Japanese Patent Application Laid-Open No. 62-018537, Japanese Patent Application Laid-Open No. 64-033104, and Research Disclosure No. 33825. More specific examples include 4,4′-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (also known as colorless crystal violet), triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, and p-methylthiodimethylaniline.

[0782] Among them, from the viewpoint of achieving more excellent effects in the present invention, the amine is preferably at least one selected from 4,4′-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane.

[0783] Examples of the amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.

[0784] Among them, N-phenylglycine is preferred as the amino acid compound from the viewpoint of achieving more excellent effects in the present invention.

[0785] Examples of hydrogen-donating compounds include organometallic compounds (tributyltin acetate, etc.) described in JP-B-48-042965, hydrogen donors described in JP-B-55-034414, and sulfur compounds (trithiane, etc.) described in JP-A-6-308727.

[0786] The hydrogen-donating compound may be used alone or in combination of two or more.

[0787] When the photosensitive resin layer contains a hydrogen-donating compound, the content of the hydrogen-donating compound is preferably 0.01% by mass to 10.0% by mass, more preferably 0.01% by mass to 8.0% by mass, and further preferably 0.03% by mass to 5.0% by mass relative to the total mass of the photosensitive resin layer, from the viewpoint of improving the curing rate by balancing the polymerization growth rate and chain transfer.

[0788] <Impurities, etc.>

[0789] The photosensitive resin layer may contain a predetermined amount of impurities.

[0790] The impurities in the photosensitive resin layer of the second embodiment are similar to the preferred aspects of the impurities in the photosensitive resin layer of the first embodiment.

[0791] <Residual monomer>

[0792] The photosensitive resin layer may contain residual monomers corresponding to the respective structural units of the above-mentioned binder polymer.

[0793] The preferred aspects of the residual monomers corresponding to the structural units of the binder polymer in the photosensitive resin layer of the second embodiment are the same as those of the residual monomers corresponding to the structural units of the alkali-soluble resin in the photosensitive resin layer of the first embodiment.

[0794] <Other ingredients>

[0795] The photosensitive resin layer may contain components other than the above components (hereinafter also referred to as "other components"). Examples of other components include colorants, antioxidants, and particles (e.g., metal oxide particles). Examples of other components include other additives described in paragraphs 0058 to 0071 of Japanese Patent Application Laid-Open No. 2000-310706.

[0796] -particle-

[0797] As the particles, metal oxide particles are preferred.

[0798] The metal in the metal oxide particles also includes metalloids such as B, Si, Ge, As, Sb, and Te.

[0799] For example, from the viewpoint of transparency of the cured film, the average primary particle size of the particles is preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm.

[0800] The average primary particle size of the particles is calculated by measuring the particle sizes of 200 random particles using an electron microscope and taking the arithmetic average of the measurement results. In addition, when the shape of the particles is not spherical, the longest side is used as the particle size.

[0801] When the photosensitive resin layer contains particles, the photosensitive resin layer may contain only one type of particles having different metal types, sizes, etc., or may contain two or more types of particles.

[0802] It is preferred that the photosensitive resin layer does not contain particles, or when the photosensitive resin layer contains particles, the content of the particles is greater than 0 mass % and less than 35 mass % relative to the total mass of the photosensitive resin layer. It is more preferred that the photosensitive resin layer does not contain particles, or the content of the particles is greater than 0 mass % and less than 10 mass % relative to the total mass of the photosensitive resin layer. It is further preferred that the photosensitive resin layer does not contain particles, or the content of the particles is greater than 0 mass % and less than 5 mass % relative to the total mass of the photosensitive resin layer. It is further preferred that the photosensitive resin layer does not contain particles, or the content of the particles is greater than 0 mass % and less than 1 mass % relative to the total mass of the photosensitive resin layer. It is particularly preferred that the photosensitive resin layer does not contain particles.

[0803] -Colorant-

[0804] The photosensitive resin layer may contain a colorant (a pigment, a dye, etc.), but preferably contains substantially no colorant, for example, from the viewpoint of transparency.

[0805] When the photosensitive resin layer contains a colorant, the content of the colorant is preferably less than 1 mass %, more preferably less than 0.1 mass %, relative to the total mass of the photosensitive resin layer.

[0806] -Antioxidants-

[0807] Examples of the antioxidant include 3-pyrazolidinones such as 1-phenyl-3-pyrazolidinone (also known as phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidinone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorohydroquinone; p-methylaminophenol, p-aminophenol, p-hydroxyphenylglycine, and p-phenylenediamine.

[0808] Among them, from the viewpoint of achieving more excellent effects in the present invention, 3-pyrazolidinones are preferred as antioxidants, and 1-phenyl-3-pyrazolidinone is more preferred.

[0809] 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, and even more preferably 0.01% by mass or more relative to the total mass of the photosensitive resin layer. The upper limit is not particularly limited, but is preferably 1% by mass or less.

[0810] <Thickness of Photosensitive Resin Layer>

[0811] The thickness of the photosensitive resin layer is not particularly limited, but is generally 30 μm or less. From the perspective of achieving superior effects in the present invention, it is preferably 20 μm or less, more preferably 15 μm or less, further preferably 10 μm or less, and particularly preferably 5.0 μm or less. As a lower limit, from the perspective of excellent strength of the film obtained by curing the photosensitive resin layer, it is preferably 0.60 μm or more, and more preferably 1.5 μm or more.

[0812] The thickness of the photosensitive resin layer can be calculated as an average value of five arbitrary points measured by cross-sectional observation using a scanning electron microscope (SEM), for example.

[0813] <Refractive Index of Photosensitive Resin Layer>

[0814] The refractive index of the photosensitive resin layer is preferably 1.47 to 1.56, more preferably 1.49 to 1.54.

[0815] Color of the photosensitive resin layer

[0816] The photosensitive resin layer is preferably colorless. Specifically, total reflection (incident angle 8°, light source: D-65 (2° field of view)) is CIE1976 (L * , a * , b * ) color space L * The value is preferably 10 to 90, a * The value is preferably -1.0 to 1.0, b * The value is preferably -1.0 to 1.0.

[0817] Moreover, the pattern obtained by curing the photosensitive resin layer (cured film of the photosensitive resin layer) is preferably colorless.

[0818] Specifically, total reflection (incident angle 8°, light source: D-65 (2° field of view)) is in CIE1976 (L * , a * , b * ) The L of the pattern in the color space * The value is preferably 10 to 90, and the pattern a * The value is preferably -1.0 to 1.0, and the b * The value is preferably -1.0 to 1.0.

[0819] Refractive Index Adjustment Layer

[0820] The photosensitive transfer material preferably has a refractive index adjusting layer.

[0821] 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.

[0822] The method for controlling the refractive index of the refractive index adjusting layer is not particularly limited, and examples thereof include a method of using a resin having a predetermined refractive index alone, a method of using a resin and particles, and a method of using a composite of a metal salt and a resin.

[0823] Examples of the binder polymer and polymerizable compound include the binder polymer and polymerizable compound described in the section "photosensitive resin layer".

[0824] Examples of the particles include metal oxide particles and metal particles.

[0825] The type of metal oxide particles is not particularly limited, and known metal oxide particles can be used. The metal in the metal oxide particles also includes metalloids such as B, Si, Ge, As, Sb, and Te.

[0826] For example, from the viewpoint of transparency of the cured film, the average primary particle size of the particles is preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm.

[0827] The average primary particle size of the particles is calculated by measuring the particle sizes of 200 random particles using an electron microscope and taking the arithmetic average of the measurement results. In addition, when the shape of the particles is not spherical, the longest side is used as the particle size.

[0828] Specifically, the metal oxide particles are preferably at least one selected from zirconium oxide particles (ZrO 2 particles), Nb 2 O 5 particles, titanium oxide particles (TiO 2 particles), silicon dioxide particles (SiO 2 particles), and composite particles thereof.

[0829] Among these, as the metal oxide particles, for example, from the viewpoint of easy adjustment of the refractive index, at least one selected from zirconium oxide particles and titanium oxide particles is more preferable.

[0830] Commercially available metal oxide particles include calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F04), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F74), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F75), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F76), zirconia particles (NanoUse OZ-S30M, manufactured by Nissan Chemical Industries, Ltd.), and zirconia particles (NanoUse OZ-S30K, manufactured by Nissan Chemical Industries, Ltd.).

[0831] The particles may be used alone or in combination of two or more.

[0832] The content of the particles in the refractive index adjusting layer is preferably 1 to 95 mass %, more preferably 20 to 90 mass %, and further preferably 40 to 85 mass %, relative to the total mass of the refractive index adjusting layer.

[0833] When titanium oxide is used as the metal oxide particles, the content of the titanium oxide particles is preferably 1 to 95 mass %, more preferably 20 to 90 mass %, and even more preferably 40 to 85 mass % relative to the total mass of the refractive index adjusting layer.

[0834] The refractive index of the refractive index adjusting layer is preferably higher than the refractive index of the photosensitive resin layer.

[0835] The refractive index of the refractive index adjusting layer is preferably 1.50 or greater, more preferably 1.55 or greater, further preferably 1.60 or greater, and particularly preferably 1.65 or greater. 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.

[0836] 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.

[0837] <Method for Manufacturing Photosensitive Transfer Material According to Second Embodiment>

[0838] The method for producing the photosensitive transfer material of the second embodiment is not particularly limited, and a known method can be used.

[0839] As Figure 2 The manufacturing method of the photosensitive transfer material 10 shown can include, for example, a method comprising the following steps: a step of applying a photosensitive resin composition to the surface of a temporary support 1 to form a coating film, and then drying the coating film to form a photosensitive resin layer 3; and a step of applying a refractive index adjustment layer forming composition to the surface of the photosensitive resin layer 3 to form a coating film, and then drying the coating film to form a refractive index adjustment layer 5.

[0840] The protective film 7 is pressure-bonded onto the refractive index adjusting layer 5 of the laminate produced by the above-described production method, thereby producing the photosensitive transfer material 10 .

[0841] As a method for manufacturing a photosensitive transfer material of the first embodiment, it is preferred to manufacture a photosensitive transfer material 10 having 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 by a process including providing a protective film 7 in contact with a surface on the side opposite to the side of the refractive index adjusting layer 5 having the temporary support 1.

[0842] After the photosensitive transfer material 10 is manufactured by the above-described manufacturing method, a roll-shaped photosensitive transfer material can be produced and stored by winding the photosensitive transfer material 10. The roll-shaped photosensitive transfer material can be directly provided to the substrate lamination step in the roll-to-roll method described later.

[0843] Furthermore, as a method for producing the photosensitive transfer material 10 , a method of forming the refractive index adjusting layer 5 on the protective film 7 and then forming the photosensitive resin layer 3 on the surface of the refractive index adjusting layer 5 may be adopted.

[0844] The photosensitive transfer material 10 may be produced by forming the photosensitive resin layer 3 on the temporary support 1 and separately forming the refractive index adjusting layer 5 on the protective film 7 , and then laminating the photosensitive resin layer 3 and the refractive index adjusting layer 5 together.

[0845] The photosensitive resin composition and the method for forming the photosensitive resin layer in the second embodiment are the same as those described above in the first embodiment, and preferred aspects are also the same.

[0846] <Refractive Index Adjusting Layer Forming Composition and Refractive Index Adjusting Layer Forming Method>

[0847] The composition for forming a refractive index adjusting layer preferably contains the various components and solvents for forming the refractive index adjusting layer as described above. Furthermore, in the composition for forming a refractive index adjusting layer, the preferred range of the content of each component relative to the total solids content of the composition is the same as the preferred range of the content of each component relative to the total mass of the refractive index adjusting layer as described above.

[0848] The solvent is not particularly limited as long as it can dissolve or disperse the components contained in the refractive index adjusting layer, but is preferably at least one selected from water and a water-miscible organic solvent, and more preferably water or a mixed solvent of water and a water-miscible organic solvent.

[0849] Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerol. Alcohols having 1 to 3 carbon atoms are preferred, and methanol or ethanol is more preferred.

[0850] The solvent may be used alone or in combination of two or more.

[0851] The content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.

[0852] The method for forming the refractive index adjusting layer is not particularly limited as long as it is a method capable of forming a layer containing the above-mentioned components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.).

[0853] Furthermore, by bonding the protective film to the refractive index adjusting layer, the photosensitive transfer material of the second embodiment can be manufactured.

[0854] The method of laminating the protective film to the refractive index adjusting layer is not particularly limited, and a known method may be used.

[0855] As an apparatus for bonding the protective film to the refractive index adjusting layer, a well-known laminator such as a vacuum laminator and an automatic cutting laminator can be mentioned.

[0856] The laminator preferably includes any heatable roller such as a rubber roller and is capable of applying pressure and heat.

[0857] (Method for Manufacturing Resin Pattern, Method for Manufacturing Laminated Body, and Etching Method)

[0858] The method for producing a resin pattern according to the present invention is a method for producing a resin pattern, comprising forming a resin pattern on a substrate using the photosensitive transfer material according to the present invention.

[0859] As a method for manufacturing a resin pattern, it is preferably a method that includes the following steps in sequence: a step of peeling off the above-mentioned protective film from the photosensitive transfer material involved in the present invention (hereinafter also referred to as "protective film peeling step"); a step of bringing the outermost layer of the photosensitive transfer material from which the above-mentioned protective film is peeled off into contact with and bonding it to a substrate (preferably a substrate having a conductive layer) (hereinafter also referred to as "bonding step"); a step of pattern-exposing the above-mentioned photosensitive resin layer with the above-mentioned temporary support interposed therebetween (hereinafter also referred to as "exposure step"); and a step of developing the exposed photosensitive resin layer to form a resin pattern (hereinafter also referred to as "development step").

[0860] The method for producing a laminated body according to the present invention is a method for producing a laminated body having a resin pattern on a substrate using the photosensitive transfer material according to the present invention.

[0861] As a method for producing a laminate, a method including the protective film peeling step, the laminating step, the exposure step, and the development step in this order is preferred.

[0862] The etching method according to the present invention is not particularly limited as long as it is a method using the photosensitive transfer material according to the present invention.

[0863] The etching method involved in the present invention is preferably a method including the following steps: in a stacked body in which the above-mentioned substrate, the above-mentioned conductive layer and the resin pattern manufactured by the resin pattern manufacturing method involved in the present invention are stacked in sequence, the above-mentioned conductive layer in the area where the above-mentioned resin pattern is not configured is etched.

[0864] The following describes the various steps included in the method for manufacturing a resin pattern, the method for manufacturing a laminate, and the etching method. However, unless otherwise specified, the description of the various steps included in the method for manufacturing a resin pattern or the method for manufacturing a laminate also applies to the various steps included in the etching method.

[0865] <Protective film peeling process>

[0866] The method for producing a resin pattern or a laminate preferably includes a step of peeling the protective film from the photosensitive transfer material of the present invention. The method for peeling the protective film is not limited, and a known method can be applied.

[0867] <Lamination process>

[0868] The method for producing a resin pattern or the method for producing a laminate preferably includes a lamination step.

[0869] During the lamination step, the substrate (or the conductive layer if a conductive layer is provided on the substrate's surface) is preferably brought into contact with the outermost layer of the photosensitive transfer material on the side having the photosensitive resin layer facing the temporary support, thereby press-bonding the photosensitive transfer material and the substrate. This aspect improves the adhesion between the outermost layer of the photosensitive transfer material on the side having the photosensitive resin layer facing the temporary support and the substrate, allowing the photosensitive resin layer formed into a pattern after exposure and development to be preferably used as an etching resist when etching the conductive layer.

[0870] Furthermore, the lamination process is as follows: when the surface of the photosensitive resin layer on the side opposite to the temporary support of the photosensitive transfer material also has a layer other than the protective film (for example, a high refractive index layer and / or a low refractive index layer), the surface of the photosensitive resin layer on the side not having the temporary support and the substrate are laminated via the layer.

[0871] There are no particular limitations on the method for pressure-bonding the substrate and the photosensitive transfer material, and a known transfer method and lamination method can be used.

[0872] The photosensitive transfer material and the substrate are preferably laminated by overlapping the outermost layer of the photosensitive transfer material on the side having the photosensitive resin layer facing the temporary support with the substrate and applying pressure and heat using a device such as a roller. For lamination, a known laminator such as a laminator, a vacuum laminator, or an automatic cutting laminator that can further improve productivity can be used.

[0873] The lamination temperature is not particularly limited, but is preferably 70°C to 130°C, for example.

[0874] The resin pattern manufacturing method and etching method including the lamination step are preferably performed by a roll-to-roll method.

[0875] The roll-to-roll method is described below.

[0876] The roll-to-roll method refers to the following method: a substrate that can be rolled up and unrolled is used as a substrate, including a process of unrolling a structure containing a substrate or a substrate before any process included in the resin pattern manufacturing method or the etching method (also referred to as an "unwinding process") and a process of winding up a structure containing a substrate or a substrate after any process (also referred to as a "winding process"), and at least any process (preferably all processes except all processes or heating processes) is performed while carrying a structure containing a substrate or a substrate.

[0877] 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 a production method to which a roll-to-roll system is applied.

[0878] <Substrate>

[0879] As the substrate used in the method for producing a resin pattern according to the present invention, a known substrate can be used. A substrate having a conductive layer is preferred, and a substrate having a conductive layer on its surface is more preferred.

[0880] The substrate may have any layer other than the conductive layer as needed.

[0881] Examples of the substrate include a resin substrate, a glass substrate, and a semiconductor substrate.

[0882] As a preferred embodiment of the substrate, for example, the description in paragraph 0140 of International Publication No. 2018 / 155193 can be cited, and the content thereof is incorporated into this specification.

[0883] Examples of the base material constituting the substrate include glass, silicon, and thin films.

[0884] The base material constituting the substrate is preferably transparent. In this specification, "transparent" means that the transmittance of light with a wavelength of 400 nm to 700 nm is 80% or more.

[0885] Furthermore, the refractive index of the base material constituting the substrate is preferably 1.50 to 1.52.

[0886] Examples of the transparent glass substrate include tempered glass such as Gorilla Glass from Corning Incorporated Co., Ltd. Furthermore, materials used in Japanese Patent Application Laid-Open Nos. 2010-86684, 2010-152809, and 2010-257492 can be used as the transparent glass substrate.

[0887] When a film substrate is used as the substrate, it is preferably a film substrate with small optical distortion and / or high transparency. Examples of such film substrates include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.

[0888] When the substrate is produced by a roll-to-roll method, a film substrate is preferred. When the circuit wiring for a touch panel is produced by a roll-to-roll method, the substrate is preferably a sheet-like resin composition.

[0889] Examples of the conductive layer included in the substrate include conductive layers used for general circuit wiring and touch panel wiring.

[0890] From the viewpoint of conductivity and thin line formability, the conductive layer is preferably at least one layer selected from a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, more preferably a metal layer, and still more preferably a copper layer or a silver layer.

[0891] The substrate may have a single conductive layer or may have two or more conductive layers. In the case of having two or more conductive layers, the conductive layers are preferably made of different materials.

[0892] Examples of the material for the conductive layer include metals and conductive metal oxides.

[0893] Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au.

[0894] Examples of the conductive metal oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO 2 .

[0895] In this specification, “conductive” means a volume resistivity of less than 1×10 6 Ωcm. The volume resistivity of the conductive metal oxide is preferably less than 1×10 4 Ωcm.

[0896] When a resin pattern is produced using a substrate having a plurality of conductive layers, it is preferred that at least one of the plurality of conductive layers contain a conductive metal oxide.

[0897] As the conductive layer, an electrode pattern of a sensor corresponding to a visual recognition portion used in a capacitive touch panel or wiring of a peripheral extraction portion is preferable.

[0898] As a preferred embodiment of the conductive layer, for example, the description in paragraph 0141 of International Publication No. 2018 / 155193 can be cited, and the content thereof is incorporated into this specification.

[0899] As the substrate having a conductive layer, a substrate having at least one of a transparent electrode and a routing wiring is preferable. Such a substrate can be preferably used as a substrate for a touch panel.

[0900] The transparent electrode can preferably function as an electrode for a touch panel and is preferably composed of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide), and a metal mesh or metal fine wires such as silver nanowires.

[0901] Examples of the metal thin wires include thin wires of silver, copper, and the like, among which silver conductive materials such as silver mesh and silver nanowires are preferred.

[0902] As a material of the bypass wiring, metal is preferably used.

[0903] Examples of metals used as the material for the lead-out wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, as well as alloys composed of two or more of these metal elements. Preferred materials for the lead-out wiring are copper, molybdenum, aluminum, and titanium, with copper being particularly preferred.

[0904] To protect electrodes and the like (ie, at least one of touch panel electrodes and touch panel wiring), the touch panel electrode protective film formed using the photosensitive transfer material of the present invention is preferably provided to cover the electrodes and the like directly or via another layer.

[0905] Exposure process

[0906] The method for producing a resin pattern or the method for producing a laminate preferably includes a step of pattern-exposing the photosensitive resin layer (exposure step) after the lamination step.

[0907] In addition, here, "pattern exposure" means a method of exposing in a pattern, that is, exposure in a method in which exposed areas and non-exposed areas exist.

[0908] The positional relationship between the exposed area and the unexposed area in pattern exposure is not particularly limited and can be adjusted appropriately.

[0909] The detailed arrangement and specific dimensions of the pattern in the pattern exposure are not particularly limited. For example, in order to improve the display quality of a display device (e.g., a touch panel) having an input device with circuit wiring produced by an etching method and to reduce the area occupied by the lead wiring, it is preferred that at least a portion of the pattern (preferably the electrode pattern and / or lead wiring portion of the touch panel) include fine lines with a width of 20 μm or less, and more preferably include fine lines with a width of 10 μm or less.

[0910] The light source used for exposure can be appropriately selected and used as long as it irradiates light of a wavelength capable of exposing the photosensitive resin layer (for example, 365 nm or 405 nm). Specific examples include ultrahigh-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes).

[0911] The exposure dose is preferably 5 mJ / cm 2 ~200mJ / cm 2 , more preferably 10 mJ / cm 2 ~100mJ / cm 2 .

[0912] Preferred embodiments of the light source, exposure amount, and exposure method used for exposure include, for example, the description in paragraphs 0146 to 0147 of International Publication No. 2018 / 155193, and these contents are incorporated into this specification.

[0913] In the exposure process, pattern exposure can be performed after the temporary support is peeled off from the photosensitive resin layer, or the temporary support can be peeled off after pattern exposure is performed across the temporary support before peeling off the temporary support. In the case of peeling off the temporary support before exposure, the mask can be exposed by contacting with the photosensitive resin layer, or it can be exposed close to the temporary support without contacting. In the case of exposure without peeling off the temporary support, the mask can be exposed by contacting with the temporary support, or it can be exposed close to the temporary support without contacting. In order to prevent mask contamination caused by contact between the photosensitive resin layer and the mask and to avoid the influence of exposure caused by impurities attached to the mask, it is preferred to pattern expose without peeling off the temporary support. In addition, when the exposure method is contact exposure, in the case of contact exposure method and non-contact exposure method, it is possible to appropriately select a close exposure method, a projection exposure method of a lens system or a reflector system, a direct exposure method using an exposure laser, etc. and use it. In the case of projection exposure of a lens system or a reflector system, an exposure machine with an appropriate lens aperture number (NA) can be used according to the required resolution and depth of focus. In the case of direct exposure, the photosensitive resin layer can be directly drawn or reduced projection exposure can be performed on the photosensitive resin layer through a lens. Furthermore, exposure can be performed not only in the atmosphere but also under reduced pressure or vacuum, and with a liquid such as water inserted between the light source and the photosensitive resin layer.

[0914] <Peeling process>

[0915] The method for producing a resin pattern, the method for producing a laminate, or the etching method may include a peeling step of peeling off the temporary support between the lamination step and the exposure step or between the exposure step and the development step.

[0916] The method of peeling the temporary support is not particularly limited, and the same mechanism as the cover film peeling mechanism described in paragraphs 0161 to 0162 of Japanese Patent Application Laid-Open No. 2010-072589 can be used.

[0917] <Development Process>

[0918] The method for producing a resin pattern or the method for producing a laminate preferably includes, after the exposure step, a step of developing the exposed photosensitive resin layer to form a resin pattern (development step).

[0919] In the development step, the other layers in the non-image area are removed together with the photosensitive resin layer in the non-image area. In addition, in the development step, other layers located on the exposed photosensitive resin layer in the exposed area may also be removed by being dissolved or dispersed in the developer.

[0920] The development of the exposed photosensitive resin layer in the development step can be performed using a developer.

[0921] The developer is not particularly limited as long as it can remove the non-image area of ​​the photosensitive resin layer. For example, a known developer such as one described in Japanese Patent Application Laid-Open No. 5-72724 can be used.

[0922] The developer is preferably an aqueous alkaline solution containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol / L to 5 mol / L (liter). The developer may contain a water-soluble organic solvent and / or a surfactant.

[0923] Examples of the alkaline compound that may be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0924] Preferred developing solutions include those described in paragraph 0194 of International Publication No. 2015 / 093271. Preferred developing methods include, for example, those described in paragraph 0195 of International Publication No. 2015 / 093271.

[0925] The developing method is not particularly limited and may be any of puddle development, shower development, shower and spin development, and immersion development. Shower development is a development process in which a developer is sprayed onto the exposed photosensitive resin layer to remove non-image areas.

[0926] After the development step, it is preferred to remove development residues by spraying a cleaning agent and wiping with a brush.

[0927] The liquid temperature of the developer is not particularly limited, but is preferably 20°C to 40°C.

[0928] Post-exposure and post-baking processes

[0929] The method for producing a resin pattern or the method for producing a laminate may include a step of exposing the resin pattern obtained in the development step (post-exposure step) and / or a step of heating the resin pattern (post-baking step).

[0930] When both the post-exposure step and the post-bake step are included, it is preferable to perform the post-bake after the post-exposure step.

[0931] Etching process

[0932] The etching method preferably includes a step of etching the substrate in a region where the resin pattern is not arranged (etching step).

[0933] In the etching step, the conductive layer is etched using the resin pattern formed by the photosensitive resin layer as an etching resist.

[0934] As the etching method, a known method can be applied, for example, the method described in paragraphs 0209 to 0210 of Japanese Patent Application Publication No. 2017-120435, the method described in paragraphs 0048 to 0054 of Japanese Patent Application Publication No. 2010-152155, wet etching by immersion in an etching solution, and dry etching methods such as plasma etching can be cited.

[0935] The etching solution used in wet etching may be an acidic or alkaline etching solution appropriately selected according to the etching target.

[0936] Examples of acidic etching solutions include aqueous solutions of a single acidic component selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, and mixed aqueous solutions of an acidic component and a salt selected from ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component may also be a combination of multiple acidic components.

[0937] Examples of alkaline etching solutions include aqueous solutions of a single alkaline component selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide), and mixed aqueous solutions of an alkaline component and a salt (e.g., potassium permanganate). The alkaline component may also be a combination of multiple alkaline components.

[0938] <Removal process>

[0939] In the etching method, it is preferable to perform a step of removing the remaining resin pattern (removal step).

[0940] The removal step is not particularly limited and can be performed as needed, but is preferably performed after the etching step.

[0941] The method for removing the residual resin pattern is not particularly limited, and examples thereof include a method of removing by chemical treatment, and a method of removing using a removing liquid is preferred.

[0942] The method for removing the photosensitive resin layer includes immersing the substrate having the remaining resin pattern in a stirring removing liquid having a liquid temperature of preferably 30° C. to 80° C., more preferably 50° C. to 80° C., for 1 to 30 minutes.

[0943] Examples of the removal liquid include those obtained by dissolving an inorganic or organic base component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixture thereof. Examples of the inorganic base component include sodium hydroxide and potassium hydroxide. Examples of the organic base component include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

[0944] Alternatively, removal may be performed using a removal liquid by a known method such as a spraying method, a shower method, or a spin-immersion method.

[0945] <Other Process>

[0946] The method for producing a resin pattern, the method for producing a laminate, and the etching method may include any steps (other steps) other than the above-mentioned steps. For example, the following steps may be mentioned, but the present invention is not limited to these steps.

[0947] Furthermore, examples of exposure steps, development steps, and other steps applicable to the etching method include steps described in paragraphs 0035 to 0051 of Japanese Patent Application Laid-Open No. 2006-23696.

[0948] In addition, as other processes, for example, the process of reducing the visible light reflectivity described in paragraph 0172 of International Publication No. 2019 / 022089, the process of forming a new conductive layer on the insulating film described in paragraph 0172 of International Publication No. 2019 / 022089, etc. can be cited, but it is not limited to these processes.

[0949] -Process for reducing visible light reflectivity-

[0950] The etching method may include a step of performing a treatment to reduce the visible light reflectivity of a portion or all of the plurality of conductive layers included in the substrate.

[0951] As a treatment for reducing visible light reflectance, oxidation treatment can be mentioned. When the substrate has a conductive layer containing copper, oxidation treatment of copper to obtain copper oxide can blacken the conductive layer, thereby reducing the visible light reflectance of the conductive layer.

[0952] The treatment for reducing the visible light reflectance is described in paragraphs 0017 to 0025 of Japanese Patent Application Laid-Open No. 2014-150118 and paragraphs 0041, 0042, 0048, and 0058 of Japanese Patent Application Laid-Open No. 2013-206315, and the contents of these publications are incorporated herein by reference.

[0953] -Step of forming an insulating film, and step of forming a new conductive layer on the surface of the insulating film-

[0954] The etching method also 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.

[0955] Through the above steps, the second electrode pattern insulated from the first electrode pattern can be formed.

[0956] The step of forming the insulating film is not particularly limited, and a known method of forming a permanent film can be used. Alternatively, an insulating film having a desired pattern can be formed by photolithography using a photosensitive material having insulating properties.

[0957] The process of forming a new conductive layer on the insulating film is not particularly limited. For example, a new conductive layer having a desired pattern can be formed by photolithography using a photosensitive material having conductivity.

[0958] The etching method also preferably uses a substrate having multiple conductive layers on both surfaces of the substrate, and circuit formation is performed sequentially or simultaneously on the conductive layers formed on both surfaces of the substrate. This structure can form a touch panel circuit wiring with a first conductive pattern formed on one surface of the substrate and a second conductive pattern formed on the other surface. Furthermore, it is also preferred to form the touch panel circuit wiring with this structure from the two basic surfaces in a roll-to-roll manner.

[0959] <Application>

[0960] The resin pattern produced by the method for producing a resin pattern according to the present invention, the laminate produced by the method for producing a laminate according to the present invention, and the circuit wiring produced by the etching method according to the present invention can be applied to various devices. Devices including the laminate include, for example, input devices, preferably touch panels, and more preferably capacitive touch panels. Furthermore, the input device can be applied to display devices such as organic electroluminescent displays and liquid crystal displays.

[0961] When the laminate is used in a touch panel, the formed resin pattern is preferably used as a protective film for touch panel electrodes or touch panel wiring. In other words, the photosensitive transfer material of the present invention is preferably used to form a touch panel electrode protective film or touch panel wiring.

[0962] (Method for Manufacturing Electronic Device)

[0963] The method for producing the electronic device according to the present invention is not particularly limited as long as it is a method using the photosensitive transfer material according to the present invention.

[0964] The method for manufacturing the electronic device involved in the present invention preferably includes, in sequence: a process of peeling off the protective film from the photosensitive transfer material involved in the present invention; a process of bringing the outermost layer of the photosensitive transfer material from which the protective film is peeled off, which has the photosensitive resin layer relative to the temporary support, into contact with and adhered to a substrate having a conductive layer; a process of pattern-exposing the photosensitive resin layer with the temporary support interposed therebetween; and a process of developing the exposed photosensitive resin layer to form a resin pattern, wherein the manufactured electronic device has the resin pattern.

[0965] The electronic device manufactured by the method for manufacturing an electronic device according to the present invention preferably has the above-mentioned resin pattern as a permanent film.

[0966] Specific aspects of each step in the method for manufacturing an electronic device and the order in which each step is performed are as described in the above sections of “method for manufacturing a resin pattern” and “etching method”, and preferred aspects are also the same.

[0967] In the method for manufacturing an electronic device, the electronic device wiring is formed by the above-mentioned method, and other matters may be referred to a known method for manufacturing an electronic device.

[0968] Furthermore, the method for manufacturing an electronic device may include any steps (other steps) other than the above steps.

[0969] There are no particular restrictions on electronic devices, and preferred examples include semiconductor packages, printed circuit boards, various wiring formation applications for sensor substrates, touch panels, electromagnetic shielding materials, conductive films such as thin film heaters, liquid crystal sealing materials, and structures in the fields of microcomputers or microelectronics.

[0970] The resin pattern is preferably used as a permanent film in the electronic device, for example, an interlayer insulating film, a wiring protection film, a wiring protection film having a refractive index matching layer, or the like.

[0971] Among them, a touch panel is particularly preferably used as the electronic device.

[0972] Figure 3 and Figure 4 An example of a mask pattern used in manufacturing a touch panel is shown.

[0973] Figure 3 The pattern A and Figure 4 In the pattern B shown, GR is a non-image portion (light shielding portion), EX is an image portion (exposed portion), and DL is a frame that virtually represents alignment. Figure 3 By exposing the photosensitive resin layer through a mask of pattern A shown in FIG. 1 , a touch panel having circuit wiring of pattern A corresponding to EX can be manufactured. Specifically, the touch panel can be formed by the method of International Publication No. 2016 / 190405. Figure 1 In one example of a touch panel manufactured, the central portion of the exposure portion EX (the pattern portion of the connection condition) is the portion where the transparent electrode (touch panel electrode) is formed, and the peripheral portion of the exposure portion EX (the thin line portion) is the portion where the wiring of the peripheral extraction portion is formed.

[0974] The above-mentioned method for manufacturing an electronic device is used to manufacture an electronic device having at least wiring for an electronic device, and preferably to manufacture, for example, a touch panel having at least wiring for a touch panel.

[0975] The touch panel preferably includes a transparent substrate, electrodes, an insulating layer, or a protective layer.

[0976] Examples of detection methods in touch panels include well-known methods such as a resistive film method, an electrostatic capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method. Among them, the electrostatic capacitance method is preferred.

[0977] Examples of touch panel types include so-called in-cell types (for example, the touch panels described in FIG. 5 , FIG. 6 , FIG. 7 , and FIG. 8 of Japanese Unexamined Patent Application Publication No. 2012-517051 ), so-called out-cell types (for example, the touch panels described in FIG. 19 of Japanese Unexamined Patent Application Publication No. 2013-168125 , and FIG. 2012-89102 ). Figure 1 and the touch panel described in FIG5 ), OGS (One Glass Solution: single glass solution) type, TOL (Touch-on-Lens: lens touch) type (for example, Japanese Patent Application Laid-Open No. 2013-54727 Figure 2 ), various plug-in types (so-called GG, G1·G2, GFF, GF2, GF1, G1F, etc.) and other structures (for example, the structure described in FIG. 6 of Japanese Patent Application Laid-Open No. 2013-164871).

[0978] As an example of a touch panel, the touch panel described in paragraph 0229 of Japanese Patent Application Laid-Open No. 2017-120435 can be cited.

[0979] Example

[0980] Below, the embodiment of the present invention is further described in detail with reference to the examples. The materials, usage amounts, ratios, processing contents and processing steps shown in the following examples can be appropriately changed as long as they do not depart from the purpose of the embodiment of the present invention. Therefore, the scope of the embodiment of the present invention is not limited to the specific examples shown below. In addition, unless otherwise specified, "parts" and "%" are based on mass.

[0981] <Preparation of Temporary Support 1>>

[0982] The temporary support body 1 was produced by the following method.

[0983] -Preparation of Particle-Containing Layer-Forming Composition 1-

[0984] The components were mixed in the following formulation to obtain a particle-containing layer-forming composition 1. After preparation, the particle-containing layer-forming composition 1 was filtered through a 6 μm filter (F20, manufactured by MAHLE Japan Ltd.) and then degassed using a 2×6 Radial Flow Super Phobic (manufactured by Polypore Co., Ltd.).

[0985] Acrylic acid polymer (AS-563A, manufactured by Daicel Fine Chem Ltd., solid content 27.5% by mass): 167 parts

[0986] Nonionic surfactant (NAROACTY CL95, manufactured by Sanyo Chemical Industries, Ltd., solid content 100% by mass): 0.7 parts

[0987] Anionic surfactant (RAPISOL A-90, manufactured by NOF CORPORATION, diluted with water to a solid content of 1% by mass): 114.4 parts

[0988] Carnauba wax dispersion (Cellulose 524, manufactured by Chukyo Yushi Co., Ltd., solid content 30% by mass): 7 parts

[0989] Carbodiimide compound (CARBODILITE V-02-L2, manufactured by Nisshinbo Co., Ltd., diluted with water to a solid content of 10% by mass): 20.9 parts

[0990] Matting agent (Snowtex XL, manufactured by Nissan Chemical Corporation, solid content 40% by mass, average particle size 50 nm): 2.8 parts

[0991] Water: 690.2 parts

[0992] 〔Extrusion molding〕

[0993] Pellets of polyethylene terephthalate (PET) described in Japanese Patent No. 5575671, using a citric acid chelate organic titanium complex as a polymerization catalyst, were dried to a moisture content of 50 ppm or less and then placed in the hopper of a 30 mm diameter uniaxial kneading extruder, melted, and extruded at 280°C. The melt was passed through a filter (pore size 2 μm) and then extruded from a die onto a chill roll at 25°C to produce an unstretched film. Furthermore, electrostatic application was used to ensure close contact between the extruded melt and the chill roll.

[0994] 〔Stretching, coating〕

[0995] The unstretched film extruded onto a cooling roll and solidified by the above method was subjected to sequential biaxial stretching by the following method to obtain a temporary support having a polyester film with a thickness of 16 μm and a particle-containing layer with a thickness of 40 nm.

[0996] (a) Longitudinal stretching

[0997] The unstretched film was stretched in the longitudinal direction (conveying direction) by passing it between two pairs of nip rolls having different peripheral speeds. The preheating temperature was set to 75°C, the stretching temperature was set to 90°C, the stretching ratio was set to 3.4 times, and the stretching speed was set to 1,300% / second.

[0998] (b) Coating

[0999] The particle-containing layer-forming composition 1 was applied to one surface of the longitudinally stretched film using a bar coater so as to have a thickness of 40 nm after film formation.

[1000] (c) Transverse stretching

[1001] The film subjected to the longitudinal stretching and coating was then transversely stretched using a tenter under the following conditions.

[1002] -Transverse stretching conditions-

[1003] Preheating temperature: 110℃

[1004] Stretching temperature: 120℃

[1005] Stretch ratio: 4.2 times

[1006] Stretching speed: 50% / second

[1007] [Heat setting, heat relaxation]

[1008] Next, the biaxially stretched film after the longitudinal and transverse stretching was heat-set under the following conditions. After the heat-setting, the width of the tenter was reduced, and the film was heat-relaxed under the following conditions.

[1009] -Heat setting conditions-

[1010] Heat setting temperature: 227℃

[1011] Heat setting time: 6 seconds

[1012] -Thermal relaxation conditions-

[1013] Thermal relaxation temperature: 190°C

[1014] Thermal relaxation rate: 4%

[1015] 〔Coiling〕

[1016] After heat setting and heat relaxation, the ends were trimmed, and the ends were extruded (knurled) to a width of 10 mm. The film was then wound at a tension of 40 kg / m. The width was 1.5 m and the roll length was 6,300 m. The resulting film roll was used as the temporary support 1.

[1017] The haze of the obtained temporary support 1 was 0.2. The haze was measured as the total optical haze using a haze meter (NDH2000 manufactured by NIPPON DENSHOKU INDUSTRIES Co., Ltd.).

[1018] The heat shrinkage ratio after heating at 150° C. for 30 minutes was 1.0% on the MD (machine direction) side and 0.2% on the TD (a direction perpendicular to the machine direction on the surface of the film).

[1019] The film thickness of the particle-containing layer was measured from a cross-sectional TEM photograph and was 40 nm. The average particle size of the particles contained in the particle-containing layer was measured using a HT-7700 transmission electron microscope (TEM) manufactured by Hitachi High-Technologies Corporation by the above method and was 50 nm.

[1020] <Preparation of Temporary Support 2>>

[1021] The temporary support body 1 was produced in the same manner as that of the temporary support body 1 except that the overall thickness was changed.

[1022] <Preparation of Photosensitive Resin Compositions 1 to 5>

[1023] After mixing so as to have the composition shown in Table 1 below, methyl ethyl ketone was added to prepare photosensitive resin compositions 1 to 5 (solid content concentration: 25% by mass).

[1024] [Table 1]

[1025]

[1026] In addition, the details of the compounds described in Table 1 are shown below.

[1027] BPE-500: 2,2-bis(4-(methacryloyloxypentaethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd.

[1028] BPE-200: 2,2-bis(4-(methacryloyloxydiethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd.

[1029] M-270: Polypropylene glycol diacrylate, manufactured by TOAGOSEI CO., LTD.

[1030] A-TMPT: trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.

[1031] SR-454: Ethoxylated (3) trimethylolpropane trimethacrylate, manufactured by Sartomer Company, Inc.

[1032] SR-502: Ethoxylated (9) trimethylolpropane trimethacrylate, manufactured by Sartomer Company, Inc.

[1033] A-9300-1CL: ε-caprolactone-modified tris-(2-acryloyloxyethyl) isocyanurate, manufactured by Shin-Nakamura Chemical Co., Ltd.

[1034] B-CIM: Photoradical generator (photopolymerization initiator), manufactured by Hampford, 2-(2-chlorophenyl)-4,5-diphenylimidazole dimer

[1035] SB-PI 701: Sensitizer, 4,4'-bis(diethylamino)benzophenone, obtained from Sanyo Trading Co., Ltd.

[1036] CBT-1: Rust inhibitor, carboxybenzotriazole, manufactured by JOHOKU CHEMICAL CO., LTD.

[1037] TDP-G: polymerization inhibitor, phenothiazine, manufactured by Kawaguchi Chemical Industry Co., LTD.

[1038] Irganox 245: Hindered phenol-based polymerization inhibitor, manufactured by BASF

[1039] F-552: Fluorine-based surfactant, Megaface F552, manufactured by DIC Corporation

[1040] <Preparation of water-soluble resin composition>

[1041] 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 part by mass.

[1042] Ion exchange water: 38.12 parts

[1043] Methanol (manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC.): 57.17 parts

[1044] KURARAY POVAL 4-88LA (polyvinyl alcohol, manufactured by KURARAY CO., LTD.): 3.22 parts

[1045] Polyvinylpyrrolidone K-30 (manufactured by NIPPON SHOKUBAI CO., Ltd.): 1.49 parts

[1046] Megaface F-444 (fluorine-based surfactant, manufactured by DIC Corporation): 0.0035 parts

[1047] <Preparation of Thermoplastic Resin Composition>

[1048] The thermoplastic resin composition was prepared by mixing the following components.

[1049] Polymer A-2 (copolymer 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

[1050] Pigment B-1 (the following compound): 0.1 part

[1051] Photoacid generator C-1 (the following compound): 0.1 part

[1052] Plasticizer D-3 (NK Ester A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.): 2.2 parts

[1053] Plasticizer D-4 (8UX-015A, manufactured by TAISEI FINE CHEMICAL CO., LTD.): 1.1 parts

[1054] Plasticizer D-5 (ARONIX TO-2349, manufactured by TOAGOSEI CO., LTD.): 0.5 parts

[1055] Megaface F-551 (fluorine-based surfactant, manufactured by DIC Corporation): 0.02 parts

[1056] Phenothiazine: 0.03 parts

[1057] CBT-1 (rust inhibitor, carboxybenzotriazole, manufactured by JOHOKU CHEMICAL CO., LTD.): 0.03 parts

[1058] Methyl ethyl ketone (manufactured by SANKYO CHEMICAL Co., Ltd.): 63.0 parts

[1059] Propylene glycol monomethyl ether (manufactured by SANWA KAGAKU SANGYO Co., Ltd.): 9.0 parts

[1060] Propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO KK): 9.0 parts

[1061] The pigment B-1 is shown below.

[1062] [Chemical Formula 25]

[1063]

[1064] The photoacid generator C-1 is shown below.

[1065] [Chemical Formula 26]

[1066]

[1067] (Examples 1 to 7 and Comparative Examples 1 and 3)

[1068] <Production of Photosensitive Transfer Materials>

[1069] To form the coating layer structures described in Tables 5 and 6, the photosensitive resin composition described in Table 6 was applied to the temporary support described in Table 5 using a slit nozzle to a coating width of 1.0 m and a layer thickness described in Table 6. The film was then passed through a drying zone at 80°C for 40 seconds to form a photosensitive resin layer. The protective film described in Table 5 was then pressure-bonded to the temporary support to produce a photosensitive transfer material, which was then wound into a roll.

[1070] (Examples 8 to 12 and Comparative Example 2)

[1071] <Production of Photosensitive Transfer Materials>

[1072] To form the coating layer structures described in Tables 5 and 6, the thermoplastic resin composition described in Table 6 was applied to the temporary support described in Table 5 using a slit nozzle to a coating width of 1.0 m and a layer thickness described in Table 6. The resulting film was then passed through a drying zone at 80°C for 40 seconds to form a thermoplastic resin layer. Subsequently, the water-soluble resin composition described in Table 6 was applied to the thermoplastic resin layer using a slit nozzle to a coating width of 1.0 m and a layer thickness described in Table 6. The resulting film was then passed through a drying zone at 80°C for 40 seconds to form a water-soluble resin layer. Furthermore, the photosensitive resin composition described in Table 6 was applied to the water-soluble resin layer using a slit nozzle to a coating width of 1.0 m and a layer thickness described in Table 6. The resulting film was then passed through a drying zone at 80°C for 40 seconds to form a photosensitive resin layer. The protective film described in Table 5 was press-bonded thereto to prepare a photosensitive transfer material, which was then wound into a roll.

[1073] (Examples 13 to 28)

[1074] <Preparation of Photosensitive Resin Composition>

[1075] Photosensitive resin compositions A-1 to A-10 were respectively prepared to have the compositions shown in the following Table 2. In addition, the numerical values ​​in the columns of each component in Table 2 represent parts by mass.

[1076] [Table 2]

[1077]

[1078] The details of the compounds other than those described above and listed in Table 2 are shown below.

[1079] Compound B and Compound C: The following compounds

[1080] [Chemical Formula 27]

[1081]

[1082] <Preparation of a 36.3% by mass solids solution of alkali-soluble resin P-1>

[1083] A 36.3 mass % solids solution of polymer P-1 having the following structure (solvent: propylene glycol monomethyl ether acetate) was used: In P-1, the numerical value on the lower right of each structural unit represents the content ratio (mol %) of each structural unit.

[1084] A solution of P-1 having a solid content of 36.3% by mass was prepared by the polymerization step and the addition step described below.

[1085] -Polymerization process-

[1086] Propylene glycol monomethyl ether acetate (manufactured by Sanwa Kagaku Sangyo Co., Ltd., trade name PGM-Ac) (60 g) and propylene glycol monomethyl ether (manufactured by Sanwa Kagaku Sangyo Co., Ltd., trade name PGM) (240 g) were introduced into a 2,000 mL flask. The resulting liquid was heated to 90° C. while stirring at a stirring speed of 250 rpm (revolutions per minute).

[1087] The dropping solution (1) was prepared by mixing 107.1 g of methacrylic acid (manufactured by Mitsubishi Rayon Co., Ltd., trade name Acrylic Ester M), 5.46 g of methyl methacrylate (manufactured by Mitsubishi Chemical Corporation, trade name MMA), and 231.42 g of cyclohexyl methacrylate (manufactured by Mitsubishi Chemical Corporation, trade name CHMA), and diluting with PGM-Ac (60 g) to obtain the dropping solution (1).

[1088] As preparation of the dropping solution (2), dimethyl 2,2'-azobis(2-methylpropionate) (manufactured by Fujifilm Wako Pure Chemical Corporation, trade name V-601) (9.637 g) was dissolved in PGM-Ac (136.56 g) to obtain the dropping solution (2).

[1089] The dropwise liquid (1) and the dropwise liquid (2) were 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.

[1090] Next, the container for the droplet (1) was rinsed with PGM-Ac (12 g), and the rinsed liquid was added dropwise to the 2,000 mL flask. Next, the container for the droplet (2) was rinsed with PGM-Ac (6 g), and the rinsed liquid was added dropwise to the 2,000 mL flask. During these additions, the reaction solution in the 2,000 mL flask was maintained at 90°C and stirred at a stirring speed of 250 rpm. Furthermore, as a post-reaction, stirring was continued at 90°C for 1 hour.

[1091] As the first additional addition of initiator, V-601 (2.401 g) was added to the reaction solution after the post-reaction. Furthermore, the container of V-601 was rinsed with PGM-Ac (6 g), and the rinse was introduced into the reaction solution. The mixture was then stirred at 90°C for 1 hour.

[1092] Next, V-601 (2.401 g) was added to the reaction solution as the second additional initiator. The V-601 container was rinsed with PGM-Ac (6 g), and the rinse was introduced into the reaction solution. The mixture was then stirred at 90°C for 1 hour.

[1093] Next, V-601 (2.401 g) was added to the reaction solution as the third additional initiator. Furthermore, the V-601 container was rinsed with PGM-Ac (6 g), and the rinse was introduced into the reaction solution. The mixture was then stirred at 90°C for 3 hours.

[1094] -Addition process-

[1095] 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 Corporation) (1.8 g) and hydroquinone monomethyl ether (manufactured by FUJIFILM Wako Pure Chemical Corporation) (0.8 g) were added to the reaction solution. Furthermore, each container was rinsed with PGM-Ac (6 g), and the rinse was introduced into the reaction solution. The temperature of the reaction solution was then raised to 100°C.

[1096] Next, glycidyl methacrylate (manufactured by NOF CORPORATION, trade name BLEMMEERG) (76.03 g) was added dropwise to the reaction solution over 1 hour. The BLEMMEERG container was rinsed with PGM-Ac (6 g), and the rinse was introduced into the reaction solution. The mixture was then stirred at 100°C for 6 hours as an addition reaction.

[1097] The reaction solution was then cooled and filtered through a 100-mesh dust removal filter to obtain a solution (1,158 g) of polymer D (solids concentration: 36.3% by mass). The resulting 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.

[1098] P-1 (In the following formula, the molar ratio of the structural repeating units is 51.5:2:26.5:20 from the left side.)

[1099] [Chemical Formula 28]

[1100]

[1101] <Preparation of a 36.5% by mass solids solution of the alkali-soluble resin P-2>

[1102] 82.4 g of propylene glycol monomethyl ether was placed in a flask and heated to 90° C. under a nitrogen stream. To this liquid, a solution of 38.4 g of styrene, 30.1 g of dicyclopentanyl methacrylate, and 34.0 g of methacrylic acid dissolved in 20 g of propylene glycol monomethyl ether and a solution of 5.4 g of polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) dissolved in 43.6 g of propylene glycol monomethyl ether acetate were added dropwise over 3 hours. After the addition was completed, 0.75 g of V-601 was added three times every hour. Then, the mixture was allowed to react for a further 3 hours. Thereafter, the mixture was diluted with 58.4 g of propylene glycol monomethyl ether acetate and 11.7 g of propylene glycol monomethyl ether. Under an air stream, the reaction solution was heated to 100° C., and 0.53 g of tetraethylammonium bromide and 0.26 g of p-methoxyphenol were added. 25.5 g of glycidyl methacrylate (BLEMMEER GH manufactured by NOF Corporation) was added dropwise thereto over a period of 20 minutes. The mixture was reacted at 100° C. for 7 hours to obtain a solution of polymer P-2. The obtained solution had a solid content concentration of 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 relative to the polymer solid content in any monomer.

[1103] P-2 (In the following formula, the molar ratio of the structural repeating units is 41.0:15.2:23.9:19.9 from the left side.)

[1104] [Chemical Formula 29]

[1105]

[1106] <Preparation of a 36.2% by mass solids solution of the alkali-soluble resin P-3>

[1107] 113.5 g of propylene glycol monomethyl ether was placed in a flask and heated to 90° C. under a nitrogen stream. To this liquid, a solution of 172 g of styrene, 4.7 g of methyl methacrylate, and 112.1 g of methacrylic acid dissolved in 30 g of propylene glycol monomethyl ether and a solution of 27.6 g of polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) dissolved in 57.7 g of propylene glycol monomethyl ether were added dropwise over 3 hours. After the addition was completed, 2.5 g of V-601 was added three times every hour. The mixture was then allowed to react for a further 3 hours. The mixture was then diluted with 160.7 g of propylene glycol monomethyl ether acetate and 233.3 g of propylene glycol monomethyl ether. The reaction solution was heated to 100° C. under an air stream, and 1.8 g of tetraethylammonium bromide and 0.86 g of p-methoxyphenol were added. 71.9 g of glycidyl methacrylate (BLEMMEER G manufactured by NOF CORPORATION) was added dropwise thereto over a period of 20 minutes. The mixture 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 relative to the polymer solid content in any monomer.

[1108] P-3 (In the following formula, the molar ratio of the structural repeating units is 55.1:26.5:1.6:16.8 from the left side.)

[1109] [Chemical formula 30]

[1110]

[1111] <Preparation of a 36.2% by mass solids solution of the alkali-soluble resin P-4>

[1112] In the synthesis of P-3, a 36.2% solids solution of P-4 (solvent: propylene glycol monomethyl ether acetate) was prepared by varying the types and amounts of monomers. The resulting 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.

[1113] P-4 (In the following formula, the molar ratio of the structural repeating units is 55.1:24.6:1.6:17.0:1.7 from the left side.)

[1114] [Chemical Formula 31]

[1115]

[1116] <Preparation of Refractive Index Adjusting Layer Forming Composition>

[1117] Next, refractive index adjusting layer-forming compositions B-1 to B-4 were prepared with the compositions described in the following Table 3. The numerical values ​​of the components in Table 3 represent "parts by mass."

[1118] [Table 3]

[1119]

[1120] Polymer A in Table 3 was prepared by the following synthesis.

[1121] 1-Methoxypropanol (manufactured by Tokyo Chemical Industry Co., Ltd.) (270.0 g) was introduced into a 1 L three-necked flask and heated to 70°C under a nitrogen stream while stirring. Separately, allyl methacrylate (45.6 g) (manufactured by FUJIFILM Wako Pure Chemical Corporation) and methacrylic acid (14.4 g) (manufactured by FUJIFILM Wako Pure Chemical Corporation) were dissolved in 1-methoxypropanol (manufactured by Tokyo Chemical Industry Co., Ltd.) (270.0 g), and 3.94 g of V-65 (manufactured by FUJIFILM Wako Pure Chemical Corporation) was further dissolved to prepare a dropping solution. This was added dropwise to the flask over 2.5 hours. The reaction was continued while stirring for 2.0 hours.

[1122] The temperature was then returned to room temperature and the mixture was added dropwise to stirred ion-exchanged water (2.7 L) for reprecipitation to obtain a suspension. The suspension was filtered through a suction filter with the filter paper removed, and the filtrate was washed with ion-exchanged water to obtain a wet powder. Air drying at 45°C was performed to confirm that the weight had been constant, yielding Polymer A as a powder with a yield of 70%.

[1123] The ratio of methacrylic acid / allyl methacrylate in the obtained polymer A was 76 / 24 (mass %) and the weight average molecular weight Mw was 38,000.

[1124] <Preparation of coating layers 11 to 26>

[1125] Using a slit nozzle, the coating amount was adjusted so that the film thickness after drying would be the thickness shown in Table 4. Any one of the photosensitive resin compositions A-1 to A-10 listed in Table 4 was applied onto a temporary support of a 16 μm thick polyethylene terephthalate film (LUMIRROR 16QS62, manufactured by Toray Industries, Inc.) to form a photosensitive resin layer.

[1126] After the solvent was evaporated in a drying zone at 100°C, at least one of the refractive index adjusting layer-forming compositions B-1 to B-4 listed in Table 4 was applied using a slit nozzle, with the coating amount adjusted to achieve the film thickness listed in Table 4 after drying. The coating was then applied onto the photosensitive resin layer and dried at 80°C to form a refractive index adjusting layer. A protective film (LUMIRROR 16QS62, manufactured by Toray Industries, Inc.) was pressure-bonded onto the refractive index adjusting layer to form coating layers 11 to 26.

[1127] [Table 4]

[1128]

[1129] <Production of PET substrate with copper layer>

[1130] A copper layer having a thickness of 200 nm was formed on a polyethylene terephthalate (PET) film having a thickness of 100 μm by sputtering, thereby producing a PET substrate with a copper layer.

[1131] [evaluate]

[1132] <Measurement of surface energy>

[1133] The surface energy (unit: mN / m) of the temporary support or the protective film was calculated by the following method.

[1134] On the measurement surface of the temporary support or protective film, the contact angles of pure water and diiodomethane were measured at three points using a contact angle meter CA-A (manufactured by Kyowa Interface Science Co., Ltd.) at room temperature of 23°C and relative humidity of 50% to 60%. The average of the measured values ​​obtained for each liquid was used as the contact angle of each of the two liquids. The dispersion force γ was calculated using the geometric mean method based on the Owens-Wendt method using the contact angles of the two liquids obtained. d , polar force γ p and the surface energy γ (=γ d +γ p ).

[1135] The specific calculation method is shown in the following table. The meaning of each symbol is as follows. SL When is the tension at the interface between the solid and the liquid, equation (1) holds true.

[1136] γ SL : Surface free energy of film surface and known liquid

[1137] γ S : Surface free energy of the film surface

[1138] γ L : Surface free energy of known liquids

[1139] γ S d : Dispersion force component of the surface free energy of the film surface

[1140] γ S p : Polar force component of the surface free energy of the film surface

[1141] γ L d :Dispersion force component of the surface free energy of a known liquid

[1142] γ L p :Polar force component of surface free energy of known liquids

[1143] γ SL =γ S +γ L -2(γ S d γ L d ) 1 / 2 -2(γ S p γ L p ) 1 / 2 ...Formula (1)

[1144] The state when a smooth solid surface contacts a liquid droplet at a contact angle (θ) is expressed by the following formula (Young's formula).

[1145] γ S =γ SL +γ L cosθ……Formula (2)

[1146] Combining these equations (1) and (2) yields the following equation.

[1147] (γ s d γ L d )1 / 2 +(γ s p γ L p ) 1 / 2 =γ L (1+cosθ) / 2……Formula (3)

[1148] In fact, the contact angle (θ) of pure water and diiodomethane, the surface energy γ of the known liquid L And each component (γ L d , γ L p ) into equation (3) to solve the simultaneous equations.

[1149] As a result, the surface energy (γ S ). In addition, the numerical values ​​of the known liquid are set to the following values.

[1150] Pure water: γ L =72.8mN / m, γ L d =21.8mN / m,γ L p =51.0mN / m

[1151] Diiodomethane: γ L =50.8mN / m,γ L d =49.5mN / m,γ L p =1.3mN / m

[1152] <Defect Evaluation>

[1153] The protective film was peeled off from the prepared photosensitive transfer material, and it was laminated on a PET substrate with a copper layer under the lamination conditions of a lamination roller temperature of 100°C, a linear pressure of 0.6 MPa,...

Claims

1. A photosensitive transfer material comprising a temporary support, a photosensitive resin layer and a protective film in this order, When the surface energy of the surface of the temporary support opposite to the photosensitive resin layer is γb and the surface energy of the surface of the protective film opposite to the photosensitive resin layer is γc, γb≥γc is satisfied, and the units of γb and γc are mN / m. The value of γb is 45mN / m to 70mN / m, the value of γc is 36mN / m to 65mN / m, and the value of γb-γc exceeds 0mN / m and is 50mN / m or less. The photosensitive transfer material is a roll-shaped photosensitive transfer material.

2. The photosensitive transfer material according to claim 1, wherein The temporary support has a thickness of 20 μm or less.

3. The photosensitive transfer material according to claim 1, wherein The photosensitive resin layer has a thickness of 10 μm or less.

4. The photosensitive transfer material according to claim 1, wherein Another layer is further provided between the temporary support and the photosensitive resin layer.

5. The photosensitive transfer material according to claim 1, wherein The temporary support has a haze value of less than 1.0%.

6. The photosensitive transfer material according to claim 1, wherein The temporary support has a peeling force of 0.5 mN / mm or more.

7. The photosensitive transfer material according to claim 1, wherein The value of the arithmetic mean roughness Ra of the surface of the temporary support on the side opposite to the photosensitive resin layer side is 50 nm or less.

8. The photosensitive transfer material according to claim 1, wherein The value of the arithmetic mean roughness Ra of the surface of the protective film on the side opposite to the photosensitive resin layer side is 50 nm or less.

9. The photosensitive transfer material according to claim 1, wherein The value of γb-γc is 2 mN / m or more and 30 mN / m or less.

10. The photosensitive transfer material according to claim 1, wherein The value of γb-γc is 7 mN / m or more and 20 mN / m or less.

11. A method for manufacturing a resin pattern, comprising: a step of peeling the protective film from the photosensitive transfer material according to any one of claims 1 to 10; a step of bringing the outermost layer of the photosensitive transfer material from which the protective film has been peeled off, the outermost layer having the photosensitive resin layer facing the temporary support, into contact with and laminating the substrate having the conductive layer; a step of pattern-exposing the photosensitive resin layer via the temporary support; and A step of developing the exposed photosensitive resin layer to form a resin pattern.

12. An etching method comprising the following steps: 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 11 are sequentially laminated, the conductive layer is etched in a region where the resin pattern is not provided.

13. A method for manufacturing an electronic device, comprising: a step of peeling the protective film from the photosensitive transfer material according to any one of claims 1 to 10; a step of bringing the outermost layer of the photosensitive transfer material from which the protective film has been peeled off, the outermost layer having the photosensitive resin layer facing the temporary support, into contact with and laminating the substrate having the conductive layer; a step of pattern-exposing the photosensitive resin layer via the temporary support; and a step of developing the exposed photosensitive resin layer to form a resin pattern, The manufactured electronic device has the resin pattern.

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