Photosensitive transfer material, method for producing resin pattern, and method for producing conductive pattern

Abstract

Provided are a photosensitive transfer material which sequentially comprises a provisional support, an intermediate layer, and a photosensitive layer, wherein the photosensitive layer has a melt viscosity at 25°C of 5.0 × 105 Pa∙s or more and a storage elastic modulus of 1.0 × 109 Pa to 4.0 × 109 Pa when cured; and a method for producing a resin pattern and a method for producing a conductive pattern, each of which uses the photosensitive transfer material.

Description

Photosensitive transfer material, method for manufacturing a resin pattern, and method for manufacturing a conductive pattern

[0001] This disclosure relates to a photosensitive transfer material, a method for manufacturing a resin pattern, and a method for manufacturing a conductive pattern.

[0002] A widely used method involves placing a photosensitive layer on any substrate using a photosensitive transfer material, exposing this photosensitive layer through a mask, and then developing it, due to the reduced number of steps required to obtain a predetermined pattern.

[0003] Conventional photosensitive transfer materials include those described in Patent Document 1 or 2. Patent Document 1 describes a transfer film comprising a temporary support, a metal layer formed on the temporary support, a transparent conductive layer formed on the metal layer, and an adhesive layer formed on the transparent conductive layer.

[0004] Patent Document 2 describes a temporary support having a thickness of 38 μm or less, and a curable transparent resin layer placed in direct contact with the temporary support, wherein the thickness of the curable transparent resin layer is 5 μm or more, the curable transparent resin layer contains a binder polymer, a polymerizable compound, and a polymerization initiator, and the melt viscosity ηc of the curable transparent resin layer measured at 100°C is 1.0 x 10⁻¹⁰. ３ The description mentions a transfer film with a Pa·s rating of 100% or higher.

[0005] Patent Document 1: Japanese Unexamined Patent Publication No. 2011-20333 Patent Document 2: Japanese Unexamined Patent Publication No. 2020-73309

[0006] One problem that one embodiment of the present invention aims to solve is to provide a photosensitive transfer material that exhibits excellent stability after peeling off a temporary support and excellent adhesion of the resulting pattern to copper. Another problem that one embodiment of the present invention aims to solve is to provide a method for manufacturing a resin pattern using the above-mentioned photosensitive transfer material, and a method for manufacturing a conductive pattern.

[0007] The means for solving the above problem include the following embodiments: <1> Having a temporary support, an intermediate layer, and a photosensitive layer in this order, wherein the melt viscosity of the photosensitive layer at 25°C is 5.0 × 10 ５The photosensitive material is Pa·s or higher, and the storage modulus of the cured photosensitive layer is 1.0 × 10⁻⁶ ９ Pa ~ 4.0 x 10 ９ A photosensitive transfer material that is Pa. <2> The photosensitive transfer material according to <1>, wherein the photosensitive layer comprises a binder. <3> The photosensitive transfer material according to <2>, wherein the glass transition temperature of the binder is 75°C or higher and 110°C or lower. <4> The photosensitive transfer material according to <2> or <3>, wherein the acid value of the binder is 80 mg KOH / g or higher. <5> The photosensitive transfer material according to any one of <2> to <4>, wherein the binder comprises a resin having constituent units derived from a styrene compound. <6> The photosensitive transfer material according to any one of <1> to <5>, wherein the temporary support and the intermediate layer are in contact. <7> The photosensitive transfer material according to any one of <1> to <6>, wherein the intermediate layer comprises a surfactant. <8> The photosensitive transfer material according to <7>, wherein the surfactant comprises a surfactant having silicon atoms. <9> The photosensitive transfer material according to any one of <1> to <8>, wherein the average thickness of the intermediate layer is 1 μm to 10 μm. <10> The photosensitive transfer material according to any one of <1> to <9>, wherein the average thickness of the photosensitive layer is 10 μm to 30 μm. <11> A method for manufacturing a resin pattern, comprising the steps of: bonding the photosensitive transfer material and the substrate so that the photosensitive layer in the photosensitive transfer material according to any one of <1> to <10> is in contact with the substrate; pattern exposure of the photosensitive layer; and developing the photosensitive layer after exposure to form a resin pattern, wherein the step of peeling off the temporary support is after the bonding step and before the step of developing the photosensitive layer after exposure. <12> A method for manufacturing a conductive pattern, comprising the steps of forming the resin pattern on a substrate using the resin pattern manufacturing method described in <11>, performing a plating treatment on an area of ​​the substrate where the resin pattern is not formed, and removing the resin pattern, in this order. <13> A method for manufacturing a conductive pattern, comprising the steps of forming the resin pattern on a substrate using the resin pattern manufacturing method described in <11>, etching an area of ​​the substrate where the resin pattern is not formed, and removing the resin pattern, in this order.

[0008] According to one embodiment of the present invention, a photosensitive transfer material can be provided that exhibits excellent stability after peeling off a temporary support and excellent adhesion of the resulting pattern to copper. Furthermore, according to one embodiment of the present invention, a method for manufacturing a resin pattern using the above-mentioned photosensitive transfer material and a method for manufacturing a conductive pattern can be provided.

[0009] This is a schematic diagram showing an example of the configuration of the photosensitive transfer material relating to this disclosure.

[0010] The present disclosure is described in detail below. In this specification, a numerical range expressed using "~" means a range that includes the numbers written before and after "~" as the lower and upper limits. In this specification, in numerical ranges described in steps, the upper or lower limit stated in one numerical range may be replaced with the upper or lower limit of another numerical range described in steps. Also, in numerical ranges described in this specification, the upper or lower limit stated in one numerical range may be replaced with the values ​​shown in the examples. In this specification, the term "process" is included not only in the sense of an independent process, but also in the sense of a process that cannot be clearly distinguished from other processes, as long as the intended purpose of that process is achieved. In this specification, "transparent" means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more, and preferably 90% or more. In this specification, the average transmittance of visible light is a value measured using a spectrophotometer, for example, it can be measured using a spectrophotometer U-3310 manufactured by Hitachi, Ltd. In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are calculated using polystyrene as the standard substance, measured by a gel permeation chromatography (GPC) analyzer using TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all product names of Tosoh Corporation) as the column, THF (tetrahydrofuran) as the eluent, a differential refractometer as the detector, and polystyrene as the standard substance. In addition, unless otherwise specified, the molecular weight of a compound with a molecular weight distribution is the weight-average molecular weight (Mw). In this specification, "(meth)acrylic" is a concept that encompasses both acrylic and methacrylic, "(meth)acryloyloxy group" is a concept that encompasses both acryloyloxy group and methacryloyloxy group, "(meth)acrylamide group" is a concept that encompasses both acrylamide group and methacrylamide group, and "(meth)acrylate" is a concept that encompasses both acrylate and methacrylate.

[0011] In this specification, "alkali-soluble" means that the solubility in 100 g of a 1% by mass sodium carbonate aqueous solution at a liquid temperature of 22°C is 0.1 g or more. Therefore, for example, an alkali-soluble resin refers to a resin that satisfies the above solubility conditions. In this specification, "water-soluble" means that the solubility in 100 g of water with a pH of 7.0 at a liquid temperature of 22°C is 0.1 g or more. Therefore, for example, a water-soluble resin refers to a resin that satisfies the above solubility conditions. In this specification, the "solid content" of a composition refers to the components that form the composition layer formed using the composition, and if the composition contains a solvent (organic solvent, water, etc.), it refers to all components excluding the solvent. Furthermore, liquid components that form the composition layer are also considered to be solid content. In this specification, the average thickness of the temporary support, intermediate layer, photosensitive layer, etc. is measured by cross-sectional observation using an SEM (Scanning Electron Microscope), and the average thickness is calculated as the average value of any five points. In this specification, the dielectric loss tangent of the substrate at 24 GHz is measured by the resonator method. As the apparatus for measuring the dielectric loss tangent, a 24 GHz split-cylinder type resonator manufactured by Kanto Electronics Applied Development Co., Ltd. or an apparatus of equivalent quality can be used.

[0012] (Photosensitive Transfer Material) The photosensitive transfer material according to this disclosure comprises a temporary support, an intermediate layer, and a photosensitive layer in this order, wherein the melt viscosity of the photosensitive layer at 25°C is 5.0 × 10 ５ The photosensitive material is Pa·s or higher, and the storage modulus of the cured photosensitive layer is 1.0 × 10⁻⁶ ９ Pa ~ 4.0 x 10 ９ It is Pa.

[0013] Conventional photosensitive transfer materials, such as those described in Patent Document 1, have a melt viscosity of 5.0 × 10 at 25°C. ５Less than Pa·s. When the intermediate layer absorbs moisture, reticulation (wrinkles on the net) occurs, and problems may arise in pattern formation. Also, in the photosensitive transfer material described in Patent Document 2, the storage elastic modulus of the photosensitive layer (pattern) after curing is too high, and the adhesion to copper is not sufficient, resulting in problems such as pattern peeling and collapse. The photosensitive transfer material according to the present disclosure has a melt viscosity of the above photosensitive layer at 25°C of 5.0×10 ５ Pa·s or more, and the storage elastic modulus of the cured photosensitive layer is 1.0×10 ９ Pa to 4.0×10 ９ Pa. By doing so, the melt viscosity when uncured can be increased, reticulation can be improved, the curability of the pattern can be lowered within a range where the shape is not a problem, the adhesion to copper can be improved, and it is presumed that the stability after peeling of the temporary support and the adhesion of the obtained pattern to copper are excellent.

[0014] The photosensitive transfer material may have a protective film on the surface opposite to the intermediate layer side of the photosensitive layer. FIG. 1 is a schematic diagram showing an example of the configuration of the photosensitive transfer material according to the present disclosure. The photosensitive transfer material 10 shown in FIG. 1 has a temporary support 16, an intermediate layer 20A, a photosensitive layer 18A, and a protective film 12 in this order. Also, the photosensitive transfer material 10 shown in FIG. 1 is in a form in which the protective film 12 is arranged, but the protective film 12 may not be arranged.

[0015] <Melt viscosity of the photosensitive layer at 25°C> The photosensitive transfer material according to the present disclosure has a melt viscosity of the above photosensitive layer at 25°C of 5.0×10 ５ Pa·s or more. From the viewpoints of stability after peeling of the temporary support and adhesion of the obtained pattern to copper, 5.0×10 ５ Pa·s to 1.0×10 ９ Pa·s is preferable, 1.0×10 ６ Pa·s to 5.0×10 ８ Pa·s is more preferable, and 2.0×10 ６ Pa·s to 1.0×10 ８ Pa·s is particularly preferable. When the melt viscosity is 5.0×10 ５If the melt viscosity is smaller than Pa·s, wrinkles will form on the surface of the intermediate layer after transfer and peeling off the temporary support, which will interfere with exposure and result in defects such as pattern loss. ９ When the density is Pa·s or lower, the photosensitive layer softens sufficiently during lamination, making it easy to transfer to substrates with copper on their surface, such as polyimide substrates with a copper layer.

[0016] In this disclosure, the melt viscosity is measured using a rheometer (e.g., an Anton Paar MCR302 rheometer), a 12 mmΦ parallel plate, and a Peltier plate (Gap: approximately 0.8 mm) under the following conditions. The melt viscosity defined in this disclosure is the melt viscosity at 25°C. (1) Temperature: 20°C to 125°C (2) Heating rate: 3°C / min (3) Frequency: 0.1 Hz (4) Strain: 0.02%

[0017] <Storage modulus of the cured photosensitive layer> The photosensitive transfer material according to this disclosure has a storage modulus of 1.0 × 10⁻¹⁰ of the cured photosensitive layer. ９ Pa ~ 4.0 x 10 ９ It is Pa, and from the viewpoint of stability after temporary support removal and adhesion of the resulting pattern to copper, 1.2 × 10 ９ Pa ~ 3.5 × 10 ９ It is preferably Pa, 1.5 × 10 ９ Pa ~ 3.2 × 10 ９ It is more preferable that it be Pa.

[0018] The measurement of the storage elastic modulus of the cured photosensitive layer in the present disclosure shall be performed by the following method. The temporary support of the photosensitive transfer material is peeled off, and a laminate is produced in which the photosensitive layer is laminated on the copper layer of the substrate having a copper layer on the surface. After this is solidly exposed, shower development is performed with a 1% by mass aqueous sodium carbonate solution at a liquid temperature of 25°C, and water washing is carried out to produce a laminate in which the cured photosensitive layer is laminated on the copper layer. In addition, for exposure, a high-pressure mercury lamp having i-line (365 nm) as the main exposure wavelength is used. The exposure amount is arbitrarily set to an amount sufficient for the photosensitive layer to be sufficiently cured. The storage elastic modulus measurement is performed on the cured photosensitive layer surface of the obtained laminate under the following conditions. Apparatus: Nano Triboindenter manufactured by Bruker Indenter: Berkovich indenter Load: 5,000 μN Penetration depth: 1 / 10 of the film thickness of the photosensitive layer after curing Measurement location: Measure at 4 locations by changing the location, and take the average value.

[0019] Hereinafter, the configuration of the photosensitive transfer material other than those described above will be described in detail.

[0020] <Temporary support> The temporary support is a member that supports the photosensitive layer and the like, and is removed by a peeling treatment before exposure.

[0021] The temporary support may have a single-layer structure or a multi-layer structure. The temporary support is preferably a film, and more preferably a resin film. As the temporary support, a film having flexibility and not causing significant deformation, shrinkage, or elongation under pressure or under pressure and heating is preferred. Examples of the above film include polyethylene terephthalate film, polymethyl methacrylate film, triacetyl cellulose film, polystyrene film, polyimide film, polycarbonate film, and the like. The resin film may be a stretched film or an unstretched film, but is preferably a stretched film, and more preferably a biaxially stretched film. Among them, as the temporary support, a polyethylene terephthalate film is preferred. In addition, the film used as the temporary support preferably has no deformation such as wrinkles or scratches.

[0022] The average thickness of the temporary support is not particularly limited, but is preferably 5.0 μm to 200.0 μm, more preferably 5.0 μm to 150.0 μm, still more preferably 5.0 μm to 50.0 μm, and particularly preferably 5.0 μm to 25.0 μm from the viewpoints of ease of handling and versatility.

[0023] From the viewpoint of imparting handling properties, a layer containing fine particles (lubricant layer) may be provided on the surface of the temporary support. The lubricant layer may be provided on one side of the temporary support or on both sides. The diameter of the particles contained in the lubricant layer is preferably 0.05 μm to 0.8 μm. Also, the film thickness of the lubricant layer is preferably 0.05 μm to 1.0 μm.

[0024] From the viewpoints of peelability and resolution of the temporary support, the surface free energy of the surface on the intermediate layer side of the temporary support is preferably 66.0 mJ / m ２ or less, more preferably 63.0 mJ / m ２ or less, and still more preferably 60.0 mJ / m ２ or less. From the viewpoint of the adhesion of the coating film, the lower limit of the surface free energy is preferably 35 mJ / m ２ or more, more preferably 40 mJ / m ２ or more, and still more preferably 45 mJ / m ２ or more.

[0025] In one embodiment, examples of the temporary support include those consisting only of a base material; a laminate including a base material and a particle-containing layer disposed on one surface of the base material; and a laminate including a base material and particle-containing layers disposed on both surfaces of the base material.

[0026] Examples of the base material constituting the temporary support include the above-described resin film, glass, paper, etc. From the viewpoints of strength, flexibility, and light transmittance, the base material constituting the temporary support is preferably a resin film. The resin film is preferably a polyethylene terephthalate film, and more preferably a biaxially stretched polyethylene terephthalate film.

[0027] If a particle-containing layer is arranged on one or both sides of the substrate, the particle-containing layer may be one layer or two or more layers.

[0028] The particle-containing layer can be formed, for example, by applying a particle-containing layer composition to a substrate and drying it. Alternatively, the particle-containing layer can be formed by co-extrusion during the manufacturing of a resin film.

[0029] The particle-containing layer composition preferably contains a binder polymer and particles. The type of binder polymer is not particularly limited and can be appropriately selected depending on the purpose. Examples of binder polymers include acrylic resins, urethane resins, olefin resins, styrene-butadiene resins, ester resins, vinyl chloride resins, and vinylidene chloride resins. When the particle-containing layer is formed by co-extrusion, polyethylene terephthalate is preferably used as the binder polymer.

[0030] The particle-containing layer may contain one type of binder polymer and one type of particle, or it may contain two or more types.

[0031] The particles contained in the particle-containing layer are not particularly limited and can be appropriately selected depending on the purpose. The particle content in the particle-containing layer can be appropriately adjusted by the amount of particles added to the particle-containing layer composition. In this specification, the particles contained in the particle-containing layer are referred to as "added particles".

[0032] The added particles are distinct from impurities that are unexpectedly introduced during the manufacturing process of the temporary support, and from particles that are formed during the manufacturing process of the temporary support. Preferably, the added particles are those that do not melt at 200°C.

[0033] In a temporary support, whether or not a particle is an added particle can be determined, for example, by the following method. Added particles usually have uniform shape and distribution, so they can be identified by observation with an optical microscope.

[0034] Examples of added particles include inorganic particles and organic particles. Examples of inorganic particles include inorganic oxide particles such as silicon dioxide (silica), titanium dioxide (titania), zirconium oxide (zirconia), magnesium oxide (magnesia), and aluminum oxide (alumina). Examples of organic particles include polymer particles such as acrylic resin, polyester, polyurethane, polycarbonate, polyolefin, and polystyrene. If the temporary support has a particle-containing layer, it is preferable that the added particles contained in the particle-containing layer are inorganic oxide particles.

[0035] The average particle size of the added particles is not particularly limited, but is, for example, 0.1 μm to 10 μm. The average particle size is measured using a TEM (transmission electron microscope) after cutting a section with an average thickness of 100 nm using an ultramicrotome.

[0036] In the photosensitive transfer material according to this disclosure, the thermal deformation rate of the temporary support is 1.0% or less, preferably 0.5% or less. The lower limit of the thermal deformation rate is not particularly limited, but is preferably 0%. By having a thermal deformation rate of 1.0% or less of the temporary support, deformation of the substrate to which the photosensitive transfer material is bonded is suppressed.

[0037] In this disclosure, the thermal deformation rate is measured by the following method. On the main surface of the temporary support, the direction parallel to one of the two opposing sets of edges is designated as direction A, and the direction perpendicular to direction A is designated as direction B. Two test specimens are prepared: one cut to a length of 30 mm in direction A and 4 mm in direction B, and another cut to a length of 30 mm in direction B and 4 mm in direction A. The following measurements are performed using the two test specimens. A thermal expansion coefficient measuring device (for example, product name "TMA450EM", manufactured by TA Instruments Co., Ltd.) is used as the measuring device. The measurement conditions are as follows: Measurement mode: tensile mode, Grip distance: 16 mm, Set load: varied from 0.05 N to 0.48 N at a rate of 6.00 N / min. Each test specimen is heated from 25°C to 100°C at a heating rate of 20°C / min, and the elongation of each test specimen is measured five times, and the average value is calculated. Of the two test specimens, the one with the higher average elongation rate will be used as the thermal deformation rate.

[0038] Methods for reducing the thermal deformation rate of the temporary support include, for example, increasing the average thickness of the temporary support, and incorporating particles into the temporary support to increase the amount of particles contained within it.

[0039] In the photosensitive transfer material according to this disclosure, it is preferable that the haze of the temporary support is greater than 2.0% from the viewpoint of suppressing deformation of the substrate to which the photosensitive transfer material is bonded.

[0040] From the above viewpoint, the haze of the temporary support is more preferably 2.5% or higher. The upper limit of the haze is not particularly limited, and is, for example, 10%.

[0041] When forming a pattern using the photosensitive transfer material according to this disclosure, it is preferable to peel off the temporary support after bonding the photosensitive transfer material to the substrate but before exposure. By peeling off the temporary support before exposure, it is unnecessary to consider the effect of high haze on exposure due to the temporary support.

[0042] In this disclosure, haze is measured using a haze meter in accordance with JIS K7136:2000. As a haze meter, for example, a product named "NDH-2000" manufactured by Nippon Denshoku Industries Co., Ltd. is used.

[0043] Furthermore, in the photosensitive transfer material relating to this disclosure, from the viewpoint of suppressing deformation of the substrate to which the photosensitive transfer material is bonded, the total number of particles with a diameter of 5 μm or more and aggregates with a diameter of 5 μm or more contained in the temporary support is 30 particles / mm². ２ A larger amount is preferable.

[0044] The total number of the above-mentioned particles and aggregates is, from the above perspective, 40 particles / mm². ２ It is more preferable that the above be true. There is no particular upper limit to the total number; for example, 50 pieces / mm ２ That is the case.

[0045] In this context, particles and aggregates refer to substances that, when observed with a polarizing microscope on a temporary support, exhibit regions where a difference in polarization from the surrounding area can be observed. Examples of particles and aggregates include resin carbides formed during the manufacturing of the substrate, and catalysts used in the manufacturing of the substrate. Furthermore, when such a particle-containing layer is provided, the added particles contained in the particle-containing layer also fall under the category of particles.

[0046] In this disclosure, the total number of particles and aggregates contained in the temporary support is measured by the following method.

[0047] First, the temporary support is observed using a polarizing microscope (a modified version of the "BX60" product with "U-POT" and "U-AN360" filters inserted, 10x objective lens, manufactured by Olympus), and areas where polarization disturbance occurs are identified as foreign matter (particles or aggregates). The identified foreign matter is then observed using an epi-illuminating laser microscope ("Confocal Laser Microscope VL2000D," manufactured by Lasertec). Additionally, the diameter of the foreign matter is measured using an optical microscope ("BX60," 100x objective lens, manufactured by Olympus), within a 1 mm observation area. ２ The number of foreign objects with a diameter of 5 μm or more is counted. If the foreign object contains voids, the diameter including the voids is measured. If the foreign object is not circular, the longest diameter is measured.

[0048] When forming a pattern using the photosensitive transfer material according to this disclosure, it is preferable to remove the temporary support after bonding the photosensitive transfer material to the substrate but before exposure. By removing the temporary support before exposure, it is unnecessary to consider the effect of the large amount of particles and aggregates contained in the temporary support on exposure.

[0049] Furthermore, in the photosensitive transfer material relating to this disclosure, from the viewpoint of suppressing deformation of the substrate to which the photosensitive transfer material is bonded, the temporary support is 13.5 mm as measured by an epi-emission laser microscope. ２ It is preferable that the region includes an area where the total area ratio of the optical anomaly region observed over that area is greater than 300 ppm.

[0050] From the above viewpoint, it is more preferable that the total area ratio of the optical anomaly region be 350 ppm or more. The upper limit of the total area ratio is not particularly limited, and is, for example, 500 ppm.

[0051] In this disclosure, the area of ​​the optical anomaly region refers to the area of ​​the optical anomaly region observed in a region extending from the center of the average thickness of the temporary support to a distance of 2 μm in either the thickness direction or the other direction.

[0052] In this disclosure, an optically anomalous region is a region of the temporary support whose optical properties differ from those of the main region (the resin constituting the temporary support) (specifically, a region where the reflectance or refractive index differs from that of the main region, or where optical phenomena such as scattering and diffraction occur more strongly than in the main region). If the temporary support contains particles, for example, the optically anomalous region may include both the light-shielding portion due to the particles and the optically anomalous region other than the particles (for example, an anomalous refractive index region having a different refractive index from that of the particles and the main region of the temporary support). Examples of optically anomalous regions include regions with different orientation and / or crystallinity from the main region of the temporary support, regions of air, regions of gases other than air, and void regions where gas is almost absent.

[0053] In this disclosure, the total area of ​​the optical anomaly region is measured by the following method.

[0054] A polarizing filter (OLS4000-QWP) is inserted above the objective lens of an epi-emission laser microscope (OLS-4100, manufactured by Olympus Co., Ltd.). Next, a temporary support cut to 30 mm x 30 mm is horizontally suction-fixed onto the laser microscope stage using a porous adsorption plate (65F-HG, manufactured by Universal Giken Co., Ltd.) and a vacuum pump. The suction-fixed temporary support is observed under conditions of 50x objective lens and laser light intensity of 60 (laser wavelength of 405 nm). At this time, the measurement area is defined as a region extending 2 μm in either direction from the center of the average thickness of the temporary support, and measurements are taken at 200 points in the measurement area of ​​259 μm x 260 μm. Therefore, the total measurement area is 0.259 mm x 0.26 mm x 200 = 13.5 mm. ２ This is the result.

[0055] The difference in light intensity between the pixel with the highest light intensity and the pixel with the lowest light intensity in the measured image is divided into 4096 gradations (where the maximum light intensity value is 4095 and the minimum light intensity value is 0). A histogram is created by graphing the light intensity distribution of pixels in the image (horizontal axis: light intensity gradation (minimum value 0, maximum value 4095), vertical axis: number of pixels). The measured image is binarized using a threshold obtained by adding 400 gradations to the value of the larger of the two tails of the created histogram. The areas of pixels with light intensity greater than the threshold are summed, and this summed area is taken as the total area of ​​the optical anomaly region. The ratio of the total area of ​​the optical anomaly region to the measured area is calculated.

[0056] The temporary support may be subjected to surface treatment such as ultraviolet irradiation, corona discharge, or plasma treatment on the surface in contact with the intermediate layer, in order to improve adhesion with the intermediate layer. When surface treatment is performed by ultraviolet irradiation, the exposure dose should be 10 mJ / cm². ２ ~2,000mJ / cm ２ Preferably, it is 50 mJ / cm ２ ~1,000mJ / cm ２ It is preferable that it be so.

[0057] Examples of light sources for ultraviolet irradiation include light sources that emit light in the wavelength range of 150 nm to 450 nm (e.g., low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes (LEDs)). Output and illuminance are not particularly limited.

[0058] From the viewpoint of better demonstrating the effects of this disclosure, it is preferable that the temporary support and the intermediate layer are in contact. From the viewpoint of transferring the unevenness of the temporary support to the intermediate layer, it is preferable that the surface roughness Rmax of the intermediate layer side surface of the temporary support is 0.5 μm or less, and more preferably 0.01 μm to 0.5 μm.

[0059] The surface roughness Rmax of the intermediate layer side surface of the temporary support is measured by the following method. In this disclosure, the surface roughness Rmax is measured using a 3D optical profiler (e.g., New View 7300, Zygo). First, the temporary support is peeled off from the photosensitive transfer material. The surface profile of the intermediate layer side surface of the temporary support is obtained. The measurement and analysis software used is the Microscope Application of MetroPro ver 8.3.2. Next, the Surface Map screen is displayed using the measurement and analysis software, and histogram data is obtained on the Surface Map screen. The surface roughness Rmax is obtained from the obtained histogram data. The surface roughness Rmax corresponds to the maximum height of the roughness curve at a reference length.

[0060] The temporary support may be made from recycled materials. Examples of recycled materials include used film, which has been washed, chipped, and then used as raw material to make film. A specific example of recycled materials is Toray's Ecouse series.

[0061] <Intermediate Layer> The photosensitive transfer material according to this disclosure has an intermediate layer between the temporary support and the photosensitive layer. Preferably, the intermediate layer has oxygen-blocking ability. The intermediate layer having oxygen-blocking ability improves sensitivity during exposure, reduces the time load on the exposure machine, and improves productivity. Furthermore, if the photosensitive layer in the photosensitive transfer material is a negative-type photosensitive layer containing a radical polymerizable compound, there is also the advantage that oxygen inhibition is less likely to occur in the polymerization reaction during exposure.

[0062] The intermediate layer may contain one or more water-soluble resins. Examples of water-soluble resins include polyvinyl alcohol, polyvinylpyrrolidone, water-soluble cellulose compounds, (meth)acrylamide, polyether compounds, gelatin, vinyl ether compounds, polyamides, phenol compounds, and copolymers thereof.

[0063] From the viewpoint of the peelability, resolution, oxygen barrier ability, and defect suppression in the pattern (hereinafter also simply referred to as "defect suppression") of the temporary support, the intermediate layer preferably contains at least one of polyvinyl alcohol and polyvinylpyrrolidone, more preferably contains polyvinyl alcohol, and even more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone.

[0064] When the intermediate layer contains polyvinyl alcohol, from the viewpoint of peelability, resolution, oxygen barrier capacity, and defect suppression of the temporary support, the content of polyvinyl alcohol relative to the total mass of the intermediate layer is preferably 5% to 95% by mass, more preferably 15% to 90% by mass, even more preferably 25% to 80% by mass, particularly preferably 50% to 75% by mass, and most preferably 55% to 70% by mass. When the intermediate layer contains polyvinylpyrrolidone, from the viewpoint of peelability, resolution, oxygen barrier capacity, and defect suppression of the temporary support, the content of polyvinylpyrrolidone relative to the total mass of the intermediate layer is preferably 20% to 98% by mass, more preferably 23% to 90% by mass, even more preferably 25% to 75% by mass, and particularly preferably 25% to 50% by mass. When the intermediate layer contains polyvinyl alcohol and polyvinylpyrrolidone, from the viewpoint of peelability, resolution, oxygen barrier ability, defect suppression, etc. of the temporary support, the sum of the content of polyvinyl alcohol and polyvinylpyrrolidone relative to the total mass of the intermediate layer is preferably 50% to 99% by mass, more preferably 70% to 99% by mass, and even more preferably 75% to 99% by mass.

[0065] From the viewpoint of the peelability, resolution, oxygen barrier capacity, and defect suppression of the temporary support, it is preferable that the intermediate layer contains one or more compounds X selected from the group consisting of water-soluble cellulose compounds, polyether compounds, phenol compounds, and polyhydric alcohol compounds. Examples of water-soluble cellulose compounds include hydroxyethylcellulose, hydroxypropyl methylcellulose, hydroxypropylcellulose, methylcellulose, and ethylcellulose. Examples of polyether compounds include polyethylene glycol and polypropylene glycol. Examples of phenol compounds include bisphenol A and bisphenol S. Examples of polyhydric alcohol compounds include glycerin, diglycerin, and diethylene glycol. From the viewpoint of the peelability, resolution, oxygen barrier capacity, and defect suppression of the temporary support, among the above, it is preferable that the intermediate layer contains one or more compounds X selected from the group consisting of hydroxypropyl methylcellulose, polyethylene glycol, bisphenol A, and glycerin, more preferably one or more compounds X selected from the group consisting of hydroxypropyl methylcellulose and polyethylene glycol, and even more preferably hydroxypropyl methylcellulose.

[0066] From the viewpoint of peelability, resolution, oxygen barrier ability, defect suppression, etc. of the temporary support, when the intermediate layer contains compound X, the sum of the content of compound X relative to the total mass of the intermediate layer is preferably 0.1% to 36% by mass, more preferably 0.5% to 20% by mass, and even more preferably 1% to 15% by mass.

[0067] From the viewpoint of the peelability, resolution, oxygen barrier capacity, and defect suppression of the temporary support, the intermediate layer preferably contains at least one of polyvinyl alcohol and polyvinylpyrrolidone and compound X, more preferably polyvinyl alcohol and compound X, and even more preferably polyvinyl alcohol, polyvinylpyrrolidone, and compound X. When the intermediate layer has the above composition, compound X tends to be more unevenly distributed on the temporary support side surface of the intermediate layer, and the formation of a WBL (weak boundary layer) due to mixing of the intermediate layer and the photosensitive layer can be suppressed. As a result, the surface free energy of the temporary support side of the intermediate layer can be adjusted to an appropriate value, and the peelability and resolution of the temporary support can be further improved.

[0068] From the viewpoint of the peelability, resolution, oxygen barrier capacity, and defect suppression of the temporary support, the weight-average molecular weight (Mw) of the water-soluble resin is preferably 5,000 to 200,000, more preferably 7,000 to 100,000, and even more preferably 7,000 to 50,000. From the viewpoint of the peelability, resolution, oxygen barrier capacity, and defect suppression of the temporary support, the dispersion degree (Mw / Mn) of the water-soluble resin is preferably 1 to 10, and more preferably 1 to 5.

[0069] From the viewpoint of the peelability, resolution, oxygen barrier capacity, and defect suppression of the temporary support, the content of the water-soluble resin relative to the total mass of the intermediate layer is preferably 60% by mass or more, preferably 80% by mass or more, preferably 95% by mass or more, and may be 100% by mass.

[0070] The intermediate layer preferably contains a surfactant, and more preferably a surfactant having silicon atoms, from the viewpoint of stability after peeling off the temporary support and adhesion of the resulting pattern to copper. The intermediate layer may contain two or more types of surfactants. Silicone-based surfactants are preferred as surfactants having silicon atoms. The surfactant preferably contains one or more selected from the group consisting of nonionic surfactants, fluorine-based surfactants, and silicone-based surfactants. From the viewpoint of peelability, resolution, oxygen barrier ability, defect suppression, etc. of the temporary support, the surfactant preferably contains a silicone-based surfactant. Furthermore, a silicone-based surfactant is also preferred from the viewpoint of improving adhesion between the intermediate layer and adjacent layers (such as the photosensitive layer) (hereinafter also referred to as "interlayer adhesion"). From the viewpoint of peelability, resolution, oxygen barrier ability, defect suppression, interlayer adhesion, etc. of the temporary support, the content of the silicone-based surfactant relative to the total mass of the surfactant is preferably 60% by mass or more, preferably 80% by mass or more, preferably 95% by mass or more, and may be 100% by mass. Examples of silicone-based surfactants include linear polymers composed of siloxane bonds, and modified siloxane polymers in which an organic group is introduced to at least one of the side chains and terminals.

[0071] From the viewpoint of the peelability, resolution, oxygen barrier ability, defect suppression, and interlayer adhesion of the temporary support, the surfactant content relative to the total mass of the intermediate layer is preferably 0.1% to 10% by mass, more preferably 0.5% to 7% by mass, and even more preferably 1% to 5% by mass.

[0072] The intermediate layer may contain a water-insoluble resin. Examples of water-insoluble resins include polyester resin and (meth)acrylic resin. When the intermediate layer contains a water-insoluble resin, the content of the water-insoluble resin relative to the total mass of the intermediate layer is preferably 10% by mass or less, preferably 5% by mass or less, and preferably 1% by mass or less.

[0073] The intermediate layer may contain additives such as colorants, flame retardants, antioxidants, rust inhibitors, and dispersants.

[0074] The average thickness of the above-mentioned intermediate layer is preferably 0.1 μm to 15 μm, more preferably 0.5 μm to 12 μm, even more preferably 1 μm to 10 μm, and particularly preferably 2 μm to 5 μm, from the viewpoint of stability after peeling off the temporary support, adhesion of the obtained pattern to copper, pattern shape, surface roughness, and resolution.

[0075] <Photosensitive layer> The photosensitive layer may be a positive-type photosensitive layer or a negative-type photosensitive layer, but in the photosensitive transfer material according to this disclosure, it is preferable that it be a negative-type photosensitive layer. A negative-type photosensitive layer is a photosensitive layer in which the solubility of the exposed area in the developer decreases upon exposure. When the photosensitive layer is a negative-type photosensitive layer, the pattern formed corresponds to the cured layer.

[0076] The photosensitive layer preferably contains a polymer (binder). The photosensitive layer may contain one or more polymers. The polymer is preferably an alkali-soluble resin. The polymer may contain structural units formed from monomers having acidic groups. Examples of acidic groups include carboxyl groups, sulfo groups, phosphoric acid groups, and phosphonic acid groups. Examples of monomers having acidic groups include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, and maleic anhydride. The polymer may also contain structural units formed from monomers that do not have acidic groups. Examples of monomers that do not have acidic groups include (meth)acrylic acid esters, vinyl alcohol ester compounds, (meth)acrylonitrile, and aromatic vinyl compounds. Examples of (meth)acrylic acid esters include 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, 2-ethylhexyl (meth)acrylate, and benzyl (meth)acrylate. Examples of vinyl alcohol ester compounds include vinyl acetate. Examples of aromatic vinyl compounds include styrene and styrene derivatives. The non-acidic monomer is preferably one or more monomers selected from the group consisting of methyl (meth)acrylate, n-butyl (meth)acrylate, styrene, styrene derivatives, and benzyl (meth)acrylate.

[0077] The above photosensitive layer preferably contains a polymer having an aromatic ring, and more preferably a polymer having a structural unit having an aromatic ring, from the viewpoint of stability after peeling off the temporary support and adhesion of the resulting pattern to copper. Furthermore, the above binder is particularly preferably a resin having a structural unit derived from a styrene compound, from the viewpoint of stability after peeling off the temporary support and adhesion of the resulting pattern to copper. The polymer having a structural unit having an aromatic ring preferably contains 10% by mass or more of the structural unit having an aromatic ring, more preferably 20% by mass or more, and even more preferably 20% by mass to 90% by mass, from the viewpoint of stability after peeling off the temporary support and adhesion of the resulting pattern to copper. Preferred monomers for forming the structural unit having an aromatic ring include styrene, styrene derivatives, benzyl (meth)acrylate, and the like.

[0078] From the viewpoint of resolution, it is preferable that the alkali-soluble resin contains at least one of styrene-derived structural units and styrene derivative-derived structural units. Specific examples of styrene derivatives include vinyltoluene, p-methylstyrene, and p-chlorostyrene.

[0079] The copolymerization ratio of styrene-derived structural units and styrene derivative-derived structural units in the alkali-soluble resin described above is preferably 5% to 60% by mass, more preferably 10% to 50% by mass, and even more preferably 15% to 40% by mass, based on the total mass of the alkali-soluble resin.

[0080] From the viewpoint of adhesion, it is preferable that the alkali-soluble resin contains constituent units derived from (meth)acrylic acid ester. When the alkali-soluble resin contains at least one of constituent units derived from styrene and constituent units derived from styrene derivatives, and constituent units derived from (meth)acrylic acid ester, when the content of constituent units derived from styrene and styrene derivatives is set to 1, from the viewpoint of achieving both resolution and adhesion, the content of constituent units derived from (meth)acrylic acid ester is preferably 0.3 to 2.5, more preferably 0.5 to 2.0, and even more preferably 0.7 to 1.7.

[0081] From the viewpoint of stability after temporary support removal, adhesion of the resulting pattern to copper, resolution, and developability, the weight-average molecular weight (Mw) of the polymer is preferably 5,000 to 500,000, more preferably 10,000 to 100,000, even more preferably 20,000 to 70,000, and particularly preferably 30,000 to 50,000. The degree of dispersion (Mw / Mn) of the polymer is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

[0082] The glass transition temperature (Tg) of the polymer is preferably 70°C or higher, more preferably 70°C to 120°C, even more preferably 75°C to 110°C, and particularly preferably 80°C to 90°C, from the viewpoint of stability after peeling off the temporary support and adhesion of the resulting pattern to copper.

[0083] In this disclosure, the glass transition temperature of a resin can be measured using differential scanning calorimetry (DSC). The specific measurement method is carried out in accordance with the method described in JIS K 7121 (1987) or JIS K 6240 (2011). In this specification, the glass transition temperature used is the extrapolation glass transition onset temperature (hereinafter sometimes referred to as Tig). The method for measuring the glass transition temperature will be described in more detail. When determining the glass transition temperature, the resin is held at a temperature approximately 50°C lower than the expected Tg until the apparatus stabilizes, and then heated at a heating rate of 20°C / min to a temperature approximately 30°C higher than the temperature at which the glass transition ends, and a differential thermal analysis (DTA) curve or DSC curve is created. The extrapolation glass transition onset temperature (Tig), i.e., the glass transition temperature Tg as defined herein, is determined as the temperature at the intersection of a straight line drawn by extending the baseline on the low-temperature side of the DTA curve or DSC curve toward the high-temperature side, and a tangent line drawn at the point where the slope of the curve representing the stepwise transition portion of the glass transition is maximum.

[0084] From the viewpoint of resolution, developability, stability after temporary support removal, and adhesion of the resulting pattern to copper, the acid value of the polymer is preferably 80 mg KOH / g or more, more preferably 100 mg KOH / g or more, even more preferably 110 mg KOH / g or more, and particularly preferably 120 mg KOH / g to 220 mg KOH / g.

[0085] The acid value (mgKOH / g) is the mass (mg) of potassium hydroxide required to neutralize 1 g of the sample. The acid value can be determined, for example, according to the method described in JIS K0070:1992. The acid value of a polymer can be adjusted by changing the type of constituent units and the content of constituent units containing acid groups.

[0086] From the viewpoint of resolution, developability, etc., the polymer content relative to the total mass of the photosensitive layer is preferably 30% to 70% by mass, more preferably 40% to 60% by mass, and even more preferably 45% to 57% by mass.

[0087] The photosensitive layer may contain one or more polymerizable compounds (monomers). The polymerizable compound is not limited, and known polymerizable compounds can be used. The polymerizable compound is preferably an ethylenically unsaturated compound. The ethylenically unsaturated compound is a compound having one or more ethylenically unsaturated groups. The ethylenically unsaturated group is preferably a (meth)acryloyl group. The ethylenically unsaturated compound is preferably a (meth)acrylate compound. Ethyleneically unsaturated compounds having a bisphenol structure are also suitably used as ethylenically unsaturated compounds. An example of an ethylenically unsaturated compound having a bisphenol structure is alkylene oxide-modified bisphenol A di(meth)acrylate. Examples of alkylene oxide-modified bisphenol A di(meth)acrylates include ethylene glycol dimethacrylate obtained by adding an average of 5 moles of ethylene oxide to each end of bisphenol A, ethylene glycol dimethacrylate obtained by adding an average of 2 moles of ethylene oxide to each end of bisphenol A, ethylene glycol dimethacrylate obtained by adding an average of 5 moles of ethylene oxide to each end of bisphenol A, alkylene glycol dimethacrylate obtained by adding an average of 6 moles of ethylene oxide and an average of 2 moles of propylene oxide to each end of bisphenol A, and alkylene glycol dimethacrylate obtained by adding an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide to each end of bisphenol A. Specific examples of alkylene oxide-modified bisphenol A di(meth)acrylates include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane and 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane. In particular, from the viewpoint of stability after peeling off the temporary support and adhesion of the resulting pattern to copper, it is preferable to include a polyfunctional (meth)acrylate compound having an aromatic ring, more preferably 20% by mass or more of the polyfunctional (meth)acrylate compound having an aromatic ring based on the total mass of the photosensitive layer, and even more preferably 30% to 60% by mass.Furthermore, from the viewpoint of stability after temporary support removal and adhesion of the resulting pattern to copper, it is preferable to include two or more polyfunctional (meth)acrylate compounds having aromatic rings. Moreover, from the viewpoint of stability after temporary support removal and adhesion of the resulting pattern to copper, the content of the polyfunctional (meth)acrylate compounds is preferably 80 parts by mass or more, more preferably 90 parts by mass or more, and particularly preferably 100 parts by mass, per 100 parts by mass of the total mass of polymerizable compounds. Furthermore, from the viewpoint of stability after temporary support removal and adhesion of the resulting pattern to copper, it is preferable to include two or more polymerizable compounds, more preferably three or more, and even more preferably three to six.

[0088] The molecular weight of the polymerizable compound is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200. If the polymerizable compound is a compound having a molecular weight distribution (e.g., a polymer), the weight-average molecular weight of the polymerizable compound is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.

[0089] The polymerizable compound content is preferably 10% to 70% by mass, more preferably 20% to 60% by mass, and even more preferably 20% to 50% by mass, based on the total mass of the photosensitive layer.

[0090] From the viewpoint of resolution, oxygen barrier ability, etc., the photosensitive layer preferably contains one or more of the above-mentioned surfactants. Preferred embodiments of the surfactants are as described in the section on the intermediate layer and are therefore omitted here. From the viewpoint of resolution, oxygen barrier ability, etc., the surfactant content relative to the total mass of the photosensitive layer is preferably 0.05% to 5% by mass, more preferably 0.1% to 3% by mass, and even more preferably 0.2% to 1% by mass.

[0091] The photosensitive layer may contain one or more polymerization initiators. Conventional known radical polymerization initiators, cationic polymerization initiators, etc., can be used as polymerization initiators.

[0092] The content of the polymerization initiator relative to the total mass of the photosensitive layer is not particularly limited and can be 1% to 10% by mass.

[0093] The photosensitive layer may contain additives such as colorants, sensitizers, chain transfer agents (e.g., N-phenylcarbamoylmethyl-N-carboxymethylaniline, N,N-tetraethyl-4,4-diaminobenzophenone), polymerization inhibitors, plasticizers, flame retardants, antioxidants, rust inhibitors, dispersants, and thermally crosslinkable compounds (e.g., methylol compounds, blocked isocyanate compounds).

[0094] The average thickness of the photosensitive layer described above is preferably 0.5 μm to 50 μm, more preferably 5 μm to 40 μm, even more preferably 10 μm to 30 μm, and particularly preferably 15 μm to 30 μm, from the viewpoint of stability after peeling off the temporary support, adhesion of the obtained pattern to copper, pattern shape, surface roughness, and resolution.

[0095] <Protective Film> The photosensitive transfer material may have a protective film on the surface opposite to the intermediate layer side of the photosensitive layer. A resin film can be used as the protective film. Examples of the above resin films include polyolefin films such as polypropylene film and polyethylene film, polyester films such as polyethylene terephthalate film, polycarbonate film, and polystyrene film. Among these, from the viewpoint of heat resistance and the like, the protective film is preferably a polyolefin film, more preferably a polypropylene film or polyethylene film, and even more preferably a polyethylene film.

[0096] The average thickness of the protective film is not particularly limited, but from the viewpoint of mechanical strength, it is preferably 1.0 μm to 100.0 μm, more preferably 5.0 μm to 50.0 μm, and even more preferably 5.0 μm to 40.0 μm.

[0097] <Applications of Photosensitive Transfer Materials> The photosensitive transfer materials according to this disclosure are preferably used to form circuit wiring that is placed on a support substrate such as a sheet, metal substrate, ceramic substrate, and glass in the manufacturing process films of semiconductor packages, printed circuit boards, flexible printed wiring boards, and interposer rewiring layers.

[0098] <Method for Manufacturing Photosensitive Transfer Material> The method for manufacturing the photosensitive transfer material according to this disclosure is not particularly limited, but it preferably includes, in this order, a step of forming the intermediate layer on one side of a temporary support by coating (hereinafter referred to as the intermediate layer formation step), and a step of forming the photosensitive layer on the side of the intermediate layer opposite to the side in contact with the temporary support by coating (hereinafter referred to as the photosensitive layer formation step). The method for manufacturing the photosensitive transfer material according to this disclosure may also include a step of providing a protective film on the surface of the photosensitive layer (hereinafter referred to as the protective film placement step). In this specification, "drying" means removing at least a portion of the solvent contained in the composition. Examples of drying methods include natural drying, heat drying, and vacuum drying. The above methods can be applied individually or in combination.

[0099] <<Intermediate Layer Formation Process>> The intermediate layer formation composition used in the intermediate layer formation process can be prepared by dissolving or dispersing the materials to be contained in the intermediate layer (surfactants, etc.) in a solvent. Examples of solvents include water and water-soluble solvents.

[0100] Any water-soluble solvent other than water is acceptable, such as alcohol compounds, ketone compounds, and ester compounds. Examples of alcohol compounds include monoalcohol compounds and polyhydric alcohol compounds, such as methanol, ethanol, 1-propanol, isopropyl alcohol, 1-butanol, isobutanol, s-butanol, t-butanol, 1-pentanol, 1-hexanol, cyclohexanol, 1-heptanol, 1-octanol, 2-octanol, 2-ethylhexanol, 2-propyl-1-hexanol, 1-nonanol, and 1-decanol. Examples include polyhydric alcohol compounds such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, glycerin, 1,2,6-hexanetriol, trimethylolpropane, 1,3-butanediol, 1,4-butanediol, 2-butene-1,4-diol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, 1,2-octanediol, 1,2-hexanediol, 1,2-pentanediol, 4-methyl-1,2-pentanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, dipropylene glycol, polyoxyethylene polyoxypropylene glycol, and (poly)alkylene glycol monoether compounds such as ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, triethylene glycol monoalkyl ether, tripropylene glycol monoalkyl ether, and polyoxypropylene glyceryl ether. Other water-soluble solvents include dimethylaminoethanol, 2-amino-2-methyl-1-propanol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, sugars, sugar alcohols, hyaluronic acid, and the like.

[0101] Methods for applying the intermediate layer-forming composition include printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (i.e., slit coating). The drying temperature can be 80°C to 130°C. Note that the drying temperature refers to the temperature of the environment in which the intermediate layer-forming composition is dried. The drying time can be 20 seconds to 600 seconds.

[0102] <<Photosensitive Layer Formation Process>> The photosensitive layer formation composition used in the photosensitive layer formation process can be prepared by dissolving or dispersing the materials to be contained in the photosensitive layer described above in a solvent. Examples of solvents include the water-soluble solvents mentioned above, alkylene glycol ethers, alkylene glycol ether acetates, ketone solvents (such as methyl ethyl ketone), aromatic hydrocarbon solvents (such as toluene), aprotic polar solvents (such as N,N-dimethylformamide), ether solvents (such as diethyl ether), ester solvents (such as n-propyl acetate), amide solvents, and lactone solvents. The application method, drying temperature, and drying time of the photosensitive layer formation composition are the same as in the intermediate layer formation process and are therefore omitted from this description.

[0103] <<Protective Film Placement Process>> The protective film placement process may include laminating a protective film onto the surface of the photosensitive layer. The protective film lamination can be performed using a known laminator such as a vacuum laminator or an auto-cut laminator. The laminator is preferably equipped with a heat-sensitive roller such as a rubber roller and capable of applying pressure and heating.

[0104] (Method for Manufacturing Resin Patterns) The method for manufacturing resin patterns according to this disclosure is a method for manufacturing resin patterns using the photosensitive transfer material according to this disclosure. The method for manufacturing resin patterns according to this disclosure comprises, in this order, a step of bonding the photosensitive transfer material and the substrate so that the photosensitive layer in the photosensitive transfer material according to this disclosure is in contact with the substrate (hereinafter sometimes referred to as the "bonding step"), a step of pattern exposure to the photosensitive layer (hereinafter sometimes referred to as the "exposure step"), and a step of developing the photosensitive layer after exposure to form a resin pattern (hereinafter sometimes referred to as the "development step"). Preferably, the method for manufacturing resin patterns according to this disclosure includes a step of preparing the substrate (hereinafter sometimes referred to as the "preparation step").

[0105] <Preparation Step> In the preparation step, the substrate is prepared. The type of substrate is not limited. Preferably, the substrate is a substrate that includes a conductive layer. Furthermore, preferably, the substrate is a substrate that includes a base material and a conductive layer on the base material, and more preferably, a substrate that includes a base material and a conductive layer in contact with the base material. The conductive layer may be arranged on one side of the base material. The conductive layer may be arranged on both sides of the base material. The substrate may also include layers other than the conductive layer.

[0106] Examples of substrates include glass, silicone, and resin films. The substrate is preferably transparent. In this disclosure, "transparent" means that the transmittance at wavelengths of 400 nm to 700 nm is 80% or more. The refractive index of the substrate is preferably 1.50 to 1.52.

[0107] Examples of transparent glass include tempered glass, such as Corning's Gorilla Glass. Materials used in Japanese Patent Publication Nos. 2010-86684, 2010-152809, and 2010-257492 may also be used as transparent glass.

[0108] The resin film is preferably one that has low optical distortion or high transparency. Examples of such resin films include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetylcellulose, and cycloolefin polymers.

[0109] In a method for manufacturing resin patterns using a roll-to-roll method, the base material is preferably a resin film.

[0110] Examples of conductive layers include those used in general circuit wiring or touch panel wiring. Preferably, the conductive layer is an electrode pattern corresponding to the sensor in the viewing area of ​​a capacitive touch panel or wiring in the peripheral extraction area.

[0111] From the viewpoint of conductivity and fine wire formation, the conductive layer is preferably at least one selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, more preferably a metal layer, and particularly preferably a copper layer or a silver layer.

[0112] Examples of components of the conductive layer include metals and conductive metal oxides. Examples of metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au. Examples of conductive metal oxides include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO ２ Examples include: In this disclosure, "conductive" means that the volume resistivity is 1 × 10⁻⁶. ６ This refers to the property of being less than Ωcm. The volume resistivity of conductive metal oxides is 1 × 10⁻⁶. ４ It is preferable that the density is less than Ωcm.

[0113] When manufacturing a resin pattern using a substrate containing multiple conductive layers, it is preferable that at least one of the conductive layers contains a conductive metal oxide.

[0114] The substrate may include one or more conductive layers. If the substrate includes two or more conductive layers, it is preferable that the substrate includes two or more conductive layers formed of different materials.

[0115] Preferred embodiments of the conductive layer are described, for example, in paragraph 0141 of International Publication No. 2018 / 155193, which are incorporated herein by reference.

[0116] A substrate having at least one of a transparent electrode and a routing wire is preferred as the substrate containing the conductive layer. Such a substrate can be suitably used as a touch panel substrate. The transparent electrode can function suitably as a touch panel electrode. The transparent electrode is preferably composed of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide), and metal fine wires such as a metal mesh and metal nanowires. Examples of metal fine wires include silver and copper fine wires. Among these, silver conductive materials such as silver mesh and silver nanowires are preferred.

[0117] Metal is preferred as the material for the wiring. Examples of metals used for wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, as well as alloys composed of two or more of these metallic elements. Copper, molybdenum, aluminum, or titanium are preferred as the material for wiring, with copper being particularly preferred.

[0118] <Bonding Process> In the bonding process, the photosensitive transfer material is brought into contact with the substrate, and the photosensitive layer and temporary support are placed on the substrate in that order.

[0119] The photosensitive transfer material is as described in the "Photosensitive Transfer Material" section above. The preferred embodiment of the photosensitive transfer material used in the bonding process is the same as the preferred embodiment of the photosensitive transfer material described in the "Photosensitive Transfer Material" section above.

[0120] In the lamination process, the photosensitive layer and temporary support placed on the substrate are, respectively, the photosensitive layer and temporary support contained in the photosensitive transfer material. That is, the layer configuration of the laminate obtained by the lamination process changes depending on the layer configuration of the photosensitive transfer material. For example, in the lamination process, if a photosensitive transfer material containing a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive layer in that order is brought into contact with the substrate, the photosensitive layer, intermediate layer, thermoplastic resin layer, and temporary support will be arranged on the substrate in that order. If the photosensitive transfer material contains a protective film, the protective film is removed from the photosensitive transfer material before bringing the photosensitive transfer material into contact with the substrate.

[0121] In the bonding process, it is preferable to bring the photosensitive transfer material into contact with the substrate and press the photosensitive transfer material onto the substrate. For example, it is preferable to bring the photosensitive transfer material into contact with the substrate and apply pressure and heat to the substrate and the photosensitive transfer material using means such as a roll, thereby pressing the photosensitive transfer material onto the substrate.

[0122] In a method for bringing a photosensitive transfer material into contact with a substrate (including a method for pressing a photosensitive transfer material onto a substrate), for example, a known transfer method or a known lamination method may be used. In a method for bringing a photosensitive transfer material into contact with a substrate, for example, a laminator, a vacuum laminator, or an auto-cut laminator that can increase productivity may be used.

[0123] <Removal Step> The method for manufacturing a resin pattern according to this disclosure preferably includes a step of removing the temporary support after the lamination step and before the step of developing the photosensitive layer after exposure, and more preferably includes a step of removing the temporary support after the exposure step and before the step of developing the photosensitive layer after exposure. In the exposure step of the method for manufacturing a resin pattern according to this disclosure, the exposure step may be either exposure through the temporary support or exposure after removal of the temporary support. There are no particular restrictions on the method of removing the temporary support in the removal step, and known removal methods can be used.

[0124] <Exposure Process> In the exposure process, the photosensitive layer is pattern-exposed. The arrangement and dimensions of the pattern in pattern exposure are not limited. At least a portion of the pattern (preferably the portion corresponding to the electrode pattern or extraction wiring of the touch panel) is preferably fine lines having a width of 20 μm or less, and more preferably fine lines having a width of 10 μm or less.

[0125] Examples of light sources used in the exposure process include those that emit light with a wavelength capable of exposing the photosensitive layer (e.g., 365 nm or 405 nm). Examples of light sources include ultra-high pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes).

[0126] The exposure dose is 5 mJ / cm². ２ ~300 mJ / cm ２ Preferably, it is 10 mJ / cm ２ ~200 mJ / cm ２ It is preferable that it be so.

[0127] In the exposure process, the photosensitive layer may be pattern-exposed after the temporary support is removed. Alternatively, in the exposure process, the photosensitive layer may be pattern-exposed through the temporary support, and then the temporary support may be removed.

[0128] In an exposure method using a photomask, if the temporary support is removed before pattern exposure, the photomask may be brought into contact with the photosensitive layer to expose it, or the photomask may be brought close to the photosensitive layer without contact to expose it. In an exposure method using a photomask, when the photosensitive layer is exposed via a temporary support, the photomask may be brought into contact with the temporary support to expose it, or the photomask may be brought close to the temporary support without contact to expose it. To prevent contamination of the photomask due to contact between the photosensitive layer and the photomask, and to avoid the influence of foreign matter adhering to the photomask on exposure, it is preferable to pattern expose the photosensitive layer via a temporary support.

[0129] The exposure method is not limited. Examples of exposure methods include contact exposure and non-contact exposure. Examples of contact exposure methods include a method in which the photosensitive layer is pattern-exposed using a photomask. Examples of non-contact exposure methods include proximity exposure, projection exposure using a lens system or mirror system, and direct exposure using an exposure laser. In projection exposure using a lens system or mirror system, an exposure machine having an appropriate numerical aperture (NA) of the lens may be used depending on the required resolution and depth of field. In direct exposure, drawing may be performed directly on the photosensitive layer, or reduction projection exposure may be performed on the photosensitive layer via a lens. Exposure may be performed in air, under reduced pressure, or under vacuum. Exposure may also be performed with a liquid such as water interposed between the light source and the photosensitive layer.

[0130] <Development Process> In the development process, the exposed photosensitive layer is developed to form a resin pattern. If the photosensitive layer is a negative-type photosensitive layer, the unexposed areas of the photosensitive layer are removed, and the exposed areas of the photosensitive layer form the resin pattern. If the photosensitive layer is a positive-type photosensitive layer, the exposed areas of the photosensitive layer are removed, and the unexposed areas of the photosensitive layer form the resin pattern. In addition, the thermoplastic resin layer and intermediate layer placed on the substrate in the lamination process are removed along with the removed photosensitive layer. The thermoplastic resin layer and intermediate layer may also be removed by dissolution or dispersion in the developer.

[0131] Development is carried out, for example, using a developer. The developer is not limited as long as it is a developer that removes the photosensitive layer of the object. Known developers can be used as the developer. For example, the developer described in Japanese Patent Publication No. 5-72724 can be cited as an example of a developer. Preferably, the developer is an alkaline aqueous solution containing a compound with a pKa of 7 to 13 at a concentration of 0.05 mol / L to 5 mol / L. The developer may also contain a water-soluble organic solvent and / or a surfactant. The developer described in paragraph 0194 of International Publication No. 2015 / 093271 is also preferred as a developer.

[0132] The temperature of the developer solution is not restricted. However, the developer solution temperature is preferably between 20°C and 40°C.

[0133] The development method is not limited. The development method may be, for example, paddle development, shower development, shower and spin development, or dip development. Shower development is a method of removing the photosensitive layer of the target by spraying the photosensitive layer with developer after exposure.

[0134] After the developing process, it is preferable to spray a cleaning agent with a shower and remove the developing residue by scrubbing with a brush.

[0135] The line width of the resin pattern obtained through the above process is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 8 μm or less. There is no lower limit to the line width of the resin pattern. The line width of the resin pattern may be, for example, 1 μm or more. The line width of the resin pattern is measured by the following method: The resin pattern is observed using a scanning electron microscope (SEM), and the line widths of 30 locations in the resin pattern are measured. The arithmetic mean of the measured values ​​is adopted as the line width of the resin pattern.

[0136] The resin pattern obtained through the above process may be used as a permanent film or an etching protective film.

[0137] <Roll-to-Roll Method> The method for manufacturing the resin pattern is preferably carried out by the roll-to-roll method. The roll-to-roll method is a method that uses a substrate that can be wound up and unwound, and includes a step of unwinding the substrate or a laminate containing the substrate (sometimes referred to as the "unwinding step") before any of the steps included in the method for manufacturing the resin pattern, and a step of winding the substrate or a laminate containing the substrate (hereinafter sometimes referred to as the "winding step") after any of the steps, wherein at least one of the steps (preferably all of the steps) is carried out while transporting the substrate or a laminate containing the substrate. For example, known methods applicable to the roll-to-roll method can be used as the unwinding method in the unwinding step and the winding method in the winding step.

[0138] (Method for Manufacturing Conductive Patterns) The method for manufacturing conductive patterns according to this disclosure is a method for manufacturing conductive patterns using a photosensitive transfer material according to this disclosure. The method for manufacturing conductive patterns according to this disclosure preferably comprises, in this order, the steps of: forming the resin pattern on a substrate using the resin pattern manufacturing method according to this disclosure; performing a plating process on areas of the substrate where the resin pattern is not formed (hereinafter sometimes referred to as the "plating step"); and removing the resin pattern (hereinafter sometimes referred to as the "removal step"). Furthermore, the method for manufacturing conductive patterns according to this disclosure preferably comprises, in this order, the steps of: forming the resin pattern on a substrate using the resin pattern manufacturing method according to this disclosure; etching areas of the substrate where the resin pattern is not formed (hereinafter sometimes referred to as the "etching step"); and removing the resin pattern.

[0139] <Plating Process> The method for manufacturing a conductive pattern according to this disclosure preferably includes a step of performing a plating process on areas of the substrate where the resin pattern is not formed. Examples of plating methods include electrolytic plating and electroless plating, and electrolytic plating is preferred from the viewpoint of productivity.

[0140] The metal used in the plating process is not particularly limited, and any known metal can be used. Examples of usable metals include copper, chromium, lead, nickel, gold, silver, tin, zinc, and alloys of these metals. From the viewpoint of electrical conductivity, copper or its alloys are preferred.

[0141] The thickness of the plating layer formed by the plating process is not particularly limited and can be between 0.1 μm and 20.0 μm.

[0142] <Etching Process> In the etching process, the conductive layer in areas where the resin pattern is not formed is etched to form the conductive pattern. In the etching process, the resin pattern functions as a protective film for the conductive layer. In the etching process, the conductive layer not covered by the resin pattern is removed by etching, and the conductive layer covered by the resin pattern forms the conductive pattern.

[0143] For example, known methods can be used as etching methods. Examples of etching methods include the method described in paragraphs 0209 to 0210 of Japanese Patent Publication No. 2017-120435, the method described in paragraphs 0048 to 0054 of Japanese Patent Publication No. 2010-152155, wet etching methods involving immersion in an etching solution, and dry etching methods (e.g., plasma etching).

[0144] For etching solutions used in wet etching, an acidic or alkaline etching solution may be appropriately selected depending on the material to be etched. Examples of acidic etching solutions include aqueous solutions containing at least one acidic component selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid. Examples of acidic etching solutions include aqueous solutions containing the above-mentioned acidic component and at least one salt selected from the group consisting of ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component may be a combination of multiple acidic components. Examples of alkaline etching solutions include aqueous solutions containing at least one alkaline component selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide). Examples of alkaline etching solutions include aqueous solutions containing the above-mentioned alkaline component and a salt (e.g., potassium permanganate). The alkaline component may be a combination of multiple alkaline components.

[0145] <Removal Step> The method for manufacturing a conductive pattern according to this disclosure preferably includes a step of removing the resin pattern after the etching step.

[0146] Methods for removing the resin pattern include, for example, using chemical treatment to remove the resin pattern. A preferred method is to remove the resin pattern using a removal solution. A preferred method for removing the resin pattern using a removal solution is to immerse the substrate containing the resin pattern in a stirring removal solution with a liquid temperature of 30°C to 80°C (preferably 50°C) for 1 to 30 minutes.

[0147] Examples of removal solutions include those comprising an inorganic alkaline component or an organic alkaline component and at least one selected from the group consisting of water, dimethyl sulfoxide, and N-methylpyrrolidone. Examples of inorganic alkaline components include sodium hydroxide and potassium hydroxide. Examples of organic alkaline components include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

[0148] The remaining resin pattern may be removed using known methods such as the spray method, shower method, and paddle method.

[0149] <Protective Layer Formation Step> The method for manufacturing a conductive pattern according to this disclosure may include a step of forming a protective layer on the surface of the plated layer after the plating step and before the removal step (sometimes referred to as the "protective layer formation step"). The material constituting the protective layer is preferably a material that does not dissolve in the removal solution or etching solution used in the pattern removal step or seed layer removal step. Examples of materials constituting the protective layer include nickel, chromium, tin, zinc, magnesium, gold, silver, alloys thereof, resins, etc. Nickel or chromium is preferred as the material constituting the protective layer.

[0150] Methods for forming the protective layer include electroless plating and electroplating, with electroplating being preferred.

[0151] The thickness of the protective layer is not particularly limited and can be between 0.3 μm and 3.0 μm.

[0152] <Protective Layer Formation Process> The method for manufacturing a conductive pattern according to this disclosure may include a step of forming a protective layer on the surface of the plating layer after the conductive pattern formation process and before the pattern removal process. The material constituting the protective layer is preferably a material that does not dissolve in the removal solution or etching solution used in the removal process or seed layer removal process. Examples of materials constituting the protective layer include nickel, chromium, tin, zinc, magnesium, gold, silver, alloys thereof, resins, etc. Nickel or chromium is preferred as the material constituting the protective layer.

[0153] Methods for forming the protective layer include electroless plating and electroplating, with electroplating being preferred.

[0154] The thickness of the protective layer is not particularly limited and can be between 0.3 μm and 3.0 μm.

[0155] <Seed layer removal step> The above substrate may have a seed layer for plating formation. If the substrate has a seed layer on its surface, the method for manufacturing a conductive pattern according to this disclosure may include a step for removing the seed layer. The seed layer removal step is a step of removing the exposed seed layer to obtain a conductive nanowire.

[0156] The method for removing the seed layer is not particularly limited and may be carried out by using a known etching solution. Examples of etching solutions include ferric chloride solution, cupric chloride solution, ammonia alkali solution, sulfuric acid-hydrogen peroxide mixture, and phosphoric acid-hydrogen peroxide mixture.

[0157] <Solder Resist Layer Formation Process> The method for manufacturing a conductive pattern according to this disclosure may include a step of forming a solder resist layer having openings on the surface of a substrate from which a seed layer has been removed, using a solder resist. Preferably, the openings expose the conductive pattern formed on the surface of the substrate. Conventionally known solder resists can be used. Examples of solder resists include azido-cyclized polyisoprene resins, azido-phenol resins, chloromethyl polystyrene resins, etc. The thickness of the solder resist layer is not particularly limited and can be 5 μm to 50 μm. The method for forming the solder resist layer is not particularly limited and can be carried out by conventionally known methods.

[0158] <Bump Electrode Formation Process> The method for manufacturing a conductive pattern according to this disclosure includes a step of forming bump electrodes in the openings of the solder resist layer. Preferably, the bump electrodes are connected to the conductor pattern exposed at the openings.

[0159] <Semiconductor Element Mounting Process> The method for manufacturing a conductive pattern according to this disclosure may include a step of mounting semiconductor elements connected to bump electrodes. The mounted semiconductor preferably has electrodes, and it is preferable that these electrodes are connected to the bump electrodes. After mounting the semiconductor, it is preferable to encapsulate the semiconductor using a conventionally known encapsulating material.

[0160] <Other Steps> The method for manufacturing a conductive pattern according to this disclosure may further include other steps in addition to the steps described above. Examples of other steps include the steps shown below. Furthermore, exposure steps, development steps and other steps applicable to the method for manufacturing a conductive pattern according to this disclosure are described in paragraphs 0035 to 0051 of Japanese Patent Application Publication No. 2006-23696. The contents described in the above publication are incorporated herein by reference.

[0161] <<Step to Reduce Visible Light Reflectance>> The method for manufacturing a conductive pattern according to the present disclosure may include a step of performing a treatment to reduce the visible light reflectance of some or all of the conductive layers of a substrate. Examples of treatments to reduce visible light reflectance include oxidation treatment. For example, if the conductive layer contains copper, the visible light reflectance of the conductive layer can be reduced by oxidizing the copper to form copper oxide and blackening the conductive layer. Treatments to reduce visible light reflectance are described in paragraphs 0017 to 0025 of Japanese Patent Application Publication No. 2014-150118 and paragraphs 0041, 0042, 0048 and 0058 of Japanese Patent Application Publication No. 2013-206315. The contents described in these publications are incorporated herein by reference.

[0162] <<Steps for forming an insulating film and forming a new conductive layer on the surface of the insulating film>> The method for manufacturing a conductive pattern according to this disclosure preferably includes the steps of forming an insulating film on the surface of a conductive pattern and forming a new conductive layer on the surface of the insulating film. By the above steps, a second electrode pattern insulated from the first electrode pattern can be formed. As a method for forming the insulating film, for example, a known method for forming a permanent film can be mentioned. An insulating film with a desired pattern may be formed by photolithography using an insulating photosensitive material. As a method for forming a new conductive layer on the surface of the insulating film, for example, a new conductive layer with a desired pattern may be formed by photolithography using a conductive photosensitive material.

[0163] In the method for manufacturing a conductive pattern according to this disclosure, it is also preferable to use a substrate having multiple conductive layers on both sides of the substrate, and to form circuits sequentially or simultaneously on the conductive layers formed on both sides of the substrate. According to the above method, a first conductive pattern can be formed on one surface of the substrate, and a second conductive pattern can be formed on the other surface of the substrate. Such a conductive pattern can be used, for example, as circuit wiring for a touch panel. Such a conductive pattern is preferably formed by a roll-to-roll method.

[0164] <Roll-to-Roll Method> The method for manufacturing a conductive pattern according to this disclosure is preferably carried out by a roll-to-roll method. The roll-to-roll method is as described in the section "Method for Manufacturing a Resin Pattern" above.

[0165] <Applications of Conductive Patterns> Conductive patterns obtained by the method for manufacturing conductive patterns according to this disclosure can be applied to various devices. Examples of devices including conductive patterns include input devices, touch panels are preferred, and capacitive touch panels are more preferred. The above input devices can be applied to display devices such as organic EL displays and liquid crystal displays. Furthermore, conductive patterns obtained by the method for manufacturing conductive patterns according to this disclosure are preferably applied to touch sensors.

[0166] <Touch Sensors> The touch sensors according to this disclosure include a conductive pattern obtained by the method for manufacturing conductive patterns according to this disclosure. The components of the touch sensors according to this disclosure are not limited except that they include a conductive pattern obtained by the method for manufacturing conductive patterns according to this disclosure. The conductive pattern is used, for example, as a transparent electrode or frame wiring of the touch sensor. The shape and dimensions of the conductive pattern are determined, for example, according to the intended touch sensor. Examples of photomask patterns used in manufacturing the conductive pattern include patterns A and B described in Japanese Patent Application Publication No. 2019-204070. Components other than the conductive pattern include, for example, components included in known touch sensors. Touch sensors are described, for example, in Japanese Patent Application Publication No. 6486341 and Japanese Patent Application Publication No. 2016-155978. These publications are incorporated herein by reference. Known methods for manufacturing touch sensors may be referenced for forming components of touch sensors other than the conductive pattern.

[0167] Touch sensors can be applied to various input devices, such as touch panels.

[0168] Examples of touch panel detection methods include resistive, capacitive, ultrasonic, electromagnetic induction, and optical methods. Among these, the capacitive method is preferred.

[0169] Examples of touch panel types include in-cell type (for example, the configurations described in Figures 5, 6, 7, and 8 of Japanese Patent Publication No. 2012-517051), on-cell type (for example, the configuration described in Figure 19 of Japanese Patent Application Publication No. 2013-168125 and the configurations described in Figures 1 and 5 of Japanese Patent Application Publication No. 2012-89102), OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (for example, the configuration described in Figure 2 of Japanese Patent Application Publication No. 2013-54727), various out-cell types (for example, GG, G1 / G2, GFF, GF2, GF1, and G1F), and other configurations (for example, the configuration described in Figure 6 of Japanese Patent Application Publication No. 2013-164871).

[0170] The present disclosure will be described in more detail below based on the examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not deviate from the spirit of the present disclosure. Therefore, the scope of the present disclosure should not be interpreted as being limited by the examples shown below. Unless otherwise specified, "parts" and "%" are based on mass. In the following examples, the weight-average molecular weight of the resin is the weight-average molecular weight obtained in polystyrene equivalent by gel permeation chromatography (GPC). The theoretical acid value was used.

[0171] [Various Components of Photosensitive Transfer Materials] Below, we will first describe the various components used in the preparation of the photosensitive transfer material.

[0172] [Intermediate Layer] The composition of intermediate layers A to E is shown in Table 1.

[0173] <<Preparation of Intermediate Layer Forming Composition>> An intermediate layer forming composition was prepared by mixing each component according to the information in Table 1. The values ​​in Table 1 represent the content of each component in parts by mass.

[0174]

[0175] <<Components of the Intermediate Layer>> The components of the photosensitive layer shown in Table 1 are as follows: PVA 4-88LA: Polyvinyl alcohol: Product name "Kuraray Poval PVA 4-88LA", manufactured by Kuraray Co., Ltd. PVA 205: Polyvinyl alcohol: Product name "Kuraray Poval PVA-205", manufactured by Kuraray Co., Ltd. PVP K30: Polypyrrolidone: Product name "Polyvinylpyrrolidone K-30", manufactured by Nippon Shokubai Co., Ltd. PVP K90: Polypyrrolidone: Product name "Polyvinylpyrrolidone K-90", manufactured by Nippon Shokubai Co., Ltd. HPMC: Hydroxypropyl methylcellulose: Product name "Metrol 60SH-03", manufactured by Shin-Etsu Chemical Co., Ltd. M-550: Polyoxyethylene monomethyl ether: Product name "Uniox M-550", manufactured by Nippon Oil & Fats Co., Ltd. F444: Fluorine-based surfactant, Product name "Megafac (registered trademark) F-444", manufactured by DIC Corporation BYK-345: Silicone-based surfactant, manufactured by Bic Chemie Japan Co., Ltd.

[0176] [Photosensitive Layer] The composition of photosensitive layers A to G is shown in Table 2. The values ​​for polymers in Table 2 represent the solid content.

[0177] <<Preparation of Photosensitive Layer Forming Composition>> A photosensitive layer forming composition was prepared by mixing each component according to the information in Table 2. The values ​​in Table 2 represent the content of each component in parts by mass.

[0178]

[0179] <<Various Components of the Photosensitive Layer>> The components of the photosensitive layer shown in Table 2 are as follows:

[0180] <Polymers (Binders)> Polymers A-1 to A-3 were synthesized using known methods. The weight-average molecular weight (Mw) of the synthesized polymers was measured by gel permeation chromatography (GPC) under the following conditions.

[0181] - GPC Conditions - Equipment: Tosoh Corporation, Tosoh High-Speed ​​GPC System HLC-8420GPC (product name) Guard column: Tosoh Corporation, HZ-L Separation column: Tosoh Corporation, three TSK gel Super HZM-N (product name) columns connected in series Measurement temperature: 40°C Eluent: THF (tetrahydrofuran) Flow rate: Sample pump 0.35 mL / min, reference pump 0.175 mL / min Injection volume: 10 μL Detector: Differential refractometer GPC column calibration standard solution: Tosoh Corporation standard polystyrene

[0182]

[0183] • Polymer A-1: ​​The acid value was 124 mgKOH / g. • Polymer A-2: The acid value was 111 mgKOH / g. • Polymer A-3: The acid value was 130 mgKOH / g.

[0184] <<Other Components>> The other components contained in the photosensitive layer shown in Table 2 are listed below.

[0185] <Polymerizable Compounds> ・BPE-500: 2,2-bis(4-(meth)acryloxypentaethoxy)phenyl)propane, manufactured by Shin Nakamura Chemical Industry Co., Ltd. ・M-270: Polypropylene glycol diacrylate (n≒12), manufactured by Toagosei Co., Ltd. ・BPE-100: 2,2-bis(4-(methacryloylethoxy)phenyl)propane, manufactured by Shin Nakamura Chemical Industry Co., Ltd. ・A-TMMT: Pentaerythritol tetraacrylate, manufactured by Shin Nakamura Chemical Industry Co., Ltd.

[0186] <Polymerization Initiator> ・B-CIM: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, Hampford

[0187] <Sensitizer> EBA-F: 4,4'-bis(diethylamino)benzophenone, obtained from Sanyo Trading Co., Ltd.

[0188] <Chain Transfer Agents> ・Leucocrystal violet: Manufactured by Tokyo Chemical Industry Co., Ltd. ・N-phenylcarbamoylmethyl-N-carboxymethylaniline: Manufactured by Fujifilm Wako Pure Chemical Corporation

[0189] <Rust Inhibitor> ・CBT-1: Carboxybenzotriazole, manufactured by Johoku Chemical Co., Ltd.

[0190] <Polymerization inhibitor> ・TDP-G: Phenothiazine, manufactured by Kawaguchi Chemical Co., Ltd.

[0191] <Surfactants> F-552: Fluorine-based surfactant, Megafac (registered trademark) F-552 EFS-701: Silicone-based surfactant, manufactured by DIC Corporation EFS-801: Silicone-based surfactant, manufactured by DIC Corporation

[0192] <Solvents> PGMEA: Propylene glycol monomethyl ether acetate MEK: Methyl ethyl ketone MFG: Propylene glycol monomethyl ether

[0193] (Example 1 and Comparative Example 1) [Production of Photosensitive Transfer Material] Photosensitive transfer materials consisting of a temporary support, an intermediate layer, and a photosensitive layer were prepared to have the configurations shown in Table 3. Specifically, the process was as follows: On a temporary support (thickness 16 μm, manufactured by Toray Industries, Inc., 16KS40), an intermediate layer forming composition for forming the intermediate layer shown in Table 2 was applied using a slit nozzle so that the coating width after drying was 1.0 m and the film thickness after drying was the value listed in Table 3. The material was then passed through a 100°C drying zone for 40 seconds to form the intermediate layer. Furthermore, on the intermediate layer, a photosensitive layer forming composition for forming the photosensitive layer shown in Table 3 was applied using a slit nozzle so that the coating width after drying was 1.0 m and the film thickness after drying was the value listed in Table 3. The material was then passed through an 80°C drying zone for 40 seconds to form a negative-type photosensitive layer. A 20 μm thick polypropylene film (Alfan E200, manufactured by Oji F-Tex Co., Ltd.) was pressed onto this as a protective film to create a photosensitive transfer material. This material was then wound up into a roll and left for more than 24 hours.

[0194] [Measurement of Melt Viscosity] In the examples and comparative examples, photosensitive transfer materials were prepared as test specimens. The melt viscosity of the photosensitive layer, from which the temporary support, intermediate layer, and protective film had been peeled off, was measured using a rheometer (Anton Paar MCR302 rheometer), a 12 mmΦ parallel plate, and a Peltier plate (Gap: approximately 0.8 mm) under the following conditions: (1) Temperature: 20°C to 125°C (2) Heating rate: 3°C / min (3) Frequency: 0.1 Hz (4) Strain: 0.02%

[0195] [Manufacturing of Laminate] A 5 nm thick nickel-chromium (8 / 2) layer and a 200 nm thick copper layer were deposited in that order on a 25 μm thick polyimide substrate by vapor deposition to prepare a copper-layered polyimide substrate. After peeling off the protective film of the fabricated photosensitive transfer material, it was laminated to the copper-layered polyimide substrate under lamination conditions of roll temperature 100°C, linear pressure 1.0 MPa, and linear speed 1.0 m / min so that the copper layer and the photosensitive layer were in contact (lamination step). Next, the temporary support was peeled off at a 180° angle (peeling step). Next, exposure was performed using a photomask having a predetermined line width (μm) / space width (μm) pattern, with the intermediate layer in contact with the mask. A high-pressure mercury lamp with the i-line (365 nm) as the main exposure wavelength was used for exposure. The exposure amount was arbitrarily set so that the top shape of each pattern matched the opening of the mask. Shower development was performed with a 1% by mass aqueous solution of sodium carbonate at a liquid temperature of 25°C, followed by washing with water to form a predetermined pattern on the copper and obtain a laminate (pattern formation step).

[0196] [Measurement of Storage Modulus of Cured Film] In the examples and comparative examples, laminates were prepared as test specimens before pattern formation. The temporary support of the photosensitive transfer material was peeled off, and a laminate was prepared in which a photosensitive layer was laminated on a copper layer. This was exposed to solid light at the exposure amount set in [Laminate Manufacturing], then shower developed with a 1% by mass aqueous sodium carbonate solution at a liquid temperature of 25°C, and washed with water to prepare a laminate in which a cured photosensitive layer was laminated on a copper layer. The storage modulus was measured on the cured photosensitive layer surface of this laminate under the following conditions. Apparatus: Bruker Nano Triboindenter Indenter: Belkovich Indenter Load: 5,000 μN Indentation depth: 1 / 10 of the film thickness of the cured photosensitive layer Measurement location: Measurements were taken at four different locations, and the average value was taken.

[0197] [Cu Peel Strength] In the examples and comparative examples, laminates were prepared as test specimens before pattern formation. The temporary support of the photosensitive transfer material was peeled off to create a laminate in which the photosensitive layer was laminated on a copper layer. This was then exposed to solid light at the exposure amount set for the manufacture of the above laminate, followed by shower development with a 1% by mass aqueous solution of sodium carbonate at a liquid temperature of 25°C, and then washed with water to create a laminate in which the hardened photosensitive layer was laminated on a copper layer. A 4.5 cm x 15 cm piece of double-sided tape (STT-125CK, manufactured by Soken Chemical Co., Ltd.) was attached to the laminate, and the opposite side was attached to soda-lime glass. The sample copper-layered substrate was peeled 180° at a peeling speed of 20 mm / min using an A&D Tensilon universal tester, and the peel strength between the hardened photosensitive layer and the copper layer was measured.

[0198] [Various Evaluations] <Stability after temporary support removal> After removing the temporary support from the laminates of the above examples and comparative examples, they were left in a yellow light environment at 23°C and 55% humidity, and the surface was evaluated based on the following evaluation criteria. Evaluations "A" to "D" were designated as examples (this disclosure). -Evaluation Criteria- "A": No change in surface even after 24 hours have passed since temporary support removal "B": No change in surface up to 5 hours after temporary support removal "C": No change in surface up to 1 hour after temporary support removal "D": No change in surface up to 0.5 hours after temporary support removal "E": Surface changes within 0.5 hours after temporary support removal

[0199] <Cu Peel Strength (Adhesion to Copper)> The Cu peel strength of the laminates of the above examples and comparative examples was evaluated based on the following evaluation criteria. The evaluation results are summarized in Table 3. Evaluations "A" to "C" are designated as examples (this disclosure). -Evaluation Criteria- "A": Cu peel strength of 60 mN / cm or more "B": Cu peel strength of 40 mN / cm or more and less than 60 mN / cm "C": Cu peel strength of 20 mN / cm or more and less than 40 mN / cm "D": Cu peel strength of less than 20 mN / cm

[0200] (Examples 2-17, and Comparative Example 2) [Manufacturing of Photosensitive Transfer Material] Photosensitive transfer materials consisting of a temporary support, an intermediate layer, and a photosensitive layer are each prepared to have the configuration shown in Table 3. Specifically, the process is as follows: On a temporary support (16 μm thick, manufactured by Toray Industries, Inc., 16KS40), an intermediate layer forming composition for forming the intermediate layer shown in Table 3 is applied using a slit nozzle so that the coating width after drying is 1.0 m and the film thickness after drying is the value shown in Table 3, and the material is passed through a 100°C drying zone for 40 seconds to form the intermediate layer. Furthermore, on the intermediate layer, a photosensitive layer forming composition for forming the photosensitive layer shown in Table 3 is applied using a slit nozzle so that the coating width after drying is 1.0 m and the film thickness after drying is the value shown in Table 3, and the material is passed through an 80°C drying zone for 40 seconds to form a negative-type photosensitive layer. A 20 μm thick polypropylene film (Alfan E200, manufactured by Oji F-Tex Co., Ltd.) is pressed onto this as a protective film to create a photosensitive transfer material. After being wound up into a roll, it is left for 24 hours or more.

[0201] A laminate is fabricated and evaluated in the same manner as in Example 1.

[0202]

[0203] The results in Table 3 show that the photosensitive transfer materials of Examples 1 to 17 exhibit superior stability after temporary support removal and better adhesion of the resulting patterns to copper compared to Comparative Examples 1 and 2.

[0204] The disclosure of Japanese Patent Application No. 2025-014310, filed on 30 January 2025, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference.

[0205] 10: Photosensitive transfer material, 12: Protective film, 16: Temporary support, 18A: Photosensitive layer, 20A: Intermediate layer

Claims

1. The material comprises a temporary support, an intermediate layer, and a photosensitive layer in this order, and the melt viscosity of the photosensitive layer at 25°C is 5.0 × 10⁻⁶. ５ The hardened photosensitive layer has a storage modulus of 1.0 × 10⁻¹⁰ or higher. ９ Pa ~ 4.0 x 10 ９ A photosensitive transfer material that is Pa.

2. The photosensitive transfer material according to claim 1, wherein the photosensitive layer includes a binder.

3. The photosensitive transfer material according to claim 2, wherein the glass transition temperature of the binder is 75°C or higher and 110°C or lower.

4. The photosensitive transfer material according to claim 2, wherein the acid value of the binder is 80 mg KOH / g or more.

5. The photosensitive transfer material according to claim 2, wherein the binder comprises a resin having structural units derived from a styrene compound.

6. The photosensitive transfer material according to claim 1, wherein the temporary support and the intermediate layer are in contact.

7. The photosensitive transfer material according to claim 1, wherein the intermediate layer contains a surfactant.

8. The photosensitive transfer material according to claim 7, wherein the surfactant comprises a surfactant having a silicon atom.

9. The photosensitive transfer material according to claim 1, wherein the average thickness of the intermediate layer is 1 μm to 10 μm.

10. The photosensitive transfer material according to claim 1, wherein the average thickness of the photosensitive layer is 10 μm to 30 μm.

11. A method for manufacturing a resin pattern, comprising the steps of: bonding a photosensitive transfer material and a substrate so that the photosensitive layer in the photosensitive transfer material according to any one of claims 1 to 10 is in contact with the substrate; pattern exposing the photosensitive layer; and developing the exposed photosensitive layer to form a resin pattern, wherein the step of peeling off the temporary support is performed after the bonding step and before the step of developing the exposed photosensitive layer.

12. A method for manufacturing a conductive pattern, comprising the steps of: forming the resin pattern on a substrate using the method for manufacturing a resin pattern described in claim 11; performing a plating treatment on an area of ​​the substrate where the resin pattern is not formed; and removing the resin pattern, in this order.

13. A method for manufacturing a conductive pattern, comprising the steps of: forming the resin pattern on a substrate using the method for manufacturing a resin pattern described in claim 11; etching a region of the substrate on which the resin pattern is not formed; and removing the resin pattern, in this order.

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