Photosensitive transfer material and method for producing circuit wiring

Abstract

This disclosure provides a photosensitive transfer material having a pseudo-support and a photosensitive resin layer, and its application. The halide ion content in the photosensitive resin layer is less than 100 ppm relative to the total mass of the photosensitive resin layer. The photosensitive resin layer contains an alkali-soluble polymer and a compound containing vinyl unsaturated bonds. The alkali-soluble polymer has constituent units derived from monomers having aromatic hydrocarbon groups. The compound containing vinyl unsaturated bonds is a difunctional vinyl unsaturated compound having a bisphenol A structure.

Description

[Technical Field]

[0001] This disclosure relates to a method for manufacturing a photosensitive transfer material and circuit wiring. [Previous Technology]

[0002] A display device (e.g., an organic light-emitting display device and a liquid crystal display device) having a touch panel (e.g., a capacitive input device) has a patterned conductive layer inside the touch panel. Examples of patterned conductive layers include electrode patterns and wiring (e.g., peripheral wiring and lead wiring) of a sensor corresponding to a visual recognition unit.

[0003] When forming a patterned conductive layer, the number of steps to obtain the desired pattern shape is small, therefore, the method of using photosensitive transfer materials is widely used (for example, Patent Document 1). For example, a photosensitive resin layer is formed on a substrate using a photosensitive transfer material, and then the photosensitive resin layer is exposed through a mask having the desired pattern, followed by development and etching processes, thereby forming a patterned conductive layer.

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2019-128445

[0005] However, in etching processes, there is a problem where necessary portions of the workpiece, such as metal, are removed due to lateral etching. Lateral etching refers to the phenomenon where the processing (i.e., removal) of the workpiece by etching proceeds not only in the depth direction (i.e., the thickness direction) of the workpiece, but also in a direction orthogonal to the depth direction. This problem, for example, can lead to a decrease in the dimensional accuracy of the pattern obtained by etching. Therefore, it is necessary to reduce the amount of lateral etching (hereinafter referred to as "lateral etching amount"). [Summary of the Invention]

[0006] This disclosure was made in view of the above circumstances. One aspect of this disclosure is to provide a photosensitive transfer material that reduces the amount of lateral etching during etching processes. Another aspect of this disclosure is to provide a method for manufacturing circuit wiring that reduces the amount of lateral etching during etching processes.

[0007] This disclosure includes the following embodiments. <1> A photosensitive transfer material comprising: a pseudo-support; and a photosensitive resin layer, wherein the content of halide ions in the photosensitive resin layer is less than 100 ppm relative to the total mass of the photosensitive resin layer, the photosensitive resin layer contains an alkali-soluble polymer and a compound containing an ethylene unsaturated bond, the alkali-soluble polymer having a constituent unit derived from a monomer having an aromatic hydrocarbon group, and the compound containing an ethylene unsaturated bond being a difunctional ethylene unsaturated compound having a bisphenol A structure. <2> The photosensitive transfer material as described in <1>, wherein the content of halide ions is from 10 ppm to 50 ppm relative to the total mass of the photosensitive resin layer. <3> The photosensitive transfer material as described in <1> or <2>, wherein the content of halide ions is from 10 ppm to 20 ppm relative to the total mass of the photosensitive resin layer. <4> The photosensitive transfer material as described in any one of <1> to <3>, wherein the halide ion is a chloride ion. <5> The photosensitive transfer material as described in any one of <1> to <4>, wherein the photosensitive resin layer contains a photopolymerization initiator. <6> A method for manufacturing circuit wiring, comprising: preparing a laminate having, in sequence, a substrate, a conductive layer, and a resin pattern formed using any one of <1> to <5>; and etching the conductive layer in areas of the laminate where the resin pattern is not disposed. [Effects of the Invention]

[0008] According to one aspect of the present disclosure, a photosensitive transfer material is provided that reduces the amount of lateral etching during an etching process. According to another aspect of the present disclosure, a method for manufacturing circuit wiring that reduces the amount of lateral etching during an etching process is provided.

Implementation Method

[0010] The embodiments of this disclosure will be described in detail below. This disclosure is not limited to any of the embodiments described below and may be implemented by appropriate modifications within the scope of the purpose of this disclosure.

[0011] When describing embodiments of this disclosure with reference to the drawings, descriptions of repeated constituent elements and symbols in the drawings may sometimes be omitted. Constituent elements shown using the same symbols in the drawings are meant to be the same constituent elements. Dimensional ratios in the drawings may not necessarily represent actual dimensional ratios.

[0012] In this disclosure, the numerical range represented by "~" indicates a range that includes the values ​​recorded before and after "~" as the lower and upper limits, respectively. Within the numerical range recorded in stages in this disclosure, the upper or lower limit value recorded in a certain numerical range can be replaced by the upper or lower limit value of other numerical ranges recorded in stages. Furthermore, within the numerical range recorded in this disclosure, the upper or lower limit value recorded in a certain numerical range can also be replaced by the values ​​shown in the embodiments.

[0013] In this disclosure, if there are multiple substances in the composition corresponding to each component, unless otherwise specified, the amount of each component in the composition means the total amount of the multiple substances present in the composition.

[0014] In this disclosure, the term "step" includes not only independent steps, but also steps that can achieve the desired purpose of the step, even if they cannot be clearly distinguished from other steps.

[0015] In this disclosure, "mass%" and "weight%" have the same meaning, and "parts of mass" and "parts of weight" have the same meaning.

[0016] In this disclosure, a combination of two or more preferred states is a better state.

[0017] In this disclosure, unsubstituted and unsubstituted groups (atomic groups) include groups without substituents and groups with substituents. For example, the term "alkyl" includes not only alkyl groups without substituents (i.e., unsubstituted alkyl groups) but also alkyl groups with substituents (i.e., substituted alkyl groups).

[0018] In this disclosure, “(meth)acrylic acid” means acrylic acid, methacrylic acid, or both acrylic acid and methacrylic acid.

[0019] In this disclosure, "(meth)acryl" means acrylonitrile, methacryl, or both acrylonitrile and methacryl.

[0020] In this disclosure, “(meth)acrylate” means acrylate, methacrylate or both acrylate and methacrylate.

[0021] In this disclosure, "alkali solubility" means the property of having a solubility of more than 0.1 g in an aqueous solution of sodium carbonate (100 g, sodium carbonate concentration: 1% by mass) at a liquid temperature of 22°C.

[0022] In this disclosure, chemical structural formulas are sometimes written with the hydrogen atom omitted.

[0023] In this disclosure, unless otherwise specified, “exposure” includes not only exposure using light, but also depiction using particle beams (e.g., electron beams and ion beams). Examples of light used for exposure include activated light (also known as active energy rays). Examples of activated light include the brightline spectrum of a mercury lamp, far-ultraviolet light represented by an excimer laser, extreme ultraviolet (EUV) light, and X-rays.

[0024] In this disclosure, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) are calculated by detecting compounds in THF (tetrahydrofuran) using a differential refractometer and by using polystyrene as a standard substance in a gel permeation chromatography (GPC) analysis apparatus with columns “TSKgel GMHxL”, “TSKgel G4000HxL” and “TSKgel G2000HxL” (all trade names of TOSOH CORPORATION).

[0025] In this disclosure, "solid component" means the component from which the solvent is removed from all components of the object.

[0026] <Photosensitive Transfer Material> The photosensitive transfer material disclosed herein comprises: a pseudo-support; and a photosensitive resin layer, wherein the content of halide ions in the photosensitive resin layer is less than 100 ppm relative to the total mass of the photosensitive resin layer. According to the photosensitive transfer material disclosed herein, the amount of side etching during etching processes can be reduced.

[0027] The reasons for the aforementioned effect of the photosensitive transfer material disclosed herein are as follows. One reason for the side etching is believed to be the generation of highly soluble metal halides in the etching solution due to the interaction between halide ions and the metal in the workpiece. When the proportion of halide ions in the photosensitive resin layer of the photosensitive transfer material is high, for example, if the metal and the photosensitive resin layer come into contact by bonding a substrate covered with metal (e.g., copper) and the photosensitive transfer material, metal halides (e.g., copper halides) will be generated at the interface between the metal and the photosensitive resin layer. The generation of metal halides is believed to be caused by the interaction between metal oxides present on the metal surface and halide ions. As a result, during the etching process, the removal of metal in contact with the photosensitive resin layer used as a protective film or its hardened form is promoted, thereby increasing the amount of side etching. On the other hand, in the photosensitive transfer material disclosed herein, the content of halide ions in the photosensitive resin layer is less than 100 ppm, thus suppressing the generation of metal halide, which is considered a cause of increased lateral etching. Therefore, according to the photosensitive transfer material disclosed herein, the amount of lateral etching in etching processes can be reduced. Furthermore, according to the photosensitive transfer material disclosed herein, for example, the amount of lateral etching in etching processes using copper, which is frequently used, can be effectively reduced.

[0028] <<Construmental Elements>> The photosensitive transfer material disclosed herein comprises a dummy support and a photosensitive resin layer. In the aforementioned photosensitive transfer material, the photosensitive resin layer can be directly or through arbitrary lamination onto the dummy support. In the aforementioned photosensitive transfer material, any layer can be deposited on the side of the photosensitive resin layer opposite to the side where the dummy support is disposed. Examples of such arbitrary layers include other layers described later. Hereinafter, the constituent elements of the photosensitive transfer material disclosed herein will be specifically described.

[0029] [Pseudo-support] The photosensitive transfer material disclosed herein has a pseudo-support. The pseudo-support system is a support that can be peeled off from the photosensitive transfer material. The pseudo-support system can at least support the photosensitive resin layer.

[0030] It is preferable that the spoofing system has light transmittance. By having a light-transmitting spoofing, the photosensitive resin layer can be exposed through the spoofing during exposure. In this disclosure, "light transmittance" means that the transmittance of light at the wavelength used for pattern exposure is 50% or more. From the viewpoint of improving the exposure sensitivity of the photosensitive resin layer, it is preferable that the transmittance of light at the wavelength used for pattern exposure (preferably 365 nm) is 60% or more, and even more preferably 70% or more. In this disclosure, "transmittance" refers to the ratio of the intensity of the emitted light to the intensity of the incident light when light is incident along a direction perpendicular to the main surface of the layer being measured (i.e., the thickness direction). The transmittance is measured using an MCPD Series manufactured by OTSUKA ELECTRONICS CO.,LTD.

[0031] Examples of pseudo-supports include glass substrates, resin films, and paper. From the viewpoints of strength, flexibility, and light transmittance, resin films are preferred as pseudo-support systems.

[0032] Examples of resin films include polyethylene terephthalate films (i.e., PET films), cellulose triacetate films, polystyrene films, and polycarbonate films. PET films are preferred, and biaxially stretched PET films are even more preferred.

[0033] The thickness of the dummy support is not limited. The thickness of the dummy support can be determined, for example, based on the strength, light transmittance, material, and flexibility required when bonding photosensitive transfer materials and substrates. An average thickness of 5 μm to 100 μm is preferred. Furthermore, from the viewpoint of ease of operation and versatility, an average thickness of 5 μm to 50 μm is preferred, 5 μm to 20 μm is more preferred, 10 μm to 20 μm is further preferred, and 10 μm to 16 μm is especially preferred.

[0034] The average thickness of the constituent elements of the photosensitive transfer material (e.g., the spurious support and the photosensitive resin layer) was determined by the following method: A cross-section perpendicular to the main surface of the photosensitive transfer material (i.e., the thickness direction) was observed using a scanning electron microscope (SEM). Based on the obtained observation images, the thickness of 10 constituent elements as objects was measured. The average thickness of the constituent elements as objects was calculated by arithmetically averaging the measured values.

[0035] The arithmetic mean roughness Ra of the surface of the dummy support on the side where the photosensitive resin layer is disposed is preferably 0.1 μm or less, more preferably 0.05 μm or less, and particularly preferably 0.02 μm or less. The lower limit of the arithmetic mean roughness Ra is not limited. The arithmetic mean roughness Ra of the surface of the dummy support on the side where the photosensitive resin layer is disposed can be determined, for example, within the range of 0 μm or more.

[0036] The arithmetic mean roughness Ra is measured by the following method. The surface profile of the object to be measured is obtained using a three-dimensional optical profilometer (New View 7300, manufactured by Zygo) under the following conditions. The Microscope Application of MetroPro ver8.3.2 is used as the measurement and analysis software. Next, the Surface Map screen is displayed using the aforementioned software, and color gradation statistics are obtained from the Surface Map screen. The arithmetic mean roughness Ra of the surface of the object to be measured is obtained from the obtained color gradation statistics. Furthermore, when the surface of the object to be measured is in contact with the surface of other layers, the arithmetic mean roughness Ra of the surface of the object to be measured exposed by peeling the object to be measured from other layers is measured.

[0037] It is preferable that the dummy support (especially the resin film) is free from deformation (e.g., wrinkles), scratches, and defects. From the viewpoint of pattern formation properties during pattern exposure via the dummy support and the transparency of the dummy support, it is preferable that the number of particles, foreign matter, defects, and precipitates contained in the dummy support is low. In the dummy support, it is preferable that the number of particles, foreign matter, and defects with a diameter of 1 μm or more is 50 or less per 10 mm², more preferably 10 or less per 10 mm², further preferably 3 or less per 10 mm², and especially preferably 0 per 10 mm².

[0038] Preferred forms of the pseudo-support are described, for example, in paragraphs 0017-0018 of Japanese Patent Application Publication No. 2014-085643, paragraphs 0019-0026 of Japanese Patent Application Publication No. 2016-027363, paragraphs 0041-0057 of International Publication No. 2012 / 081680, paragraphs 0029-0040 of International Publication No. 2018 / 179370, and paragraphs 0012-0032 of Japanese Patent Application Publication No. 2019-101405. The contents of these publications are incorporated herein by reference.

[0039] [Photosensitive Resin Layer] The photosensitive transfer material disclosed herein has a photosensitive resin layer. It is preferable that the photosensitive resin layer is a negative photosensitive resin layer in which the solubility of the exposed portion in the developer is reduced by exposure and the unexposed portion is removed by development. However, the photosensitive resin layer is not limited to a negative photosensitive resin layer; it can also be a positive photosensitive resin layer in which the solubility of the exposed portion in the developer is increased by exposure and the exposed portion is removed by development.

[0040] (Halide ions) The content of halide ions in the photosensitive resin layer is 100 ppm or less relative to the total mass of the photosensitive resin layer. By ensuring that the content of halide ions in the photosensitive resin layer is 100 ppm or less, the amount of side etching during the etching process can be reduced.

[0041] From the viewpoint of reducing the amount of side etching during the etching process, the lower the proportion of halide ions in the photosensitive resin layer, the better. Specifically, the proportion of halide ions in the photosensitive resin layer is preferably 85 ppm or less relative to the total mass of the photosensitive resin layer, more preferably 50 ppm or less, further preferably 30 ppm or less, and especially preferably 20 ppm or less. The proportion of halide ions in the photosensitive resin layer can also be 15 ppm or less or 10 ppm or less relative to the total mass of the photosensitive resin layer. By keeping the proportion of halide ions within the above range, the amount of side etching during the etching process can be further reduced.

[0042] From the viewpoint of reducing the amount of side etching in the etching process, the lower limit of the content ratio of halide ions in the photosensitive resin layer is not limited. When setting the lower limit of the content ratio of halide ions, the content ratio of halide ions in the photosensitive resin layer can be determined in a range of, for example, 1 ppm or more relative to the total mass of the photosensitive resin layer.

[0043] The content of halide ions was determined by the following method. 100 mg of photosensitive resin layer collected from photosensitive transfer material was dissolved in 1 g of ethyl acetate. 2 g of ultrapure water was added to the ethyl acetate, and after thorough stirring, the resulting mixture was allowed to stand for 1 hour. The aqueous layer was extracted from the mixture, and the content of halide ions was determined by ion chromatography. The determination conditions for ion chromatography are shown below. Based on the determination results, the content of halide ions in the photosensitive resin layer was calculated. (1) Measuring equipment: Dionex INTEGRION HPIC (Thermo Fisher Scientific Inc.) (2) Column: Dionex IonPac AS22 (anion analysis column, size (mm): 4×250) (3) Flow rate: 1 min / mL (4) Temperature: 35℃ (5) Sample for calibration curve preparation: Anion mixed standard solution IV (Kanto Chemical Co., Inc.) (6) Eluent: An aqueous solution obtained by mixing sodium carbonate (4.5 mmol / L) and sodium bicarbonate solution (1.4 mmol / L).

[0044] Examples of halide ions include fluoride ions (F-), chloride ions (Cl-), bromide ions (Br-), and iodide ions (I-). From the viewpoint of reducing lateral etching, it is preferable to limit the proportion of chloride ions in the photosensitive resin layer.

[0045] It is believed that most of the halide ions in the photosensitive resin layer originate from the raw materials of the photosensitive resin layer. For example, by removing halide ions contained in the raw materials of the photosensitive resin layer, the proportion of halide ions in the photosensitive resin layer can be reduced. Methods for removing halide ions include, for example, distillation, using cation exchange resins, using ultrafiltration membranes, and using adsorbent materials. Zeolite can be used as an example of an adsorbent material. However, the methods for removing halide ions are not limited to the above methods, and known methods can also be used. Furthermore, not limited to methods for removing halide ions contained in the raw materials, the proportion of halide ions in the photosensitive resin layer can also be reduced by selectively using raw materials with a low proportion of halide ions.

[0046] (Polymer A) It is preferable that the photosensitive resin layer system contains polymer A. It is preferable that polymer A is an alkali-soluble polymer. Alkali-soluble polymers include polymers that are easily soluble in alkaline substances.

[0047] From the viewpoint of improving resolution by suppressing the swelling of the photosensitive resin layer caused by the developer, the acid value of polymer A is preferably below 250 mg KOH / g, more preferably below 230 mg KOH / g, and particularly preferably below 210 mg KOH / g. The lower limit of the acid value is not limited. From the viewpoint of improving developability, the acid value of polymer A is preferably above 60 mg KOH / g, more preferably above 120 mg KOH / g, further preferably above 150 mg KOH / g, and particularly preferably above 170 mg KOH / g. The acid value of polymer A can be adjusted, for example, according to the types of constituent units constituting polymer A and the content of constituent units containing acid groups.

[0048] In this disclosure, the acid value refers to the mass (mg) of potassium hydroxide required to neutralize 1g of the sample. In this disclosure, the unit of acid value is expressed as mgKOH / g. The acid value can be calculated, for example, based on the average content of acid groups in the compound.

[0049] The weight-average molecular weight (Mw) of polymer A is preferably between 5,000 and 500,000. From the viewpoint of improving resolution and developability, it is preferable to set the weight-average molecular weight to 500,000 or less. The weight-average molecular weight of polymer A is more preferably 100,000 or less, further preferably 60,000 or less, and especially preferably 50,000 or less. On the other hand, from the viewpoint of controlling the properties of the developed aggregates, edge melting properties, and chipping properties, it is preferable to set the weight-average molecular weight to 5,000 or more. The weight-average molecular weight of polymer A is more preferably 10,000 or more, further preferably 15,000 or more, and especially preferably 20,000 or more. Edge melting properties refer to the degree to which the photosensitive resin layer easily overflows from the end face of the roll when the photosensitive transfer material is rolled into a roll. Chipping properties refer to the degree to which chips easily splatter when the unexposed film is cut with a cutter. For example, if chips adhere to the surface of the photosensitive transfer material, the chips will be transferred to the mask during the exposure step, resulting in a defective product.

[0050] The dispersity of polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, further preferably 1.0 to 4.0, and especially preferably 1.0 to 3.0. In this disclosure, the dispersity is the ratio of weight average molecular weight to number average molecular weight (weight average molecular weight / number average molecular weight).

[0051] From the viewpoint of suppressing the deterioration of line width and resolution when the focus position shifts during exposure, it is preferable that polymer A has constituent units derived from monomers with aromatic hydrocarbon groups.

[0052] As aromatic hydrocarbon groups, examples include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups.

[0053] The proportion of monomers derived from aromatic hydrocarbon groups in polymer A is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, particularly preferably 45% by mass or more, and most preferably 50% by mass or more, relative to the total mass of polymer A. There is no upper limit to the proportion of monomers derived from aromatic hydrocarbon groups in polymer A. The proportion of monomers derived from aromatic hydrocarbon groups in polymer A is preferably 95% by mass or less, and more preferably 85% by mass or less, relative to the total mass of polymer A. Furthermore, when the photosensitive resin layer contains multiple types of polymer A, the proportion of monomers derived from aromatic hydrocarbon groups is calculated as a weight average.

[0054] Examples of monomers having an aromatic hydrocarbon group include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tributoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimers, and styrene trimers). Monomers having an aromatic hydrocarbon group, aralkyl groups, or styrene are preferred.

[0055] As an aralkyl group, examples include substituted or unsubstituted phenylalkyl groups (excluding benzyl) and substituted or unsubstituted benzyl groups, with substituted or unsubstituted benzyl groups being preferred.

[0056] Examples of monomers having a phenyl alkyl group include phenyl ethyl (meth)acrylate.

[0057] Examples of monomers having a benzyl group include (meth)acrylates having a benzyl group (e.g., benzyl (meth)acrylate and benzyl chloride (meth)acrylate) and vinyl monomers having a benzyl group (e.g., vinyl benzyl chloride and vinyl benzyl alcohol). Monomers having a benzyl group are preferred.

[0058] In one embodiment, when the constituent unit of the monomer having an aromatic hydrocarbon group in polymer A is a constituent unit derived from benzyl methacrylate, the content ratio of the constituent unit derived from the benzyl methacrylate monomer in polymer A is preferably 50% to 95% by mass relative to the total mass of polymer A, more preferably 60% to 90% by mass, further preferably 70% to 90% by mass, and especially preferably 75% to 90% by mass.

[0059] In one embodiment, when the constituent unit of the monomer having an aromatic hydrocarbon group in polymer A is a constituent unit derived from styrene, the content ratio of the constituent unit derived from styrene in polymer A is preferably 20% to 70% by mass relative to the total mass of polymer A, more preferably 25% to 60% by mass, further preferably 30% to 60% by mass, and especially preferably 30% to 55% by mass.

[0060] In one embodiment, it is preferable that polymer A, having constituent units derived from monomers having aromatic hydrocarbon groups, is a copolymer obtained by polymerizing monomers having aromatic hydrocarbon groups and at least one selected from the group consisting of a first monomer and a second monomer described later. The copolymer described above has constituent units derived from monomers having aromatic hydrocarbon groups and at least one selected from the group consisting of constituent units derived from a first monomer and constituent units derived from a second monomer.

[0061] Polymer A can be a polymer that does not have constituent units derived from monomers having aromatic hydrocarbon groups. It is preferable that polymer A, which does not have constituent units derived from monomers having aromatic hydrocarbon groups, is obtained by polymerizing at least one of the first monomers (excluding monomers having aromatic hydrocarbon groups) described later, and even more preferably, a copolymer obtained by polymerizing at least one of the first monomers (excluding monomers having aromatic hydrocarbon groups) described later and at least one of the second monomers (excluding monomers having aromatic hydrocarbon groups) described later.

[0062] In one embodiment, polymer A is preferably a polymer obtained by polymerizing at least one of the first monomers described later, and a copolymer obtained by polymerizing at least one of the first monomers described later and at least one of the second monomers described later is more preferably. The copolymer has constituent units derived from the first monomer and constituent units derived from the second monomer.

[0063] The first monomer system is a monomer having a carboxyl group and a polymerizable unsaturated group in the molecule. The first monomer system can also be a monomer that does not have an aromatic hydrocarbon group in the molecule. Examples of first monomers include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. The first monomer system (meth)acrylic acid is preferred.

[0064] The proportion of the constituent units derived from the first monomer in polymer A is preferably 5% to 50% by mass relative to the total mass of polymer A, more preferably 10% to 40% by mass, and especially preferably 15% to 30% by mass.

[0065] The second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in its molecule. The second monomer may also be a monomer that does not have an aromatic hydrocarbon group in its molecule. Examples of second monomers include (meth)acrylate compounds, esters of vinyl alcohol, and (meth)acrylonitrile. In this disclosure, "(meth)acrylonitrile" includes acrylonitrile, methacrylonitrile, or both acrylonitrile and methacrylonitrile.

[0066] Examples of (meth)acrylate compounds include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tributyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, cyclohexyl methacrylate, and 2-ethylhexyl methacrylate.

[0067] Examples of ester compounds of vinyl alcohol include vinyl acetate.

[0068] The second monomer is preferably selected from at least one of the group consisting of methyl methacrylate, 2-ethylhexyl methacrylate and n-butyl methacrylate, with methyl methacrylate being more preferred.

[0069] The proportion of the constituent units derived from the second monomer in polymer A is preferably 5% to 60% by mass relative to the total mass of polymer A, more preferably 10% to 50% by mass, and especially preferably 15% to 45% by mass.

[0070] From the viewpoint of suppressing the deterioration of line width and resolution when the focus position shifts during exposure, polymer A is preferably composed of at least one of the group consisting of constituent units derived from monomers having an aryl group and constituent units derived from styrene. For example, polymer A is preferably composed of at least one of the group consisting of copolymers containing constituent units derived from methacrylic acid, constituent units derived from benzyl methacrylate, and constituent units derived from styrene, and copolymers containing constituent units derived from methacrylic acid, constituent units derived from methyl methacrylate, constituent units derived from benzyl methacrylate, and constituent units derived from styrene.

[0071] In one embodiment, polymer A is preferably a polymer containing 25% to 60% by mass of a monomer having an aromatic hydrocarbon group, 20% to 55% by mass of a first monomer, and 15% to 55% by mass of a second monomer. Polymer A is even more preferably a polymer containing 25% to 40% by mass of a monomer having an aromatic hydrocarbon group, 20% to 35% by mass of a first monomer, and 30% to 45% by mass of a second monomer.

[0072] In one embodiment, polymer A is preferably a polymer containing 70% to 90% by mass of a monomer having an aromatic hydrocarbon group and 10% to 25% by mass of a first monomer.

[0073] Polymer A can have any of the following structures among straight-chain, branched, and alicyclic structures in its side chains. By using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain, the branched or alicyclic structure can be introduced into the side chains of polymer A. The alicyclic group can be monocyclic or polycyclic. Specific examples of monomers containing a group having a branched structure in the side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, dibutyl (meth)acrylate, tributyl (meth)acrylate, isoamyl (meth)acrylate, tripentyl (meth)acrylate, dipentyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and trioctyl (meth)acrylate. Among these, isopropyl (meth)acrylate, isobutyl (meth)acrylate, and tributyl (meth)acrylate are preferred, and isopropyl (meth)acrylate or tributyl (meth)acrylate is even more preferred. Specific examples of monomers containing a group having an alicyclic structure in the side chain include monomers having a monocyclic aliphatic hydrocarbon group and monomers having a polycyclic aliphatic hydrocarbon group. Also, (meth)acrylates having an alicyclic hydrocarbon group having 5 to 20 carbon atoms can be cited. More specific examples include (meth)acrylate (bicyclo[2.2.1]heptyl-2), (meth)acrylate-1-adamantane, (meth)acrylate-2-adamantane, (meth)acrylate-3-methyl-1-adamantane, (meth)acrylate-3,5-dimethyl-1-adamantane, (meth)acrylate-3-ethyladamantane, (meth)acrylate-3-methyl-5-ethyl-1-adamantane, (meth)acrylate-3,5,8-triethyl-1-adamantane, (meth)acrylate-3,5-dimethyl-8-ethyl-1-adamantane, (meth)acrylate-2-methyl-2-adamantane, (meth)acrylate-2-ethyl-2-adamantane. Adamantane ester, 3-hydroxy-1-adamantane ester of (meth)acrylate, octahydro-4,7-methyleneindene-5-yl ester of (meth)acrylate, octahydro-4,7-methyleneindene-1-yl methyl ester of (meth)acrylate, 1-menthol ester of (meth)acrylate, tricyclodecane ester of (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl ester of (meth)acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl ester of (meth)acrylate, (nor)camphene ester of (meth)acrylate, isocamphene ester of (meth)acrylate, fumarate ester of (meth)acrylate, 2,2,5-trimethylcyclohexyl ester of (meth)acrylate, and cyclohexyl ester of (meth)acrylate, etc.Among these (meth)acrylates, cyclohexyl (meth)acrylate, norborneol (meth)acrylate, isoborneol (meth)acrylate, 1-adamantane (meth)acrylate, 2-adamantane (meth)acrylate, fenbyl (meth)acrylate, 1-mentholyl (meth)acrylate, or tricyclodecane (meth)acrylate are preferred, and cyclohexyl (meth)acrylate, norborneol (meth)acrylate, isoborneol (meth)acrylate, 2-adamantane (meth)acrylate, or tricyclodecane (meth)acrylate are even more preferred.

[0074] The glass transition temperature (Tg) of polymer A is preferably between 30°C and 180°C. In the photosensitive resin layer, by having a Tg of polymer A below 180°C, the deterioration of linewidth and resolution due to focus position shift during exposure can be suppressed. From the above viewpoint, a Tg of polymer A below 170°C is more preferable, and below 160°C is even more preferable. Furthermore, from the viewpoint of improving edge melt resistance, a Tg of polymer A above 30°C is more preferable. From the above viewpoint, a Tg of polymer A above 40°C is more preferable, above 50°C is even more preferable, above 60°C is particularly preferable, and above 70°C is optimal.

[0075] Polymer A can be a commercially available product or a synthetic product. The synthesis of polymer A is preferably carried out as follows: A suitable amount of free radical polymerization initiator (e.g., benzoyl peroxide or azoisobutyronitrile) is added to a solution obtained by diluting at least one of the monomers described above with a solvent (e.g., acetone, methyl ethyl ketone, or isopropanol), followed by heating and stirring. Sometimes, a portion of the mixture is added dropwise to the reaction solution while the synthesis is being carried out. After the reaction is complete, solvent is sometimes further added to adjust to the desired concentration. In addition to solution polymerization, monolithic polymerization, suspension polymerization, or emulsion polymerization can also be used as synthesis methods.

[0076] The photosensitive resin layer system may contain one or more polymers A. When the photosensitive resin layer contains two or more polymers A, it is preferable that the photosensitive resin layer system contains two or more polymers A having constituent units derived from monomers having aromatic hydrocarbon groups, or contains polymers A having constituent units derived from monomers having aromatic hydrocarbon groups and polymers A not having constituent units derived from monomers having aromatic hydrocarbon groups. In the latter case, it is preferable that the proportion of polymers A having constituent units derived from monomers having aromatic hydrocarbon groups is 50% by mass or more relative to the total mass of polymers A, more preferably 70% by mass or more, further preferably 80% by mass or more, and especially preferably 90% by mass or more.

[0077] The content ratio of polymer A relative to the total mass of the photosensitive resin layer is preferably 10% to 90% by mass, more preferably 30% to 70% by mass, and particularly preferably 40% to 60% by mass. From the viewpoint of controlling the development time, it is preferable to set the content ratio of polymer A relative to the photosensitive resin layer to 90% by mass or less. On the other hand, from the viewpoint of improving edge melting resistance, it is preferable to set the content ratio of polymer A relative to the photosensitive resin layer to 10% by mass or more.

[0078] (Polymerizable Compound B) It is preferable that the photosensitive resin layer system contains polymerizable compound B. In this disclosure, "polymerizable compound" means a compound polymerized under the action of the polymerization initiator described later. Furthermore, polymerizable compound B is a compound different from polymer A described above.

[0079] Polymerizable compound B has bonds or polymerizable groups that are related to polymerization reactions. Examples of bonds related to polymerization reactions include vinyl unsaturated bonds.

[0080] The polymerizable group in polymerizable compound B is not limited as long as it is a group related to the polymerization reaction. Examples of polymerizable groups in polymerizable compound B include groups containing vinyl unsaturated bonds (e.g., vinyl, acrylonitrile, methacrylonitrile, styrene, and maleicadiimino) and cationic polymerizable groups (e.g., epoxy and oxetane). It is preferred that the polymerizable group contains a vinyl unsaturated bond (hereinafter, sometimes referred to as "vinyl unsaturated group"), and acrylonitrile or methacrylonitrile are more preferred.

[0081] From the viewpoint of superior photosensitivity of the photosensitive resin layer, it is preferable that the polymeric compound B is a compound containing ethylene unsaturated bonds, more preferably a compound having one or more ethylene unsaturated groups in one molecule (i.e., an ethylene unsaturated compound), and especially preferably a compound having two or more ethylene unsaturated groups in one molecule (i.e., a polyfunctional ethylene unsaturated compound). Furthermore, from the viewpoint of superior resolution and peelability, it is preferable that the number of ethylene unsaturated groups contained in one molecule of the ethylene unsaturated compound is six or less, more preferably three or less, and especially preferably two or less.

[0082] Ethylene unsaturated compounds are preferably (meth)acrylate compounds having one or more (meth)acrylic groups in one molecule.

[0083] From the viewpoint of achieving a better balance between photosensitivity, resolution and peelability in the photosensitive resin layer, it is preferable that the polymerizable compound B is selected from at least one of the group consisting of compounds having two vinyl unsaturated groups in one molecule (i.e., difunctional vinyl unsaturated compounds) and compounds having three vinyl unsaturated groups in one molecule (i.e., trifunctional vinyl unsaturated compounds), and it is more preferable that the compound having two vinyl unsaturated groups in one molecule is preferred.

[0084] From the viewpoint of excellent peelability of the photosensitive resin layer, the ratio of the content of difunctional vinyl unsaturated compound to the content of polymeric compound B is preferably 60% by mass or more, more preferably 70% by mass, and especially preferably 90% by mass or more. The upper limit of the proportion of difunctional vinyl unsaturated compound relative to the content of polymeric compound B is not limited and can be 100% by mass. That is, all polymeric compound B contained in the photosensitive resin layer can be difunctional vinyl unsaturated compounds.

[0085] - Polymerizable Compound B1 - The photosensitive resin layer system preferably contains a polymerizable compound B1 having one or more aromatic rings and two vinyl unsaturated groups in one molecule. Polymerizable compound B1 is a difunctional vinyl unsaturated compound of the aforementioned polymerizable compound B having one or more aromatic rings in one molecule.

[0086] In the photosensitive resin layer, from the viewpoint of superior resolution, the ratio of the content of polymeric compound B1 to the content of polymeric compound B is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 55% by mass or more, and especially preferably 60% by mass or more. The upper limit of the ratio of the content of polymeric compound B1 to the content of polymeric compound B is not limited. From the viewpoint of peelability, the ratio of the content of polymeric compound B1 to the content of polymeric compound B is preferably 99% by mass or less, more preferably 95% by mass or less, further preferably 90% by mass or less, and especially preferably 85% by mass or less.

[0087] Examples of aromatic rings in polymerizable compound B1 include aromatic hydrocarbon rings (e.g., benzene rings, naphthalene rings, and anthracene rings), aromatic heterocycles (e.g., thiophene rings, furan rings, pyrrole rings, imidazole rings, triazole rings, and pyridine rings), and condensed rings of the like. Aromatic hydrocarbon rings are preferred, and benzene rings are even more preferred. Furthermore, aromatic ring systems may have substituents.

[0088] From the viewpoint of improving resolution by suppressing the swelling of the photosensitive resin layer caused by the developer, it is preferable that the polymeric compound B1 has a bisphenol structure. Examples of bisphenol structures include bisphenol A (i.e., 2,2-bis(4-hydroxyphenyl)propane), bisphenol F (i.e., 2,2-bis(4-hydroxyphenyl)methane), and bisphenol B (i.e., 2,2-bis(4-hydroxyphenyl)butane). The bisphenol A structure is preferred.

[0089] As a polymerizable compound B1 having a bisphenol structure, examples include compounds having a bisphenol structure and two polymerizable groups (preferably (meth)acrylic acid) bonded to both ends of the bisphenol structure. Each polymerizable group can be directly bonded to the bisphenol structure. Each polymerizable group can also be bonded to the bisphenol structure via one or more alkoxy groups. The alkoxy groups added to both ends of the bisphenol structure are preferably ethoxy or propoxy, with ethoxy being more preferred. The number of alkoxy groups added to the bisphenol structure is not limited, but 4 to 16 in each molecule is preferred, and 6 to 14 is even more preferred.

[0090] Regarding polymeric compound B1 having a bisphenol structure, it is described in paragraphs 0072 to 0080 of Japanese Patent Application Publication No. 2016-224162. The contents of the above publication are incorporated herein by reference.

[0091] It is preferred that the polymerizable compound B1 is a difunctional vinyl unsaturated compound having a bisphenol A structure, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is even more preferred.

[0092] Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentethoxy)phenyl)propane (BPE-500, SHIN-NAKAMURA CHEMICAL CO, LTD.), 2,2-bis(4-(methacryloxydodecethoxytetrapropoxy)phenyl)propane (FA-3200MY, Hitachi Chemical Co., Ltd.), and 2,2-bis(4-(methacryloxydecadecaethoxy)phenyl)propane (BPE-1300, SHIN-NAKAMURA CHEMICAL CO, LTD.). LTD.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, SHIN-NAKAMURA CHEMICAL CO, LTD.) and ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, SHIN-NAKAMURA CHEMICAL CO, LTD.).

[0093] As a polymeric compound B1, a compound represented by the following general formula (I) can also be cited.

[0094] [Chemical Formula 1]

[0095] In general formula (I), R1 and R2 independently represent hydrogen atoms or methyl groups, A represents C2H4, B represents C3H6, n1 and n3 are independently integers from 1 to 39, n1+n3 are integers from 2 to 40, n2 and n4 are independently integers from 0 to 29, n2+n4 are integers from 0 to 30, and the arrangement of repeating units of -(AO)- and -(BO)- can be random or block. In the case of block, either -(AO)- or -(BO)- can be a biphenyl side. For n2+n4, integers from 0 to 10 are preferred, integers from 0 to 4 are more preferred, integers from 0 to 2 are further preferred, and 0 is especially preferred. For n1+n2+n3+n4, integers from 2 to 20 are preferred, integers from 2 to 16 are more preferred, and integers from 4 to 12 are especially preferred.

[0096] The photosensitive resin layer system may contain one or more polymeric compounds B1.

[0097] From the viewpoint of superior resolution, it is preferable that the content of polymeric compound B1 in the photosensitive resin layer is 10% by mass or more, and more preferably 20% by mass or more, relative to the total mass of the photosensitive resin layer. There is no upper limit to the content of polymeric compound B1. From the viewpoint of transferability and resistance to edge melting, it is preferable that the content of polymeric compound B1 in the photosensitive resin layer is 70% by mass or less, and more preferably 60% by mass or less, relative to the total mass of the photosensitive resin layer.

[0098] The photosensitive resin layer system may contain polymeric compound B1 and polymeric compound B other than polymeric compound B1. Examples of polymeric compound B other than polymeric compound B1 include monofunctional vinyl unsaturated compounds (i.e., compounds having one vinyl unsaturated group in one molecule), difunctional vinyl unsaturated compounds without an aromatic ring (i.e., compounds without an aromatic ring and having two vinyl unsaturated groups in one molecule), and trifunctional or more vinyl unsaturated compounds (i.e., compounds having three or more vinyl unsaturated groups in one molecule).

[0099] Examples of monofunctional vinyl unsaturated compounds include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate and phenoxyethyl (meth)acrylate.

[0100] Examples of difunctional vinyl unsaturated compounds that do not have an aromatic ring include alkyl diol di(meth)acrylate, polyalkyl diol di(meth)acrylate, urethane di(meth)acrylate and trimethylolpropane diacrylate.

[0101] Examples of tricyclodecanediol dimethacrylates include tricyclodecanediol dimethacrylate (A-DCP, SHIN-NAKAMURA CHEMICAL CO, LTD.), tricyclodecanediol dimethacrylate (DCP, SHIN-NAKAMURA CHEMICAL CO, LTD.), 1,9-nonanediol dimethacrylate (A-NOD-N, SHIN-NAKAMURA CHEMICAL CO, LTD.), 1,6-hexanediol dimethacrylate (A-HD-N, SHIN-NAKAMURA CHEMICAL CO, LTD.), ethylene glycol dimethacrylate, 1,10-decanediol dimethacrylate, and neopentyl glycol dimethacrylate.

[0102] As polyalkyl diol di(meth)acrylate, examples include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate and polypropylene glycol di(meth)acrylate.

[0103] Examples of urethane dimethacrylates include propylene oxide-modified urethane dimethacrylates and ethylene oxide and propylene oxide-modified urethane dimethacrylates. Commercially available examples include 8UX-015A (TAISEI FINE CHEMICAL CO,.LTD.), UA-32P (SHIN-NAKAMURA CHEMICAL CO, LTD.), and UA-1100H (SHIN-NAKAMURA CHEMICAL CO, LTD.).

[0104] Examples of trifunctional or higher ethylene unsaturated compounds include, for example, dinepentetreol (tri / tetra / penta / hexa)methacrylate, neopentetreol (tri / tetra)methacrylate, trimethylolpropane tri(methacrylate), ditrimethylolpropane tetra(methacrylate), trimethylolethane tri(methacrylate), isocyanurate tri(methacrylate), glycerol tri(methacrylate), and epoxide-modified forms of the like. In this disclosure, "(tri / tetra / penta / hexa)methacrylate" includes the concepts of tri(methacrylate), tetra(methacrylate), penta(methacrylate), and hexa(methacrylate).

[0105] Examples of epoxide-modified compounds that are trifunctional or higher-functionalized ethylene unsaturated compounds include caprolactone-modified (meth)acrylate compounds (e.g., KAYARAD DPCA-20 manufactured by Nippon Kayaku Co., Ltd. and A-9300-1CL manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD.), epoxide-modified (meth)acrylate compounds (e.g., KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD., A-9300 manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD., and EBECRYL 135 manufactured by DAICEL-ALLNEX LTD.), and ethoxylated glycerol triacrylates (e.g., SHIN-NAKAMURA CHEMICAL CO, LTD.). A-GLY-9E (manufactured by LTD.), ARONIX (registered trademark) TO-2349 (TOAGOSEI CO., LTD.), ARONIX M-520 (TOAGOSEI CO., LTD.) and ARONIX M-510 (TOAGOSEI CO., LTD.).

[0106] Other than polymerizable compound B1, polymerizable compound B may also include polymerizable compounds with acid groups described in paragraphs 0025 to 0030 of Japanese Patent Application Publication No. 2004-239942.

[0107] In one embodiment, it is preferable that the photosensitive resin layer system contains a polymeric compound B1 and a trifunctional or higher vinyl unsaturated compound, and it is even more preferable that it contains a polymeric compound B1 and two or more trifunctional or higher vinyl unsaturated compounds. In the above embodiment, the mass ratio of polymeric compound B1 to trifunctional or higher vinyl unsaturated compounds ([total mass of polymeric compound B1]:[total mass of trifunctional or higher vinyl unsaturated compounds]) is preferably 1:1 to 5:1, more preferably 1.2:1 to 4:1, and particularly preferably 1.5:1 to 3:1.

[0108] The molecular weight of polymeric compound B (in the case where polymeric compound B has a molecular weight distribution, it refers to the weight average molecular weight (Mw)) is preferably 200 to 3,000, more preferably 280 to 2,200, and particularly preferably 300 to 2,200.

[0109] The photosensitive resin layer system may contain one or more polymeric compounds B.

[0110] The proportion of polymeric compound B in the photosensitive resin layer is preferably 10% to 70% by mass relative to the total mass of the photosensitive resin layer, more preferably 20% to 60% by mass, and especially preferably 20% to 50% by mass.

[0111] (Any component) The photosensitive resin system may contain components other than those described above (hereinafter, sometimes referred to as "any component"). Examples of arbitrary components include photopolymerization initiators, pigments, surfactants, and additives other than those described above.

[0112] -Photopolymerization Initiator- It is preferable that the photosensitive resin layer system contains a photopolymerization initiator. The photopolymerization initiator is a compound that receives activating light (e.g., ultraviolet light, visible light, and X-rays) and initiates the polymerization of a polymerizable compound (e.g., polymerizable compound B).

[0113] There are no limitations on the photopolymerization initiator used; any known photopolymerization initiator may be used. Examples of photopolymerization initiators include photoradical polymerization initiators and photocationic polymerization initiators, with photoradical polymerization initiators being preferred.

[0114] Examples of photoradical polymerization initiators include photopolymerization initiators having an oxime ester structure, photopolymerization initiators having an α-aminoalkylphenyl ketone structure, photopolymerization initiators having an α-hydroxyalkylphenyl ketone structure, photopolymerization initiators having a nitrophosphine oxide structure, and photopolymerization initiators having an N-phenylglycine structure.

[0115] From the viewpoints of photosensitivity, visual recognizability of the exposed portion, visual recognizability of the unexposed portion, and resolution, it is preferable that the photosensitive resin layer system contains at least one selected from the group consisting of 2,4,5-triarylimidazolium dimers and derivatives of 2,4,5-triarylimidazolium dimers as a photoradical polymerization initiator. Furthermore, the two 2,4,5-triarylimidazolium structures in the 2,4,5-triarylimidazolium dimer and its derivatives may be identical or different.

[0116] As derivatives of 2,4,5-triarylimidazolium dimers, examples include 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazolium dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazolium dimer and 2-(p-methoxyphenyl)-4,5-diphenylimidazolium dimer.

[0117] As photoradical polymerization initiators, examples include the polymerization initiators described in sections 0031 to 0042 of Japanese Patent Application Publication No. 2011-095716 and sections 0064 to 0081 of Japanese Patent Application Publication No. 2015-014783.

[0118] Examples of photoradical polymerization initiators include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoyl methyl ether, anisyl (p,p'-dimethoxybenzyl) and benzophenone.

[0119] Commercially available products that serve as photoradical polymerization initiators include, for example, TAZ-110 (Midori Kagaku Co., Ltd.), TAZ-111 (Midori Kagaku Co., Ltd.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(o-benzoxime) (trade name: IRGACURE (registered trademark) OXE-01, BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethylenedione-1-(o-acetyloxime) (trade name: IRGACURE OXE-02, BASF), IRGACURE OXE-03 (BASF), IRGACURE OXE-04 (BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-amorpholinyl)phenyl]-1-butanone (trade names: Omnirad 379EG, IGM Resins BV), 2-methyl-1-(4-methylthiophenyl)-2-amorpholinylprop-1-one (trade names: Omnirad 907, IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionic)benzyl]phenyl}-2-methylprop-1-one (trade names: Omnirad 127, IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-amorpholinylphenyl)butanone-1 (trade names: Omnirad 369, IGM Resins) (BV Company), 2-hydroxy-2-methyl-1-phenylprop-1-one (trade names: Omnirad 1173, IGM Resins BV Company), 1-hydroxycyclohexylphenyl ketone (trade names: Omnirad 184, IGM Resins BV Company), 2,2-dimethoxy-1,2-diphenylethyl-1-one (trade names: Omnirad 651, IGM Resins BV Company), 2,4,6-trimethylbenzoxy-diphenylphosphine oxide (trade names: Omnirad TPO H, IGM Resins BV Company), bis(2,4,6-trimethylbenzoxy)phenylphosphine oxide (trade names: Omnirad 819, IGM Resins BV Company), and oxime ester-based photopolymerization initiators (trade names: Lunar 6, DKSH Management Ltd.).

[0120] A photocationic polymerization initiator (i.e., a photoacid generator) is a compound that generates acid upon receiving activation light. As a photocationic polymerization initiator, a compound that generates acid upon sensing activation light with a wavelength of 300 nm or higher, preferably 300 nm to 450 nm, is preferred. However, the chemical structure of the photocationic polymerization initiator is not limited. Furthermore, regarding photocationic polymerization initiators that do not directly sense activation light with a wavelength of 300 nm or higher, as long as they are compounds that generate acid upon sensing activation light with a wavelength of 300 nm or higher by simultaneously using a sensitizer, they can also be used in combination with a sensitizer for better results.

[0121] It is preferable that the photocationic polymerization initiator produces an acid with a pKa of 4 or less, more preferably a photocationic polymerization initiator producing an acid with a pKa of 3 or less, and especially preferably a photocationic polymerization initiator producing an acid with a pKa of 2 or less. The lower limit of pKa is not limited. It is preferable that the pKa of the acid produced by the photocationic polymerization initiator is, for example, -10.0 or more.

[0122] As photocationic polymerization initiators, examples include ionic photocationic polymerization initiators and nonionic photocationic polymerization initiators.

[0123] Examples of ionic photocationic polymerization initiators include onium salt compounds (e.g., diaryliodositol compounds and triarylstromium salt compounds) and quaternary ammonium salt compounds.

[0124] As an ionic photocationic polymerization initiator, the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of Japanese Patent Application Publication No. 2014-085643 can also be cited.

[0125] Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triazine compounds, diazomethane compounds, aceimide sulfonate compounds, and oxime sulfonate compounds. Examples of trichloromethyl-s-triazine compounds, diazomethane compounds, and aceimide sulfonate compounds include compounds described in paragraphs 0083 to 0088 of Japanese Patent Application Publication No. 2011-221494. Examples of oxime sulfonate compounds include compounds described in paragraphs 0084 to 0088 of International Patent Publication No. 2018 / 179640.

[0126] It is preferable that the photosensitive resin layer system contains a photoradical polymerization initiator, and it is even more preferable that it contains at least one of the group consisting of 2,4,5-triarylimidazolium dimers and derivatives of 2,4,5-triarylimidazolium dimers.

[0127] The photosensitive resin system may contain one or more photopolymerization initiators.

[0128] The proportion of the photopolymerization initiator in the photosensitive resin layer is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and especially preferably 1.0% by mass or more, relative to the total mass of the photosensitive resin layer. There is no upper limit to the proportion of the photopolymerization initiator. The proportion of the photopolymerization initiator is preferably 10% by mass or less, and more preferably 5% by mass or less, relative to the total mass of the photosensitive resin layer.

[0129] - Pigment- From the viewpoints of visual recognition of the exposed area, visual recognition of the unexposed area, visual recognition of the pattern after development, and resolution, it is preferable for the photosensitive resin layer to contain a pigment (hereinafter sometimes referred to as "pigment N") with a maximum absorption wavelength of 450 nm or higher in the wavelength range of 400 nm to 780 nm during color development, and whose maximum absorption wavelength changes due to acids, alkalis, or free radicals. The detailed mechanism is not yet clear, but by containing pigment N in the photosensitive resin layer, the adhesion to layers adjacent to the photosensitive resin layer (e.g., dummy support and intermediate layer) can be improved, resulting in better resolution.

[0130] In this disclosure, the term “the maximum absorption wavelength changes due to acid, base or free radical” used for pigments can mean any of the following states: a pigment in a chromogenic state that is decolorized due to acid, base or free radical; a pigment in a decolorized state that is chromogenic due to acid, base or free radical; and a pigment in a chromogenic state that is chromogenic in a state that changes to another hue.

[0131] Specifically, the pigment N-based can be a compound that changes from a decolorized state to a colored state upon exposure, or it can be a compound that changes from a colored state to a decolorized state upon exposure. In the above-mentioned states, the pigment N-based can be a pigment whose colored or decolorized state changes under the action of acids, bases, or free radicals generated by exposure. Furthermore, the pigment N-based can also be a pigment whose colored or decolorized state changes due to the following: the state within the photosensitive resin layer (e.g., pH) changes due to acids, bases, or free radicals generated by exposure. On the other hand, the pigment N-based can also be a pigment whose colored or decolorized state changes directly upon stimulation by acids, bases, or free radicals without exposure.

[0132] From the viewpoints of visual recognition of the exposed part, visual recognition of the unexposed part, and resolution, pigments whose maximum absorption wavelength of N-type pigments changes due to acid or free radicals are preferred, and pigments whose maximum absorption wavelength changes due to free radicals are even better.

[0133] From the viewpoints of visual recognition of the exposed part, visual recognition of the unexposed part, and resolution, it is preferable that the photosensitive resin layer contains a pigment whose maximum absorption wavelength changes due to free radicals and a photoradical polymerization initiator as pigment N.

[0134] From the perspective of visual recognition of the exposed part and visual recognition of the unexposed part, pigment N is better as it is a pigment that is colored by acid, alkali or free radical.

[0135] As an example of the color development mechanism of pigment N, one can cite the state in which free radical reactive pigments, acid reactive pigments or base reactive pigments (e.g. colorless pigments) develop color by free radicals, acids or bases, which are generated by exposing a photosensitive resin layer containing a photoradical polymerization initiator, a photocationic polymerization initiator (i.e., a photoacid generator) or a photobase generator.

[0136] In pigment N, from the viewpoint of visual recognition of the exposed part and visual recognition of the unexposed part, the wavelength range during color development, that is, the maximum absorption wavelength in the range of 400nm to 780nm, is preferably 550nm or higher, 550nm to 700nm is even better, and 550nm to 650nm is particularly good.

[0137] Furthermore, pigment N may have one or more maximum absorption wavelengths in the wavelength range of color development, i.e., 400 nm to 780 nm. When pigment N has two or more maximum absorption wavelengths in the wavelength range of color development, i.e., 400 nm to 780 nm, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or higher.

[0138] The maximum absorption wavelength of pigment N was determined as follows: In an atmospheric environment, the transmission spectrum of a solution containing pigment N (liquid temperature 25°C) was measured in the range of 400 nm to 780 nm using a spectrophotometer (UV3100, Shimadzu Corporation). Then, the wavelength at which the light intensity was minimized (maximum absorption wavelength) was detected.

[0139] Examples of pigments that develop or decolorize upon exposure include colorless compounds. Examples of pigments that decolorize upon exposure include colorless compounds, diarylmethane pigments, acetylene pigments, sigmazone pigments, iminonaphthoquinone pigments, azomethine pigments, and anthraquinone pigments. From the viewpoint of visual recognizability of both the exposed and unexposed areas, N-based colorless compounds are preferred.

[0140] Examples of colorless compounds include colorless compounds having a triarylmethane skeleton (triarylmethane pigments), colorless compounds having a spiropyran skeleton (spiropyran pigments), colorless compounds having a fluorane skeleton (fluorane pigments), colorless compounds having a diarylmethane skeleton (diarylmethane pigments), colorless compounds having a rhodamine lactone skeleton (rhodamine lactone pigments), colorless compounds having an indolephthalide skeleton (indolephthalide pigments), and colorless compounds having a colorless auramine skeleton (colorless auramine pigments). Colorless compounds that are triarylmethane pigments or fluorane pigments are preferred, and colorless compounds having a triphenylmethane skeleton (triphenylmethane pigments) or fluorane pigments are even more preferred.

[0141] From the viewpoint of visual recognizability of both the exposed and unexposed portions, it is preferable that the colorless compound has a lactone ring, a sulfinolone ring, or a sulfonolone ring. By reacting the lactone ring, sulfinolone ring, or sulfonolone ring contained in the colorless compound with a free radical generated by a photoradical polymerization initiator or an acid generated by a photocationic polymerization initiator, the colorless compound can be decolorized by changing to a closed-ring state or made color-developing by changing to an open-ring state. It is preferable that the colorless compound has a lactone ring, a sulfinolone ring, or a sulfonolone ring and that the lactone ring, sulfinolone ring, or sulfonolone ring develops color by ring-opening with a free radical or acid, and it is even more preferable that the compound has a lactone ring and that the lactone ring develops color by ring-opening with a free radical or acid.

[0142] Specific examples of colorless compounds include p,p',p”-hexamethyltriaminetriphenylmethane (colorless crystal violet), Pergascript Blue SRB (Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoxide colorless methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-p-tolylamino)fluorane, 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, 3-(N-cyclohexyl-N-methylamino)-6- Methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorane, 3-(N,N-diethylamino)-6-methoxy-7-aminofluorane, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluorane, 3-(N,N-diethylamino)-7-chlorofluorane, 3-(N,N- (N,N-diethylamino)-7-benzylaminofluorane, 3-(N,N-diethylamino)-7,8-benzofluorane, 3-(N,N-dibutylamino)-6-methyl-7-anilinefluorane, 3-(N,N-dibutylamino)-6-methyl-7-anilinefluorane, 3-hexahydropyridyl-6-methyl-7-anilinefluorane, 3-pyrrolidyl-6-methyl-7-anilinefluorane, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalolide, 3,3-bis(1-n-butyl) 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophenyl phthaloyl ...

[0143] As a pigment N, dyes can also be cited as an example. Specific examples of dyes include Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuchsin, Methyl Violet 2B, Quinaldinine Red, Rose Red, Meta-amine Yellow, Thymol Blue, Succinate Blue, Methyl Orange, p-Methyl Red, Congo Red, Benzoinviolet 4B, α-Naphthalene Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Para-Fuchsin, Victoria Brilliant Blue-Naphthalene Sulfonate, Victoria Brilliant Blue BOH (Hodogaya Chemical Co., Ltd.), Oil Blue #603 (ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Pink #312 (ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Red 5B (ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Scarlet #308 (ORIENT CHEMICAL INDUSTRIES CO., LTD.), and Oil Red OG (ORIENT CHEMICAL INDUSTRIES CO., LTD.). CO., LTD.), Oil Red RR (ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Green #502 (ORIENT CHEMICAL INDUSTRIES CO., LTD.), Spiron Red BEH Special (Hodogaya Chemical Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0144] From the perspective of visual recognition of the exposed part, visual recognition of the unexposed part, visual recognition of the pattern after development and resolution, pigments whose maximum absorption wavelength of N-type pigments changes due to free radicals are better, and pigments that develop color by free radicals are even better.

[0145] The preferred pigments are colorless crystal violet, crystal violet lactone, bright green or Victoria Blue-naphthalene sulfonate.

[0146] The photosensitive resin layer system may contain one or more pigments N.

[0147] From the viewpoints of visual recognizability of the exposed part, visual recognizability of the unexposed part, visual recognizability and resolution of the pattern after development, the content ratio of pigment N relative to the total mass of the photosensitive resin layer is preferably 0.1% by mass or more, 0.1% to 10% by mass is more preferably, 0.1% to 5% by mass is further preferably, and 0.1% to 1% by mass is particularly preferably.

[0148] The content ratio of pigment N refers to the proportion of pigment that makes all pigment N contained in the photosensitive resin layer reach a colored state. Hereinafter, a quantitative method for determining the content ratio of pigment N will be explained using a pigment that develops color via free radicals as an example. Two solutions were prepared by dissolving pigment (0.001 g) and pigment (0.01 g) separately in methyl ethyl ketone (100 mL). IRGACURE OXE-01 (BASF) was added to each of the resulting solutions as a photoradical polymerization initiator, and free radicals were generated by irradiating with 365 nm light, causing all pigments to reach a colored state. Next, in an atmospheric environment, the absorbance of each solution at a liquid temperature of 25°C was measured using a spectrophotometer (UV3100, Shimadzu Corporation), and a calibration curve was created. Next, instead of pigment, the photosensitive resin layer (3 g) was dissolved in methyl ethyl ketone, and the absorbance of the solution that developed color for all pigments was measured using the same method as described above. The content of pigment in the photosensitive resin layer is calculated based on the absorbance of the obtained solution containing the photosensitive resin layer and the calibration curve.

[0149] -Surfactant- From the viewpoint of thickness uniformity, it is preferable for photosensitive resin layers to contain a surfactant. Examples of surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants, with nonionic surfactants being preferred.

[0150] Examples of nonionic surfactants include polyoxyethylene higher alkyl ether compounds, polyoxyethylene higher alkyl phenyl ether compounds, higher fatty acid diesters of polyoxyethylene glycol, silicone-based nonionic surfactants, and fluorinated nonionic surfactants.

[0151] From the perspective of superior resolution, it is preferable for photosensitive resin layers to contain fluorinated nonionic surfactants. This is because the presence of fluorinated nonionic surfactants in the photosensitive resin layer can inhibit the penetration of etchant into the photosensitive resin layer, thereby reducing lateral etching. Commercially available fluorinated nonionic surfactants include, for example, MEGAFACE (registered trademark) F-551 (DIC Corporation), MEGAFACE F-552 (DIC Corporation), and MEGAFACE F-554 (DIC Corporation).

[0152] Furthermore, commercially available fluorinated surfactants include, for example, MEGAFACE. F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (all manufactured by DIC Corporation), Fluorad FC430, FC431, FC171 (all manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by ASAHI GLASS CO.,LTD.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA Solutions Inc.), FTERGENT 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (all models manufactured by NEOS COMPANY LIMITED), etc.

[0153] Furthermore, acrylic compounds that have a molecular structure containing functional groups with fluorine atoms, and whose functional groups containing fluorine atoms are cleaved upon heating, causing the fluorine atoms to volatilize, are also preferred as fluorine-based surfactants. Examples of such fluorine-based surfactants include the MEGAFACE DS series manufactured by DIC Corporation (Chemical Industry Daily (February 22, 2016), Nikkei Industrial News (February 23, 2016)), such as MEGAFACE DS-21.

[0154] Furthermore, polymers of vinyl ether compounds having fluorinated atoms with fluorinated alkyl or fluorinated alkyl ether groups and hydrophilic vinyl ether compounds are also preferred as fluorinated surfactants.

[0155] Furthermore, block polymers can also be used as fluorinated surfactants.

[0156] Furthermore, as a fluorinated surfactant, a fluorinated polymeric compound containing a (meth)acrylate compound having a fluorine atom and a (meth)acrylate compound having two or more (preferably five or more) alkoxy groups (preferably ethoxy or propoxy groups) can also be preferred.

[0157] Furthermore, as a fluorinated surfactant, it can also be used on fluorinated polymers with ethylene-containing unsaturated bonds in the side chains. Examples include MEGAFACE RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0158] From the perspective of improving environmental adaptability, surfactants derived from perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), which are straight-chain perfluoroalkyl compounds with 7 or more carbon atoms, are preferred as fluorinated surfactants.

[0159] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylated and propoxylated derivatives (e.g., glycerol propoxylated, glycerol ethoxylated, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oil ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (all manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (all manufactured by BASF), and Solsperse 20000 (all manufactured by Lubrizol Japan). (Manufactured by FUJIFILM Wako Pure Chemical Corporation), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, D-6315 (manufactured by TAKEMOTO OIL & FAT Co., Ltd.), OLFINE E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd.), etc.

[0160] As silicone-based surfactants, examples include linear polymers composed of siloxane bonds and modified siloxane polymers with organic groups introduced into the side chains or ends.

[0161] Specific examples of surfactants include DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (the above are from Dow Corning Toray Co., Ltd.). (manufactured by Shin-Etsu Chemical Co., Ltd.) and X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (manufactured by Shin-Etsu Chemical Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc.), BYK307, BYK323, BYK330 (manufactured by BYK Chemie Co., Ltd.), etc.

[0162] Examples of surfactants include those described in paragraphs 0120 to 0125 of International Publication No. 2018 / 179640, those described in paragraph 0017 of Japanese Patent No. 4502784, and those described in paragraphs 0060 to 0071 of Japanese Patent Application Publication No. 2009-237362.

[0163] The photosensitive resin layer system may contain one or more surfactants.

[0164] The content of surfactant is preferably 0.001% to 10% by mass relative to the total mass of the photosensitive resin layer, and even more preferably 0.01% to 3% by mass.

[0165] -Additives- In addition to the above-mentioned components, the photosensitive resin system may also contain known additives as needed. Examples of additives include free radical polymerization inhibitors, sensitizers, plasticizers, heterocyclic compounds, benzotriazole compounds, carboxybenzotriazole compounds, resins other than polymer A, and solvents. The photosensitive resin system may contain one or more additives.

[0166] The photosensitive resin layer system may contain a free radical polymerization inhibitor. Examples of free radical polymerization inhibitors include the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784. Phenylephrine, phenytoin, or 4-methoxyphenol are preferred free radical polymerization inhibitors. Examples of other free radical polymerization inhibitors include naphthylamine, cuprous chloride, aluminum nitrosophenylhydroxylamine, and diphenylnitrosamine. Using aluminum nitrosophenylhydroxylamine as a free radical polymerization inhibitor is preferred to avoid impairing the sensitivity of the photosensitive resin layer.

[0167] The photosensitive resin layer system may contain a benzotriazole compound. Examples of benzotriazole compounds include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.

[0168] The photosensitive resin layer system may contain a carboxybenzotriazole compound. Examples of carboxybenzotriazole compounds include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylene carboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylene carboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylcarboxybenzotriazole. Commercially available carboxybenzotriazole compounds include, for example, CBT-1 (JOHOKU CHEMICAL CO.,LTD).

[0169] The total content ratio of the free radical polymerization inhibitor, benzotriazole compound, and carboxybenzotriazole compound is preferably 0.01% to 3% by mass relative to the total mass of the photosensitive resin layer, and more preferably 0.05% to 1% by mass. From the viewpoint of imparting storage stability to the photosensitive resin layer, it is preferable to set the total content ratio of the above components to 0.01% by mass or more. On the other hand, from the viewpoint of maintaining sensitivity and inhibiting dye decolorization, it is preferable to set the total content ratio of the above components to 3% by mass or less.

[0170] The photosensitive resin layer system may contain a sensitizer. There are no limitations on the type of sensitizer; known sensitizers may be used. Furthermore, dyes and pigments may also be used as sensitizers. Examples of sensitizers include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthonesone compounds, 9-oxothiobenzoxazine compounds, acridinone compounds, succinazole compounds, benzo[a]succinazole compounds, thiazole compounds, benzo[a]thiazole compounds, triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalenedimethylimine compounds, triarylamine compounds, and aminoacridine compounds.

[0171] The photosensitive resin layer system may contain one or more sensitizers.

[0172] When the photosensitive resin layer contains a sensitizer, the proportion of the sensitizer can be appropriately selected according to the purpose. However, from the viewpoint of improving the sensitivity to the light source and improving the curing speed by balancing the polymerization rate and chain transfer, it is better to have 0.01% to 5% by mass relative to the total mass of the photosensitive resin layer, and even better to have 0.05% to 1% by mass.

[0173] The photosensitive resin layer system may contain at least one selected from the group consisting of plasticizers and heterocyclic compounds. Examples of plasticizers and heterocyclic compounds include those described in paragraphs 0097 to 0103 and 0111 to 0118 of International Publication No. 2018 / 179640.

[0174] The photosensitive resin system may contain resins other than polymer A. Examples of resins other than polymer A include acrylic resins, styrene-acrylic acid copolymers (limited to copolymers containing styrene at a content of 40% by mass or less), polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0175] The photosensitive resin layer system may contain a solvent. In the case where a photosensitive resin layer is formed from a photosensitive resin composition containing a solvent, the solvent may sometimes remain in the photosensitive resin layer. The solvent will be discussed later.

[0176] The photosensitive resin layer system may contain, for example, at least one additive selected from the group consisting of metal oxide particles, antioxidants, dispersants, acid proliferation agents, development promoters, conductive fibers, thermal free radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, organic precipitation inhibitors, and inorganic precipitation inhibitors. Regarding additives, for example, paragraphs 0165 to 0184 of Japanese Patent Application Publication No. 2014-085643 are described. The contents of the aforementioned publication are incorporated herein by reference.

[0177] Hereinafter, preferred combinations of the above-mentioned components will be described. In one embodiment, the photosensitive resin layer system preferably contains polymer A, polymeric compound B, and a photopolymerization initiator. The photosensitive resin layer system preferably contains 10% to 90% by mass of polymer A, 5% to 70% by mass of polymeric compound B, and 0.01% to 20% by mass of photopolymerization initiator relative to the total mass of the photosensitive resin layer. In one embodiment, the photosensitive resin layer system preferably contains an alkali-soluble polymer, a compound containing ethylene unsaturated bonds, and a photopolymerization initiator. The alkali-soluble polymer is one of the above-mentioned polymer A. The compound containing ethylene unsaturated bonds is one of the above-mentioned polymeric compound B.

[0178] (Thickness) The average thickness of the photosensitive resin layer is typically 0.1 μm to 300 μm. An average thickness of 0.1 μm or more is preferred, 0.2 μm or more is even better, 0.5 μm is further preferred, and 1 μm or more is particularly preferred. An average thickness of 100 μm or less is preferred, 50 μm or less is even better, 15 μm or less is further preferred, and 8 μm or less is particularly preferred. By ensuring the average thickness of the photosensitive resin layer is within the above range, the developability of the photosensitive resin layer can be improved, and the resolution can be increased.

[0179] In one embodiment, the average thickness of the photosensitive resin layer is preferably 0.1 μm to 15 μm, more preferably 0.5 μm to 5 μm, further preferably 0.5 μm to 4 μm, and especially preferably 0.5 μm to 3 μm.

[0180] (Transmittance) From the viewpoint of superior adhesion, a transmittance of 365nm light of 10% or higher is preferred in the photosensitive resin layer, 30% or higher is even better, and 50% or higher is exceptionally good. There is no upper limit to the transmittance. A transmittance of 365nm light of 99.9% or lower in the photosensitive resin layer is also preferred.

[0181] (Forming Method) The method for forming the photosensitive resin layer is not limited as long as it is a method capable of forming a layer containing the above-mentioned components. For example, a method for forming the photosensitive resin layer can be described as follows: coating the photosensitive resin composition onto the surface of the dummy support, and then drying the coating of the photosensitive resin composition.

[0182] Examples of photosensitive resin compositions include those containing polymer A, polymeric compound B, any other components, and a solvent. It is preferable that the photosensitive resin composition contains a solvent in order to adjust the viscosity of the photosensitive resin composition and facilitate the formation of the photosensitive resin layer.

[0183] As a solvent, there are no limitations as long as it is a solvent capable of dissolving or dispersing polymer A, polymeric compound B, and any component; known solvents may be used. Examples of solvents include alkyl glycol ether solvents, alkyl glycol ether acetate solvents, alcohol solvents (e.g., methanol and ethanol), ketone solvents (e.g., acetone and methyl ethyl ketone), aromatic hydrocarbon solvents (e.g., toluene), aprotic polar solvents (e.g., N,N-dimethylformamide), cyclic ether solvents (e.g., tetrahydrofuran), ester solvents, amide solvents, and lactone solvents.

[0184] It is preferable that the photosensitive resin composition system contains at least one selected from the group consisting of alkyl glycol ether solvents and alkyl glycol ether acetate solvents. It is even more preferable that the photosensitive resin composition system contains at least one selected from the group consisting of alkyl glycol ether solvents and alkyl glycol ether acetate solvents, and at least one selected from the group consisting of ketone solvents and cyclic ether solvents. It is particularly preferable that the photosensitive resin composition system contains at least one selected from the group consisting of alkyl glycol ether solvents and alkyl glycol ether acetate solvents, a ketone solvent, and a cyclic ether solvent.

[0185] Examples of alkyl glycol ether solvents include, for example, ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether and dipropylene glycol dialkyl ether.

[0186] Examples of solvents for alkyl glycol ether acetates include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate and dipropylene glycol monoalkyl ether acetate.

[0187] Solvents described in paragraphs 0092 to 0094 of International Publication No. 2018 / 179640 and paragraph 0014 of Japanese Patent Application Publication No. 2018-177889 may also be used as solvents. These contents are incorporated herein by reference.

[0188] The photosensitive resin composition system may contain one or more solvents alone.

[0189] The solvent content in the photosensitive resin composition is preferably 50 to 1,900 parts by weight relative to 100 parts by weight of all solid components in the photosensitive resin composition, and more preferably 100 to 900 parts by weight.

[0190] The method for preparing the photosensitive resin composition is not limited. Examples of methods for preparing the photosensitive resin composition include: pre-preparing solutions in which each component is dissolved in a solvent, mixing the resulting solutions in a predetermined ratio, and thereby preparing the photosensitive resin composition. It is preferable to filter the photosensitive resin composition using a filter with a pore size of 0.2 μm to 30 μm before forming the photosensitive resin layer.

[0191] There are no limitations on the coating method for the photosensitive resin composition, and known methods can be used. Examples of coating methods include slit coating, spin coating, curtain coating, and inkjet coating.

[0192] Furthermore, the photosensitive resin layer system can also be formed by coating the photosensitive resin composition onto the cover film described later and drying it.

[0193] (Impurities, etc.) The photosensitive resin layer system may contain a predetermined amount of impurities. Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Among the above, halide ions, sodium ions, and potassium ions are easily mixed in as impurities, so the following contents are preferred.

[0194] Based on mass, it is preferable that the impurity content in the photosensitive resin layer is below 80 ppm, more preferably below 10 ppm, and further preferably below 2 ppm. Based on mass, the impurity content in the photosensitive resin layer can be set to above 1 ppb or above 0.1 ppm.

[0195] As a method for limiting impurities within the above-mentioned range, examples include selecting raw materials with lower impurity content as raw materials for the photosensitive resin layer, preventing impurities from being introduced during the formation of the photosensitive resin layer, and cleaning the manufacturing equipment to remove impurities. By such methods, the amount of impurities can be limited to the above-mentioned range.

[0196] Impurities can be quantified by known methods, such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, or ion chromatography.

[0197] It is preferable that the content of benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive resin layer is low. As for the content of the above compounds in the photosensitive resin layer, it is preferable that it is 100 ppm or less by mass, more preferably 20 ppm or less, and further preferably 4 ppm or less by mass. The content of the above compounds in the photosensitive resin layer can be set to 10 ppb or more or 100 ppb or more by mass. The content of the above compounds can be suppressed using the same method as for the above-mentioned metal impurities. Furthermore, it can be quantified by a known determination method.

[0198] From the point of view of improving reliability and lamination, the water content in the photosensitive resin layer is preferably 0.01% to 1.0% by mass, and even more preferably 0.05% to 0.5% by mass.

[0199] [Other Layers] The photosensitive transfer material disclosed herein may have layers other than those described above (hereinafter referred to as "other layers"). Examples of other layers include a cover film, a thermoplastic resin layer, an intermediate layer, and a contrast-enhancing layer.

[0200] (Covering film) The photosensitive transfer material disclosed herein may have a covering film (also called a protective film). According to the covering film, the surface of the layer (e.g., a photosensitive resin layer) in contact with the covering film can be protected.

[0201] In one embodiment, the photosensitive transfer material preferably comprises a dummy support, a photosensitive resin layer, and a cover film in sequence. In the above-described photosensitive transfer material, the photosensitive resin layer can be directly or through any lamination layer onto the dummy support. In the above-described photosensitive transfer material, the cover film can be directly or through any lamination layer onto the photosensitive resin layer. Examples of any layer in the above-described photosensitive transfer material include, for example, the thermoplastic resin layer, intermediate layer, and contrast-enhancing layer described later. However, the layer system is not limited to those described above.

[0202] In one embodiment, it is preferable that the photosensitive transfer material has a cover film that contacts the side of the photosensitive resin layer opposite to the side where the dummy support is disposed.

[0203] Examples of cover films include resin films and paper. From the viewpoint of strength and flexibility, resin films are preferred as cover films.

[0204] Examples of resin films include polyethylene films, polypropylene films, polyethylene terephthalate films, cellulose triacetate films, polystyrene films, and polycarbonate films. Polyethylene films, polypropylene films, or polyethylene terephthalate films are preferred as resin films.

[0205] The thickness of the cover film is not limited. The average thickness of the cover film is preferably 5μm to 100μm, more preferably 10μm to 50μm, and especially preferably 10μm to 20μm.

[0206] From the viewpoint of superior resolution, it is preferable that the arithmetic mean roughness Ra of the surface of the cover film on the side where the photosensitive resin layer is disposed is 0.3 μm or less, more preferably 0.1 μm or less, and especially preferably 0.05 μm or less. By ensuring that the arithmetic mean roughness of the surface of the cover film on the side where the photosensitive resin layer is disposed is within the above range, the uniformity of the thickness of the photosensitive resin layer and the formed resin pattern can be improved. The lower limit of the arithmetic mean roughness Ra is not limited. It is preferable that the arithmetic mean roughness Ra of the surface of the cover film on the side where the photosensitive resin layer is disposed is 0.001 μm or more. The arithmetic mean roughness Ra of the surface of the cover film on the side where the photosensitive resin layer is disposed is measured by the method based on the arithmetic mean roughness Ra measurement method described in the "Pseudo-support" section above.

[0207] (Thermoplastic Resin Layer) The photosensitive transfer material disclosed herein may have a thermoplastic resin layer. In one embodiment, it is preferable that the photosensitive transfer material has a thermoplastic resin layer between the dummy support and the photosensitive resin layer. This is because, by having a thermoplastic resin layer between the dummy support and the photosensitive resin layer, the tracking of the substrate during the bonding process can be improved, thereby suppressing air bubbles from entering between the substrate and the photosensitive transfer material, and consequently improving the adhesion between the layers.

[0208] -Alkali-soluble resin- Thermoplastic resin layer system containing alkali-soluble resin is preferred as a thermoplastic resin.

[0209] Examples of alkali-soluble resins include acrylic resins, polystyrene resins, styrene-acrylic acid copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0210] From the viewpoint of developability and adhesion to layers adjacent to the thermoplastic resin layer, alkali-soluble acrylic resin is preferred. Here, "acrylic resin" means a resin having at least one of the group consisting of constituent units derived from (meth)acrylic acid, constituent units derived from (meth)acrylate, and constituent units derived from (meth)acrylamide.

[0211] In the acrylic resin, the ratio of the total content of constituent units derived from (meth)acrylic acid, constituent units derived from (meth)acrylate, and constituent units derived from (meth)acrylamide is preferably 50% by mass or more relative to the total mass of the acrylic resin. In the acrylic resin, the ratio of the total content of constituent units derived from (meth)acrylic acid and constituent units derived from (meth)acrylate is preferably 30% to 100% by mass relative to the total mass of the acrylic resin, and more preferably 50% to 100% by mass.

[0212] Furthermore, the alkali-soluble resin is preferably a polymer containing an acid group. Examples of acid groups include carboxyl, sulfonyl, phosphate, and phosphonic acid groups, with carboxyl being preferred.

[0213] From the viewpoint of developability, alkali-soluble resins with an acid value of 60 mg KOH / g or higher are preferred, and carboxyl-containing acrylic resins with an acid value of 60 mg KOH / g or higher are even better. There is no upper limit to the acid value. For alkali-soluble resins, an acid value of 200 mg KOH / g or lower is preferred, and 150 mg KOH / g or lower is even better.

[0214] There are no limitations on the type of acrylic resin containing carboxyl groups with an acid value of 60 mg KOH / g or higher, and it can be appropriately selected from known resins. Examples of acrylic resins containing carboxyl groups with an acid value of 60 mg KOH / g or higher include the acrylic resin containing carboxyl groups with an acid value of 60 mg KOH / g or higher described in paragraph 0025 of Japanese Patent Application Publication No. 2011-095716, the acrylic resin containing carboxyl groups with an acid value of 60 mg KOH / g or higher described in paragraphs 0033 to 0052 of Japanese Patent Application Publication No. 2010-237589, and the acrylic resin containing carboxyl groups with an acid value of 60 mg KOH / g or higher described in paragraphs 0053 to 0068 of Japanese Patent Application Publication No. 2016-224162.

[0215] The proportion of the carboxyl-containing acrylic resin containing the carboxyl-containing unit is preferably 5% to 50% by mass relative to the total mass of the carboxyl-containing acrylic resin, more preferably 10% to 40% by mass, and especially preferably 12% to 30% by mass.

[0216] From the viewpoint of developability and adhesion to layers adjacent to the thermoplastic resin layer, alkali-soluble resins are preferably acrylic resins with constituent units derived from (meth)acrylic acid.

[0217] Alkali-soluble resin systems may have reactive groups. Reactive groups may be, for example, addition-polymerizable groups. Examples of reactive groups include vinyl unsaturated groups, condensation polymerizable groups (e.g., hydroxyl and carboxyl groups), and addition polymerizable reactive groups (e.g., epoxy and (block) isocyanate groups).

[0218] The weight average molecular weight (Mw) of the alkali-soluble resin is preferably above 1,000, even better is 10,000 to 100,000, and particularly good is 20,000 to 50,000.

[0219] Thermoplastic resin layer system may contain one or more alkali-soluble resins alone.

[0220] From the viewpoint of developability and adhesion to layers adjacent to the thermoplastic resin layer, the content of alkali-soluble resin is preferably 10% to 99% by mass relative to the total mass of the thermoplastic resin layer, more preferably 20% to 90% by mass, further preferably 40% to 80% by mass, and especially preferably 50% to 70% by mass.

[0221] - Pigment - The thermoplastic resin layer system preferably contains a pigment (hereinafter, sometimes referred to as "pigment B") whose maximum absorption wavelength in the wavelength range of color development, i.e., 400 nm to 780 nm, is 450 nm or higher, and whose maximum absorption wavelength changes due to acid, alkali, or free radicals. Except as described below, the preferred state of pigment B is the same as the preferred state of pigment N described above.

[0222] From the perspective of visual recognition of the exposed part, visual recognition of the unexposed part and resolution, pigments of pigment B whose maximum absorption wavelength changes due to acid or free radicals are better, and pigments whose maximum absorption wavelength changes due to acid are even better.

[0223] From the viewpoints of visual recognizability of the exposed part, visual recognizability of the unexposed part, and resolution, it is preferable that the thermoplastic layer contains a pigment whose maximum absorption wavelength changes due to acid and a compound that generates acid by light as described later as pigment B.

[0224] Thermoplastic resin layer system may contain one or more pigments B alone.

[0225] From the viewpoint of visual recognizability of the exposed part and visual recognizability of the unexposed part, the content ratio of pigment B relative to the total mass of the thermoplastic resin layer is preferably 0.2% by mass or more, 0.2% to 6% by mass is more preferably, 0.2% to 5% by mass is even more preferably, and 0.25% to 3.0% by mass is particularly preferred.

[0226] Here, the content ratio of pigment B refers to the proportion of pigment that makes all pigment B contained in the thermoplastic resin layer in a colored state. The following describes the quantitative method for the content ratio of pigment B using a pigment that develops color via free radicals. Two solutions were prepared by dissolving pigment (0.001 g) and pigment (0.01 g) separately in methyl ethyl ketone (100 mL). IRGACURE OXE-01 (BASF) was added to each of the resulting solutions as a photoradical polymerization initiator, and free radicals were generated by irradiating with 365 nm light, causing all pigments to develop color. Next, in an atmospheric environment, the absorbance of each solution at a liquid temperature of 25°C was measured using a spectrophotometer (UV3100, Shimadzu Corporation), and a calibration curve was created. Then, instead of pigment, the thermoplastic resin layer (0.1 g) was dissolved in methyl ethyl ketone, and the absorbance of the solution that made all pigments colored was measured using the same method as described above. The amount of pigment contained in the thermoplastic resin layer is calculated based on the absorbance of the obtained solution containing the thermoplastic resin layer and the calibration curve.

[0227] -Compounds that generate acids, bases, or free radicals by light- Thermoplastic resin systems may contain compounds that generate acids, bases, or free radicals by light (hereinafter, sometimes referred to as "Compound C"). It is preferable that Compound C is a compound that generates acids, bases, or free radicals upon receiving activating light (e.g., ultraviolet and visible light). Known photoacid generators, photobase generators, and photofree radical polymerization initiators (photofree radical generators) can be cited as Compound C. It is preferable that Compound C is a photoacid generator.

[0228] [Photoacid Generator] From the viewpoint of resolution, it is preferable that the thermoplastic resin layer contains a photoacid generator. As a photoacid generator, photocationic polymerization initiators that may be contained in the above-mentioned photosensitive resin layer can be cited, and the preferred form is the same as described below.

[0229] From the viewpoint of sensitivity and resolution, it is preferable that the photoacid generator contains at least one of the group consisting of onium salt compounds and oxime sulfonate compounds, and from the viewpoint of sensitivity, resolution and contact, it is even more preferable that it contains oxime sulfonate compounds.

[0230] Furthermore, photoacid generating agents having the following structure are also preferred.

[0231] [Chemical Formula 2]

[0232] 〔Photoalkali generating agent〕 The thermoplastic resin layer system may contain a photoalkali generating agent. Examples of photoalkali generating agents include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-aminomethylhydroxylamine, O-aminomethyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, and bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine. 4-(methylthiobenzoyl)-1-methyl-1-oxophyllylethane, (4-oxophyllylbenzoyl)-1-benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaaminocobalt(III)tris(triphenylmethylboronic acid ester), 2-benzyl-2-dimethylamino-1-(4-oxophyllylphenyl)-butanone, 2,6-dimethyl-3,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydroxypyridine and 2,6-dimethyl-3,5-diacetyl-4-(2,4-dinitrophenyl)-1,4-dihydroxypyridine.

[0233] [Photoradical polymerization initiator] The thermoplastic resin layer system may contain a photoradical polymerization initiator. Examples of photoradical polymerization initiators that may be contained in the above-mentioned photosensitive resin layer are as follows, and the preferred form is also the same.

[0234] Thermoplastic resin layer systems may contain one or more compounds C alone.

[0235] From the viewpoint of visual recognizability of the exposed part, visual recognizability of the unexposed part, and resolution, the content ratio of compound C is preferably 0.1% to 10% by mass relative to the total mass of the thermoplastic resin layer, and more preferably 0.5% to 5% by mass.

[0236] (Plasticizer) From the viewpoints of resolution, adhesion to layers adjacent to the thermoplastic resin layer, and developability, it is preferable that the thermoplastic resin layer contains a plasticizer.

[0237] It is preferable that the molecular weight of the plasticizer (the molecular weight of oligomers or polymers is referred to as the weight average molecular weight (Mw). The same applies below.) is less than that of the alkali-soluble resin. It is preferable that the molecular weight of the plasticizer is between 200 and 2,000.

[0238] Plasticizers are not limited to compounds that exhibit plasticity by being miscible with alkali-soluble resins. From the viewpoint of imparting plasticity, plasticizers containing alkoxy groups in the molecule are preferred, and polyalkylene glycol compounds are even more preferred. It is preferable that the alkoxy group contained in the plasticizer has a polyvinyloxy or polyacryloxy structure.

[0239] From the viewpoint of resolution and storage stability, it is preferable that the plasticizer contains a (meth)acrylate compound. From the viewpoint of compatibility, resolution, and adhesion to layers adjacent to the thermoplastic resin layer, it is even better that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound.

[0240] Examples of (meth)acrylate compounds used as plasticizers include those described in section "Polymerizable Compound B" above. In photosensitive transfer materials, when the thermoplastic resin layer and the photosensitive resin layer are disposed in direct contact, it is preferable that both the thermoplastic resin layer and the photosensitive resin layer contain the same (meth)acrylate compound. This is because, by having both the thermoplastic resin layer and the photosensitive resin layer contain the same (meth)acrylate compound, the diffusion of components between layers can be suppressed, thus improving storage stability.

[0241] When the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, from the viewpoint of the adhesion between the layers adjacent to the thermoplastic resin layer, it is preferable that the (meth)acrylate compound does not polymerize in the exposed portion after exposure.

[0242] In one embodiment, from the viewpoint of resolution, adhesion to layers adjacent to the thermoplastic resin layer, and developability, it is preferable that the (meth)acrylate compound used as a plasticizer is a (meth)acrylate compound having two or more (meth)acrylic groups in one molecule.

[0243] In one embodiment, it is preferred that the (meth)acrylate compound used as a plasticizer is a (meth)acrylate compound having an acid group or a carbamate (meth)acrylate compound.

[0244] Thermoplastic resin layers may contain one or more plasticizers.

[0245] From the viewpoints of resolution, adhesion to layers adjacent to the thermoplastic resin layer, and developability, the content of plasticizer is preferably 1% to 70% by mass relative to the total mass of the thermoplastic resin layer, more preferably 10% to 60% by mass, and especially preferably 20% to 50% by mass.

[0246] (Surfactant) From the viewpoint of thickness uniformity, it is preferable for thermoplastic resin layers to contain a surfactant. Examples of surfactants that may be contained in the aforementioned photosensitive resin layers are also preferred.

[0247] Thermoplastic resin layer systems may contain one or more surfactants.

[0248] The content of surfactant is preferably 0.001% to 10% by mass relative to the total mass of the thermoplastic resin layer, and even more preferably 0.01% to 3% by mass.

[0249] (Sensitizer) The thermoplastic resin layer system may contain a sensitizer. Examples of sensitizers include those found in the aforementioned photosensitive resin layer.

[0250] Thermoplastic resin layer systems may contain one or more sensitizers.

[0251] From the viewpoint of improving the sensitivity to light source, the visual recognizability of the exposed part and the visual recognizability of the unexposed part, the content ratio of sensitizer is preferably 0.01% to 5% by mass relative to the total mass of the thermoplastic resin layer, and even more preferably 0.05% to 1% by mass.

[0252] (Additives) In addition to the above-mentioned components, the thermoplastic resin layer system may also contain known additives as needed.

[0253] Furthermore, regarding the thermoplastic resin layer, it is described in paragraphs 0189 to 0193 of Japanese Patent Application Publication No. 2014-085643. The contents of the aforementioned publication are incorporated herein by reference.

[0254] (Thickness) The thickness of the thermoplastic resin layer is not limited. From the viewpoint of the adhesion between the thermoplastic resin layer and the adjacent layers, it is preferable that the average thickness of the thermoplastic resin layer is 1 μm or more, and more preferably 2 μm or more. The upper limit of the average thickness of the thermoplastic resin layer is not limited. From the viewpoint of developability and resolution, it is preferable that the average thickness of the thermoplastic resin layer is 20 μm or less, more preferably 10 μm or less, and especially preferably 5 μm or less.

[0255] (Forming Method) The method for forming the thermoplastic resin layer is not limited as long as it is a method capable of forming a layer containing the above-mentioned components. As a method for forming the thermoplastic resin layer, for example, the following method can be used: coating the thermoplastic resin composition onto the surface of the dummy support and drying the coating of the thermoplastic resin composition.

[0256] Examples of thermoplastic resin compositions include those containing the above-mentioned components. It is preferable that the thermoplastic resin composition contains a solvent in order to adjust the viscosity of the thermoplastic resin composition and facilitate the formation of the thermoplastic resin layer.

[0257] - Solvent - As a solvent contained in the thermoplastic resin composition, it is not limited as long as it is a solvent capable of dissolving or dispersing the components contained in the thermoplastic resin layer. Examples of solvents that may be contained in the above-mentioned photosensitive resin composition can be cited as solvents, and the preferred form is also the same.

[0258] Thermoplastic resin composition systems may contain one or more solvents alone.

[0259] The solvent content in the thermoplastic resin composition is preferably 50 parts to 1,900 parts by weight relative to 100 parts by weight of all solid components in the thermoplastic resin composition, and more preferably 100 parts to 900 parts by weight.

[0260] The preparation of the thermoplastic resin composition and the formation of the thermoplastic resin layer can be carried out according to the above-described methods for preparing the photosensitive resin composition and forming the photosensitive resin layer. For example, a solution containing each component of the thermoplastic resin layer dissolved in a solvent is prepared in advance, and the solutions are mixed in a predetermined ratio to prepare the thermoplastic resin composition. The obtained thermoplastic resin composition is then coated onto the surface of the dummy support, and the coating of the thermoplastic resin composition is dried to form the thermoplastic resin layer. Alternatively, the thermoplastic resin layer can be formed on the surface of the photosensitive resin layer after the photosensitive resin layer is formed on the cover film described later.

[0261] (Intermediate Layer) The photosensitive transfer material disclosed herein preferably has an intermediate layer between the thermoplastic resin layer and the photosensitive resin layer. Based on the intermediate layer, mixing of components can be suppressed when forming and storing multiple layers.

[0262] From the viewpoint of developability and the inhibition of mixing of components during coating of multiple layers and storage after coating, it is preferable that the intermediate layer is a water-soluble layer. In this disclosure, "water-soluble" means having a solubility of 0.1g or more in 100g of water at pH 7.0 and a liquid temperature of 22°C.

[0263] As an intermediate layer, an oxygen barrier layer with oxygen barrier function, as described in Japanese Patent Application Publication No. 5-072724 as a "separation layer," can be cited as an example. By using an oxygen barrier layer as the intermediate layer, the sensitivity during exposure can be improved, thereby reducing the time load on the exposure machine, and as a result, productivity can be improved. The oxygen barrier layer used as the intermediate layer can be appropriately selected from known layers. It is preferable that the oxygen barrier layer used as the intermediate layer exhibits low oxygen permeability and is dispersed or dissolved in water or alkaline aqueous solution (a 1% by mass aqueous solution of sodium carbonate at 22°C).

[0264] It is preferable that the intermediate layer contains a resin. Examples of resins contained in the intermediate layer include polyvinyl alcohol resins, polyvinylpyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof. It is preferable that the resin contained in the intermediate layer is a water-soluble resin.

[0265] From the viewpoint of suppressing the mixing of components between multiple layers, it is preferable that the resin system contained in the intermediate layer is different from the polymer A contained in the photosensitive resin layer and the thermoplastic resin (alkali-soluble resin) contained in the thermoplastic resin layer.

[0266] From the viewpoint of oxygen barrier properties and the inhibition of mixing of components during coating of multiple layers and storage after coating, it is preferable that the intermediate layer contains polyvinyl alcohol, and even more preferable that it contains both polyvinyl alcohol and polyvinylpyrrolidone.

[0267] The intermediate layer system may contain one or more resins.

[0268] From the viewpoint of oxygen barrier properties and the inhibition of mixing of components during coating of multiple layers and storage after coating, the resin content in the intermediate layer is preferably 50% to 100% by mass relative to the total mass of the intermediate layer, more preferably 70% to 100% by mass, further preferably 80% to 100% by mass, and especially preferably 90% to 100% by mass.

[0269] Furthermore, the intermediate layer system may contain additives as needed. Examples of additives include surfactants.

[0270] The thickness of the intermediate layer is not limited. The average thickness of the intermediate layer is preferably 0.1 μm to 5 μm, and more preferably 0.5 μm to 3 μm. By keeping the thickness of the intermediate layer within the above range, it is possible to suppress the mixing of components when forming and storing multiple layers without reducing oxygen barrier properties, and also to suppress the increase in the removal time of the intermediate layer during development.

[0271] The method for forming the intermediate layer is not limited as long as it is a method capable of forming a layer containing the above-mentioned components. For example, a method for forming the intermediate layer may be as follows: after coating the intermediate layer with the composition onto the surface of the thermoplastic resin layer or the photosensitive resin layer, the coating film of the intermediate layer with the composition is dried.

[0272] Examples of intermediate layer compositions include those containing resin and any additives. To adjust the viscosity of the intermediate layer composition and facilitate intermediate layer formation, it is preferable that the intermediate layer composition contains a solvent. The solvent is not limited to any solvent capable of dissolving or dispersing the resin. It is preferable that the solvent is selected from at least one of the groups consisting of water and water-miscible organic solvents, with water or a mixture of water and water-miscible organic solvents being more preferred.

[0273] Examples of water-miscible organic solvents include alcohols with 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerol. Alcohols with 1 to 3 carbon atoms are preferred as water-miscible organic solvents, with methanol or ethanol being even more preferred.

[0274] (Contrast Enhancement Layer) The photosensitive transfer material disclosed herein may have a contrast enhancement layer. Contrast enhancement layers are described, for example, in paragraph 0134 of International Publication No. 2018 / 179640 and paragraphs 0194 to 0196 of Japanese Patent Application Publication No. 2014-085643. The contents of these publications are incorporated herein by reference.

[0275] <<Average Thickness>> The average thickness of the photosensitive transfer material is preferably 5μm to 55μm, more preferably 10μm to 50μm, and particularly preferably 20μm to 40μm. The average thickness of the photosensitive transfer material is determined by the following method: A cross-section perpendicular to the main surface of the photosensitive transfer material (i.e., the thickness direction) is observed using a scanning electron microscope (SEM). Based on the obtained observation images, the thickness of 10 photosensitive transfer materials is measured. The average thickness of the photosensitive transfer material is obtained by arithmetic averaging the measured values.

[0276] <<Shape>> The shape of the photosensitive transfer material disclosed herein is not limited. From the point of view of versatility and transportability, the shape of the photosensitive transfer material disclosed herein is preferably in roll form. By rolling up the photosensitive transfer material, the shape of the photosensitive transfer material can be made into a roll.

[0277] <<Manufacturing Method>> In the manufacturing method of the photosensitive transfer material disclosed herein, for example, the layer formation methods described in the "Constituent Elements" section above can be used. Hereinafter, a preferred example of the manufacturing method of the photosensitive transfer material will be described with reference to FIG1. ​​However, the manufacturing method of the photosensitive transfer material is not limited to the method described below.

[0278] Figure 1 is a schematic diagram showing an example of the composition of a photosensitive transfer material. As a method for manufacturing the photosensitive transfer material 100 shown in Figure 1, an example method may include the following steps: forming a photosensitive resin layer 12 by coating a photosensitive resin composition onto a dummy support 10; and disposing a cover film 14 on the photosensitive resin layer 12. In the above method, the photosensitive resin composition coated on the dummy support 10 may be dried as needed. There are no limitations on the drying method; known drying methods may be used.

[0279] As a method for disposing the cover film 14 on the photosensitive resin layer 12, for example, a method of pressing the cover film 14 onto the photosensitive resin layer 12 can be described.

[0280] By going through the above steps, a photosensitive transfer material 100 having a pseudo-support 10, a photosensitive resin layer 12, and a cover film 14 can be manufactured. The manufactured photosensitive transfer material 100 can be rolled into a roll. The roll-shaped photosensitive transfer material 100 can, for example, be used in a bonding step of bonding to a substrate using a roll-to-roll method.

[0281] <<Applications>> The photosensitive transfer material disclosed herein can be used, for example, for the formation of resin patterns and the formation of circuit wiring. However, the applications of the photosensitive transfer material disclosed herein are not limited to the above-mentioned applications.

[0282] <Method for Manufacturing Resin Patterns and Method for Manufacturing Circuit Wiring> The method for manufacturing resin patterns disclosed herein is not limited as long as it uses the photosensitive transfer material disclosed herein. For example, when using a photosensitive transfer material including a dummy support and a photosensitive resin layer, the method for manufacturing resin patterns disclosed herein preferably includes the following steps in sequence: a step of bonding the photosensitive transfer material disclosed herein and the substrate (preferably a conductive substrate) in such a way that the side of the photosensitive resin layer opposite to the side where the dummy support is disposed is in contact with the substrate (hereinafter, sometimes referred to as the "bonding step"); a step of exposing the photosensitive resin layer to a pattern (hereinafter, sometimes referred to as the "exposure step"); and a step of developing the photosensitive resin layer to form a resin pattern (hereinafter, sometimes referred to as the "development step").

[0283] The method for manufacturing circuit wiring disclosed herein is not limited as long as it is a method for manufacturing circuit wiring using the photosensitive transfer material disclosed herein. The method for manufacturing circuit wiring disclosed herein preferably includes the following steps: preparing a laminate having a substrate, a conductive layer, and a resin pattern formed using the photosensitive transfer material disclosed herein in sequence; and etching the conductive layer in areas of the laminate where the resin pattern is not disposed (hereinafter, sometimes referred to as the "etching step").

[0284] It is preferable that the method for manufacturing the resin pattern and the method for manufacturing the circuit wiring disclosed herein are performed using a roll-to-roll method. The roll-to-roll method refers to the following: using a rollable and unrollable substrate as the substrate, and before any step included in the method for manufacturing the resin pattern or the method for manufacturing the circuit wiring, unwinding the substrate or the structure including the substrate (also referred to as the "unwinding step"); and after any step, winding the substrate or the structure including the substrate (also referred to as the "winding step"), while transporting the substrate or the structure including the substrate, performing at least one step (preferably all steps or all steps except the heating step). There are no limitations on the unwinding method in the unwinding step and the winding method in the winding step; any known method may be used in the manufacturing method to which the roll-to-roll method applies.

[0285] Hereinafter, the steps included in the method for manufacturing the resin pattern and the method for manufacturing the circuit wiring disclosed herein will be described. However, unless otherwise specified, the description of the steps included in the method for manufacturing the resin pattern disclosed herein can also be applied to the steps included in the method for manufacturing the circuit wiring disclosed herein.

[0286] <<Lamination Step>> The method for manufacturing the resin pattern disclosed herein preferably includes a step of bonding the photosensitive transfer material and the substrate (preferably a conductive substrate) in such a way that the side of the photosensitive resin layer in the above-mentioned photosensitive transfer material opposite to the side where the dummy support is disposed (hereinafter, sometimes referred to as "first side") is in contact with the substrate.

[0287] In the bonding step, it is preferable to press the photosensitive transfer material and the substrate together by contacting the first side of the photosensitive resin layer with the substrate (or, if a conductive layer is provided on the surface of the substrate). Based on the above, the adhesion between the first side of the photosensitive resin layer and the substrate can be improved, and thus the formed resin pattern can be appropriately used as an etching resist.

[0288] When the photosensitive transfer material has a cover film, after removing the cover film from the photosensitive transfer material, the photosensitive transfer material and the substrate can be bonded together.

[0289] In the case where a layer other than a cover film (e.g., a high refractive index layer and / or a low refractive index layer) is disposed on the first surface of the photosensitive resin layer, the first surface of the photosensitive resin layer and the substrate can be bonded together via the layer other than the cover film.

[0290] There are no limitations on the method for bonding the photosensitive transfer material and the substrate; known transfer and lamination methods can be used. It is preferable to bond the photosensitive transfer material and the substrate by overlapping the first surface of the photosensitive resin layer with the substrate and applying pressure and heat using a mechanism such as rollers. Furthermore, laminators, vacuum laminators, and automated cutting laminators that can further improve productivity can be used during bonding.

[0291] [Substrate] There are no limitations on the substrate, and known substrates can be used. It is preferable that the substrate has a conductive layer, and it is even more preferable that the substrate has a substrate and a conductive layer disposed on part or all of the surface of the substrate. The substrate may have any layer other than the conductive layer as needed.

[0292] As a substrate, examples include glass, silicon and films.

[0293] A transparent substrate is preferred. In this disclosure, "transparent" means that the transmittance of light with a wavelength of 400 to 700 nm is 80% or more.

[0294] A refractive index of 1.50 to 1.52 is preferred for the substrate.

[0295] Examples of transparent glass substrates include, for example, tempered glass, such as Corning Incorporated's Gorilla Glass. Furthermore, materials used in Japanese Patent Application Publication Nos. 2010-086684, 2010-152809, and 2010-257492 can also be used as transparent glass substrates.

[0296] When a membrane substrate is used as the substrate, it is preferable to use a membrane substrate with low optical strain and / or high transparency. Examples of such membrane substrates include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cyclic olefin polymers.

[0297] It is preferable that the substrate used in the roll-to-roll method is a film substrate. Furthermore, when manufacturing circuit wiring for a touch panel using the roll-to-roll method, it is preferable that the substrate is a sheet resin composition.

[0298] As a conductive layer, examples include conductive layers used for general circuit wiring or touch panel wiring. From the viewpoint of conductivity and fine line formation, it is preferable that the conductive layer is selected from at least one of the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, with a metal layer being more preferred, and a copper layer or a silver layer being particularly preferred.

[0299] The substrate may have one or more conductive layers. It is preferable that the substrate having two or more conductive layers has multiple conductive layers of different materials.

[0300] Materials used as the conductive layer include, for example, 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 SiO2. In this disclosure, "conductivity" refers to a volume resistivity of less than 1 × 10⁶ Ωcm. Preferably, the volume resistivity of the conductive metal oxide is less than 1 × 10⁴ Ωcm.

[0301] When a resin pattern is manufactured using a substrate having a plurality of conductive layers, it is preferable that at least one of the conductive layers contains a conductive metal oxide.

[0302] As a conductive layer, it is preferable to use an electrode pattern or wiring of a sensor for a visual recognition section of a capacitive touch panel.

[0303] <<Exposure Step>> The method for manufacturing resin patterns disclosed herein is preferably a step of exposing the photosensitive resin layer to the pattern after the above-mentioned bonding step.

[0304] The detailed configuration and specific dimensions of the pattern in the pattern exposure are not limited. In order to improve the display quality of the display device (e.g., touch panel) having an input device with circuit wiring manufactured by a circuit wiring manufacturing method, and to reduce the area occupied by the lead wiring, at least a portion of the pattern (preferably the electrode pattern and / or the lead wiring portion of the touch panel) preferably includes fine lines with a width of 20 μm or less, and more preferably includes fine lines with a width of 10 μm or less.

[0305] The light source used in the exposure is a light source that illuminates the photosensitive resin layer at a wavelength that can expose the light (e.g., 365nm or 405nm). Specific light sources include, for example, ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (light emitting diodes).

[0306] The exposure level is better at 5mJ / cm2 to 200mJ / cm2, and even better at 10mJ / cm2 to 100mJ / cm2.

[0307] In the exposure step, pattern exposure can be performed after the dummy support is peeled off from the photosensitive resin layer, or pattern exposure can be performed through the dummy support and then the dummy support is peeled off. To prevent contamination of the photosensitive resin layer due to contact between the photosensitive resin layer and the mask, and to avoid the influence of foreign matter attached to the mask on the exposure, pattern exposure through the dummy support is preferable. Furthermore, pattern exposure can be performed through the mask, or it can be performed directly using an exposure mechanism such as a laser.

[0308] <<Development Step>> The method for manufacturing resin patterns disclosed herein preferably includes a step of developing a photosensitive resin layer to form a resin pattern after the above-mentioned exposure step.

[0309] The development system of the photosensitive resin layer can be performed using a developer. The type of developer is not limited as long as it can remove the image portion (exposed portion) or the non-image portion (unexposed portion) of the photosensitive resin layer. As the developer, known developers can be used (for example, the developer described in Japanese Patent Application Publication No. 5-072724).

[0310] The developer is preferably 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 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.

[0311] There are no particular limitations on the development method; it can be any of the following: spin-dip development, shower development, shower and spin development, and dip coating development. Shower development refers to the development process in which the exposed or unexposed areas are removed by spraying the developer onto the exposed photosensitive resin layer using a shower.

[0312] After the developing step, it is better to use a shower spray cleaner and a brush to wipe away developing residue.

[0313] The liquid temperature of the developer is not limited. However, a liquid temperature of 20°C to 40°C is preferred.

[0314] For example, when the photosensitive transfer material includes a thermoplastic resin and an intermediate layer, the thermoplastic resin and the intermediate layer are removed together with the image portion (exposed portion) or the non-image portion (unexposed portion) of the photosensitive resin layer during the developing step. Furthermore, during the developing step, the thermoplastic resin layer and the intermediate layer can be removed by dissolving or dispersing them in the developing solution.

[0315] <<Etching Step>> The method for manufacturing circuit wiring disclosed herein preferably includes the following steps: preparing a laminate having a substrate, a conductive layer, and a resin pattern formed using the photosensitive transfer material disclosed herein in sequence; and etching the conductive layer in the laminate in areas where the resin pattern is not disposed. The resin pattern is preferably formed by a resin pattern manufacturing method including the bonding step, the exposure step, and the development step. The step of preparing the laminate preferably includes the bonding step, the exposure step, and the development step.

[0316] In the etching step, the conductive layer is etched by using a resin pattern as an etching resist. Known methods can be applied as etching methods. Examples of etching methods include those described in paragraphs 0209 to 0210 of Japanese Patent Application Publication No. 2017-120435, those described in paragraphs 0048 to 0054 of Japanese Patent Application Publication No. 2010-152155, wet etching by immersion in an etching solution, and methods using dry etching (e.g., plasma etching).

[0317] The etching solution used in wet etching is an acidic or alkaline etching solution that is appropriately selected according to the object being etched.

[0318] Examples of acidic etching solutions include aqueous solutions of an acidic component selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, as well as aqueous solutions of an acidic component and a 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.

[0319] Examples of alkaline etching solutions include aqueous solutions of an alkaline component selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide), as well as aqueous solutions of a mixture of an alkaline component and a salt (e.g., potassium permanganate). The alkaline component may be a combination of multiple alkaline components.

[0320] <<Removal Step>> The method for manufacturing circuit wiring disclosed herein preferably includes a step of removing residual resin patterns (hereinafter, sometimes referred to as the "removal step"). It is preferable that the removal step is performed after the etching step.

[0321] As a method for removing residual resin patterns, for example, a method of removing residual resin patterns by chemical treatment can be cited. A method of removing residual resin patterns using a removal liquid is preferred. As a method of using a removal liquid, for example, a method of immersing a substrate with residual resin patterns in a removal liquid at a preferred temperature of 30°C to 80°C, more preferably 50°C to 80°C, while stirring, for 1 minute to 30 minutes can be cited.

[0322] Examples of removal solutions include those in which an inorganic or organic base component is dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixture thereof. Examples of inorganic base components include sodium hydroxide and potassium hydroxide. Examples of organic base components include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

[0323] The method of removing residual resin patterns using a removal solution is not limited to the immersion method, but may also be a known method other than the immersion method (e.g., spraying method, showering method and spin-dip method).

[0324] <<Other Steps>> The method for manufacturing circuit wiring disclosed herein may include any steps other than those described above (hereinafter, sometimes referred to as "other steps"). Examples of exposure steps, development steps, and other steps applicable to the method for manufacturing circuit wiring disclosed herein include paragraphs 0035 to 0051 of Japanese Patent Application Publication No. 2006-023696. Furthermore, examples of other steps include the steps shown below. However, other steps are not limited to the steps shown below.

[0325] [Cover film peeling step] When the photosensitive transfer material disclosed herein has a cover film, it is preferable that the method for manufacturing the resin pattern disclosed herein includes the step of peeling the cover film from the photosensitive transfer material. There are no limitations on the method for peeling the cover film, and known methods may be used.

[0326] [Steps to reduce visible light reflectivity] The method for manufacturing circuit wiring disclosed herein may include steps of performing a process to reduce the visible light reflectivity of part or all of the conductive layer in the substrate.

[0327] As a process to reduce the visible light reflectance of the conductive layer, an oxidation process can be cited as an example. When the conductive layer contains copper, by oxidizing the copper to make it copper oxide and blackening the conductive layer, the visible light reflectance of the conductive layer can be reduced.

[0328] Regarding the treatment of reducing the visible light reflectivity of the conductive layer, it is 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 of these publications are incorporated herein by reference.

[0329] [Steps for forming an insulating film and forming a new conductive layer on the surface of the insulating film] The method for manufacturing circuit wiring disclosed herein preferably includes the steps of forming an insulating film on the surface of the circuit wiring and forming a new conductive layer on the surface of the insulating film. Through these steps, two electrode patterns insulated by the insulating film can be formed.

[0330] The method for forming the insulating film is not limited. In the step of forming the insulating film, for example, the insulating film can be formed by a known method for forming a permanent film. Alternatively, an insulating film with a desired pattern can be formed by photolithography using a photosensitive material with insulating properties.

[0331] In the step of forming a new conductive layer on the insulating film, for example, a photosensitive material with conductivity can be used to form a new conductive layer with the desired pattern by photolithography.

[0332] In the method for manufacturing circuit wiring disclosed herein, it is preferable to use a substrate having conductive layers on both surfaces of the substrate, and to form circuits sequentially or simultaneously on the conductive layers. According to the above method, for example, a circuit wiring for a touch panel can be formed with a first conductive pattern formed on one surface of the substrate and a second conductive pattern formed on the other surface of the substrate. Furthermore, by the method for manufacturing circuit wiring disclosed herein, it is preferable to form the circuit wiring for the touch panel by winding it from one surface to the other on the substrate.

[0333] <<Applications of Circuit Wiring>> The circuit wiring manufactured by the method disclosed herein can be applied to various devices. Examples of devices equipped with the circuit wiring manufactured by the method disclosed herein include input devices, with touch panels being preferred, and capacitive touch panels being even more preferred. Furthermore, the aforementioned input devices can be applied to various display devices (e.g., organic EL display devices and liquid crystal display devices).

[0334] <Manufacturing Method of Touch Panel> The manufacturing method of the touch panel disclosed herein is not limited as long as it is a manufacturing method of a touch panel using the photosensitive transfer material disclosed herein.

[0335] The method for manufacturing a touch panel disclosed herein preferably includes the following steps: preparing a laminate having a substrate, a conductive layer, and a resin pattern formed using the photosensitive transfer material disclosed herein in sequence; and forming wiring for a touch panel by etching the conductive layer in areas of the laminate where the resin pattern is not disposed. The resin pattern is preferably formed by a resin pattern manufacturing method including the bonding step, the exposure step, and the development step. The step of preparing the laminate preferably includes the bonding step, the exposure step, and the development step.

[0336] Regarding the forms of each step in the manufacturing method of the touch panel disclosed herein, as described in the section on "Method for Manufacturing Resin Patterns and Method for Manufacturing Circuit Wiring" above, the preferred forms are also the same. For the manufacturing method of the touch panel disclosed herein, in addition to forming the wiring for the touch panel by the above method, refer to known methods for manufacturing touch panels. Furthermore, the manufacturing method of the touch panel disclosed herein may include any steps other than those described above.

[0337] The pattern of the mask used in manufacturing a touch panel will be explained with reference to Figures 2 and 3. Figure 2 is a schematic diagram showing an example of the pattern of the mask used in manufacturing a touch panel. Figure 3 is a schematic diagram showing another example of the pattern of the mask used in manufacturing a touch panel. In Figures 2 and 3, DL represents an imaginary alignment frame, and G represents a non-image portion (light-shielding portion). In Figure 2, SL represents a non-image portion (light-shielding portion). In the touch panel manufacturing method disclosed herein, for example, by exposing a photosensitive resin layer through a mask having the pattern shown in Figure 2, a touch panel having circuit wiring with patterns corresponding to SL and G can be manufactured. Specifically, a touch panel can be manufactured by the method described in Figure 1 of International Publication No. 2016 / 190405. In an example of the manufactured touch panel, G forms the portion forming the transparent electrode (i.e., the electrode for the touch panel), and SL forms the portion forming the wiring of the peripheral lead-out portion.

[0338] According to the manufacturing method of the touch panel disclosed herein, a touch panel having at least touch panel wiring can be manufactured. It is preferable that the touch panel has a transparent substrate, electrodes, and an insulating layer or protective layer.

[0339] Examples of detection methods for touch panels include resistive film detection, capacitive detection, ultrasonic detection, electromagnetic induction detection, and optical detection. Among these, capacitive detection is preferred.

[0340] As types of touch panels, examples include embedded types (e.g., the configurations described in Figures 5, 6, 7, and 8 of Japanese Patent Application Publication No. 2012-517051), on-screen types (e.g., the configurations described in Figure 19 of Japanese Patent Application Publication No. 2013-168125, and Figures 1 and 5 of Japanese Patent Application Publication No. 2012-089102), OGS (One Glass Solution) types, TOL (Touch-on-Lens) types (e.g., the configuration described in Figure 2 of Japanese Patent Application Publication No. 2013-054727), various external types (e.g., GG, G1 / G2, GFF, GF2, GF1, and G1F), and other configurations (e.g., the configuration described in Figure 6 of Japanese Patent Application Publication No. 2013-164871). [Example]

[0341] Hereinafter, the present disclosure will be described in detail by way of embodiments. However, the present disclosure is not limited to the following embodiments.

[0342] <Synthesis of Polymer A-1> Propylene glycol 1-monomethyl ether (75.0 g) was placed in a three-necked flask, and the liquid temperature was raised to 90°C under nitrogen. A solution containing styrene (32.0 g), methacrylic acid (28.0 g), methyl methacrylate (40.0 g), 2,2'-azobis(isobutyronitrile) (0.8 g), and propylene glycol 1-monomethyl ether (75.0 g) was added dropwise to the liquid in the three-necked flask maintained at 90°C ± 2°C over 2 hours. After the addition was completed, the mixture was stirred at 90°C ± 2°C for 2 hours to obtain a solution containing polymer A-1 (solid content concentration: 40.0% by mass). The weight average molecular weight of polymer A-1 is 40,000.

[0343] <Synthesis of Polymer A-2> A solution containing polymer A-2 (solid content concentration: 40.0% by mass) was obtained using the same method as polymer A-1, except that the amount of monomer used was changed as described below. The weight average molecular weight of polymer A-2 was 60,000. (1) Styrene: 52.0 g (2) Methacrylic acid: 29.0 g (3) Methyl methacrylate: 19.0 g

[0344] <Synthesis of Polymer A-3> The monomers (styrene, methacrylic acid, and methyl methacrylate) used in the synthesis of polymer A-1 were changed to the following monomers. Otherwise, a solution containing polymer A-3 (solid content concentration: 40.0% by mass) was obtained by the same method as polymer A-1. The weight average molecular weight of polymer A-3 is 40,000. (1) Benzyl methacrylate (81.0 g) (2) Methacrylic acid (19.0 g)

[0345] <Synthesis of 2-functional methacrylates> Bisphenol A (22.83 g, 0.1 mol), toluene (30 g) as solvent, and triethylamine (0.3 g) as catalyst were added to a pressure-resistant reaction vessel with a capacity of 500 mL. After purging the inside of the pressure-resistant reaction vessel with nitrogen, the nitrogen pressure was adjusted to 0.2 kg / cm², and the mixture was heated to 80°C while stirring. Ethylene oxide (132.15 g, 3.0 mol) and propylene oxide (23.24 g, 0.4 mol) were introduced sequentially to maintain a pressure of approximately 2 kg / cm² while the temperature was raised to 150°C. The mixture was kept at 150°C for 1 hour and then cooled. The mixture was neutralized with oxalic acid, and then ion-exchanged water (50 g) was added to the mixture and stirred. The mixture was then allowed to stand, thereby separating the organic layer, which was then extracted. The resulting organic layer was washed three times with ion-exchanged water (50 g), and then the solvent was removed by reducing the pressure to 30 Torr at 50 °C to obtain a diol (105.1 g). The diol (100.0 g, 0.044 mol), methacrylic acid (11.5 g), 70% methanesulfonic acid aqueous solution (0.9 g), hydroquinone (0.2 g), and toluene (200 mL) were added to a 1 L three-necked flask, and esterification was carried out under reflux of toluene for 8 hours. Water produced during the reaction was removed using a Dean-Stark apparatus. After the reaction, the mixture was cooled to room temperature, and the resulting organic layer was washed once with 5% sodium hydroxide aqueous solution (50 g), followed by three washes with ion-exchanged water (50 g). Hydroquinone monomethyl ether (0.09 g) was added to the organic layer, and the solvent was removed by reducing the pressure to 30 Torr at 50 °C, thereby obtaining dimethacrylate of polyethylene glycol (90.0 g) with an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide added to both ends of bisphenol A.

[0346] <Examples 1-6 and Comparative Example 1> A photosensitive transfer material was prepared according to the following steps.

[0347] (Preparation of the photosensitive resin composition) After mixing the selected components according to Table 1, methyl ethyl ketone was added to prepare the photosensitive resin composition (solid component concentration: 25% by mass). The values ​​corresponding to the components listed in Table 1 represent the mass parts of the solid component. In Examples 1 to 6, raw materials for which halide ions were removed by the method described later were used.

[0348] (Removal of halide ions) The halide ions in the raw material were removed according to the following steps.

[0349] -Polymer A- A solution containing 250g of the polymer corresponding to Polymer A in Table 1, with 250g of acetone added dropwise, was added to a mixture containing 250g of methanol and 2,250g of deionized water. The mixture was then filtered to obtain a white solid polymer. The polymer was dried at 50°C to remove the solvent, and then dissolved again in propylene glycol 1-monomethyl ether to obtain a solution containing the target polymer (solid content concentration: 40.0% by mass).

[0350] -Polymerizable Compound B- The compound corresponding to polymerizable compound B in Table 1 (50 g) was dissolved in ethyl acetate (200 g), followed by the addition of ion-exchanged water (100 g) and stirring for 5 minutes. After stirring, the mixture was allowed to stand, thereby separating the organic layer, which was then extracted. The resulting organic layer was washed twice with ion-exchanged water (100 g), and then hydroquinone monomethyl ether (0.02 g) was added, followed by solvent removal under reduced pressure to 30 Torr at 50°C.

[0351] -Photopolymerization Initiator- The compound corresponding to the photopolymerization initiator in Table 1 (10 g) was dissolved in ethyl acetate (400 g), and then ion-exchanged water (100 g) was added and stirred for 5 minutes. After stirring, the mixture was allowed to stand to separate the organic layer, which was then extracted. The resulting organic layer was washed twice with ion-exchanged water (100 g) and then the solvent was removed by reducing the pressure to 30 Torr at 50°C.

[0352] [Table 1] Element [Unit of value: parts by mass] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Polymer A Polymer A-1 - 55.00 - 62.20 - - - Polymer A-2 50.00 - - - - 51.00 30.00 Polymer A-3 - - 52.00 - 59.20 - 20.00 Polymer compound B BPE-500 (SHIN-NAKAMURA CHEMICAL CO, LTD.) 36.20 20.20 7.40 - 27.00 15.00 10.00 BPE-200 (SHIN-NAKAMURA CHEMICAL CO, LTD.) - 9.80 10.00 20.00 - - 10.00 2-functional methacrylates - - - - - 10.00 5.00 M-270 (TOAGOSEI CO., LTD.) 5.00 - - - - - - A-TMPT (SHIN-NAKAMURA CHEMICAL CO, LTD.) - 10.00 10.00 6.00 - 5.00 17.27 SR-454 (ARKEMA KK Japan) - - 15.00 9.00 - 5.00 - SR-502 (ARKEMA KK Japan) - - - - 4.00 - - A-9300-CL1 (SHIN-NAKAMURA CHEMICAL CO, LTD.) - - - - 7.80 9.77 - Photopolymerization initiator 2,2'-Bis(2-chlorophenyl)-4,4',5,5'-tetracycline Phenylon-1,2'-Bimidazole (Tokyo Chemical Industry Co., Ltd.) 7.00 3.00 3.80 1.90 1.10 3.00 6.00 Sensitizer 4,4'-Bis(diethylamine)benzophenone (Tokyo Chemical Industry Co., Ltd.) 0.50 0.50 0.30 0.30 0.10 0.30 0.40 Chain transfer agent Colorless crystal violet (Tokyo Chemical Industry Co., Ltd.) 0.40 0.90 - 0.40 0.66 0.60 0.50 N-phenylglycine (Tokyo Chemical Industry Co., Ltd.) 0.20 - 1.00 - - - 0.50 Colorant (pigment) Bright green (Tokyo Chemical Industry Co., Ltd.) - 0.05 0.05 0.05 - 0.02 0.02 Rust inhibitor CBT-1 (JOHOKU CHEMICAL CO.,LTD) 0.10 - 0.05 0.03 0.03 - 0.10 Two benzotriazole compounds mixture - 0.14 0.05 - - 0.10 0.10 Polymer inhibitors TDP-G (Kawaguchi Chemical Industry Co., LTD.) 0.30 0.10 - - - - - Irganox245 (BASF) - - 0.20 0.10 0.10 0.20 0.10 N-nitrosophenylhydroxy Aluminum amine salts (FUJIFILM Wako Pure Chemical Corporation) - - 0.01 0.02 0.01 0.01 0.01 antioxidants phenidone (Tokyo Chemical Industry Co., Ltd.) 0.01 0.01 0.01 - - - - surfactants F-552 (DIC Corporation) 0.29 0.30 0.13 - - - -

[0353] In Table 1, “-” indicates that the amount used is 0 parts by mass.

[0354] In Table 1, “difunctional methacrylate” refers to a dimethacrylate of polyethylene glycol with an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide added to both ends of bisphenol A.

[0355] In Table 1, “mixture of two benzotriazole compounds” refers to a mixture of 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole. The mass ratio of 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole to 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole is 1:1.

[0356] (Preparation of Photosensitive Transfer Material) A PET film (TORAY INDUSTRIES, INC., Lumirror 16KS40, thickness: 16 μm, arithmetic mean roughness Ra: 0.02 μm) was prepared as a dummy support. A photosensitive resin composition was coated onto the surface of the dummy support using a slit nozzle with a coating width of 1.0 μm and a dried thickness of 10.0 μm. The formed photosensitive resin composition coating was dried at 95°C for 100 seconds to form a photosensitive resin layer. A polyethylene film (TAMAPOLY CO., LTD., GF-818, thickness: 19 μm) was pressed onto the surface of the formed photosensitive resin layer as a cover film to produce a photosensitive transfer material. The obtained photosensitive transfer material was rolled up to produce a roll of photosensitive transfer material.

[0357] <Quantitative Analysis of Halogen Ions> 100 mg of photosensitive resin layer collected from photosensitive transfer material was dissolved in 1 g of ethyl acetate. 2 g of ultrapure water was added to the ethyl acetate, and after thorough stirring, the resulting mixture was allowed to stand for 1 hour. The aqueous layer was extracted from the mixture, and the content of halide ions was determined by ion chromatography. The determination conditions for ion chromatography are shown below. Based on the determination results, the content of halide ions in the photosensitive resin layer was calculated. The determination results are shown in Table 2. (1) Measuring equipment: Dionex INTEGRION HPIC (Thermo Fisher Scientific Inc.) (2) Column: Dionex IonPac AS22 (anion analysis column, size (mm): 4×250) (3) Flow rate: 1 min / mL (4) Temperature: 35℃ (5) Sample for calibration curve preparation: Anion mixed standard solution IV (Kanto Chemical Co., Inc.) (6) Eluent: An aqueous solution obtained by mixing sodium carbonate (4.5 mmol / L) and sodium bicarbonate solution (1.4 mmol / L).

[0358] <Evaluation of Lateral Etching Amount> A copper layer with a thickness of 500 nm was formed on a PET film with a thickness of 188 μm by sputtering, thereby fabricating a PET substrate with a copper layer. After laminating a photosensitive transfer material onto the PET substrate with the copper layer under the following lamination conditions, it was left to stand for 5 hours. (1) Temperature of the crimping roller: 120℃ (2) Linear pressure: 1.0 MPa (3) Linear speed: 0.5 m / min

[0359] After 5 hours, without removing the dummy support, the photosensitive resin layer was exposed via a mask (duty ratio = 1:1) used to form a line and spatial pattern with a line width of 15 μm. An ultra-high pressure mercury lamp was used as the exposure light source. The exposure amount was adjusted within a range where the line width of the resin pattern formed by development was 15 μm.

[0360] The dummy support was peeled off from the surface of the photosensitive resin layer, and the photosensitive resin layer was developed. Specifically, it was developed using a 1.0% by mass sodium carbonate aqueous solution at 25°C for 30 seconds.

[0361] The copper layer was etched using a copper etching solution (Kanto Chemical Co., Inc., Cu-02). Specifically, a shower etching was performed at 26°C for 40 seconds.

[0362] The residual resin pattern was removed using a stripping solution (Kanto Chemical Co., Inc., KP-301). The linewidth of the resulting copper pattern was measured using an optical microscope. The difference between the target linewidth value (15 μm) and the measured linewidth value was evaluated as the lateral etching amount. The evaluation results are shown in Table 2. In practical use, a lateral etching amount of 1.5 μm or less is preferred.

[0363] [Table 2] The proportion of halide ions [ppm] Lateral erosion [μm] Fluorides ion chloride ion bromide ion iodide ion total Example 1 0 9 1 0 10 1.0 Example 2 0 12 2 0 14 0.9 Example 3 0 20 1 0 twenty one 1.1 Example 4 0 26 0 0 26 0.8 Example 5 0 20 0 0 20 1.1 Example 6 0 80 3 0 83 1.5 Comparative Example 1 0 130 3 1 134 2.1

[0364] Table 2 shows the following results. The lateral corrosion amount of Examples 1 to 6 is less than that of Comparative Example 1. The disclosure of Japanese Patent Application No. 2020-034791, filed on March 2, 2020, is incorporated herein by reference in its entirety. All documents, patent applications and technical standards described in this specification are incorporated herein by reference to the same extent as those specifically described and cited separately. [Simplified Explanation of the Diagram]

[0009] Figure 1 is a schematic diagram showing an example of the composition of a photosensitive transfer material. Figure 2 is a schematic diagram showing an example of the pattern of a mask used in the manufacture of a touch panel. Figure 3 is a schematic diagram showing another example of the pattern of a mask used in the manufacture of a touch panel.

Claims

1. A photosensitive transfer material comprising: a pseudo-support; and a photosensitive resin layer, wherein the content of halide ions in the photosensitive resin layer is less than 100 ppm relative to the total mass of the photosensitive resin layer, the photosensitive resin layer contains an alkali-soluble polymer and a compound containing ethylene unsaturated bonds, the alkali-soluble polymer having a constituent unit derived from a monomer having an aromatic hydrocarbon group, the compound containing ethylene unsaturated bonds being 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane, the content of the alkali-soluble polymer being 30% to 70% by mass relative to the total mass of the photosensitive resin layer, and the content of the 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane being 10% to 70% by mass relative to the total mass of the photosensitive resin layer. The aforementioned proportion of the constituent units derived from monomers having aromatic hydrocarbon groups is 20% by mass or more and 95% by mass or less relative to the total mass of the aforementioned base-soluble polymer.

2. The photosensitive transfer material as claimed in claim 1, wherein the content of the aforementioned halide ions is 10 ppm to 50 ppm relative to the total mass of the aforementioned photosensitive resin layer.

3. The photosensitive transfer material as described in claim 1 or claim 2, wherein the content of the aforementioned halide ions is 10 ppm to 20 ppm relative to the total mass of the aforementioned photosensitive resin layer.

4. The photosensitive transfer material as described in claim 1 or claim 2, wherein the aforementioned halide ions are chloride ions.

5. The photosensitive transfer material as described in claim 1 or claim 2, wherein the aforementioned photosensitive resin layer contains a photopolymerization initiator.

6. A method for manufacturing circuit wiring, comprising: The steps include preparing a laminate having a substrate, a conductive layer, and a resin pattern formed using any one of claims 1 to 5; and etching the conductive layer in areas of the laminate where the resin pattern is not disposed.

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