Photosensitive transfer material, resin pattern manufacturing method, circuit wiring manufacturing method, and touch panel manufacturing method

Abstract

A photosensitive transfer material according to the present invention and applications therefor, the photosensitive transfer material comprising a temporary support and a photosensitive resin layer disposed on the temporary support, wherein a solution obtained by dissolving 0.1 m2 of the photosensitive transfer material in 1 liter of a 30°C 1 mass% aqueous solution of sodium carbonate has a haze of 60% or less.

Description

[Technical Field]

[0001] The present disclosure relates to a photosensitive transfer material, a method for manufacturing a resin pattern, a method for manufacturing circuit wiring, and a method for manufacturing a touch panel. [Background technology]

[0002] In display devices (organic electroluminescence (EL) display devices, liquid crystal display devices, etc.) equipped with a touch panel such as a capacitance-type input device, an electrode pattern corresponding to the sensor of the visible area, a conductive layer pattern such as wiring for the peripheral wiring portion and the extraction wiring portion, etc. is provided inside the touch panel.

[0003] Generally, the formation of a patterned layer requires only a small number of steps to obtain the desired pattern shape, and therefore a widely adopted method involves providing a layer of a photosensitive resin composition (photosensitive layer) on a substrate using a photosensitive transfer material, exposing the photosensitive layer through a mask having the desired pattern, and then developing it.

[0004] For example, Japanese Patent Application Laid-Open No. 2008-94803 describes a photosensitive resin laminate having a photosensitive resin layer provided on a support layer and made of a photosensitive resin composition containing 20 to 90 mass % of a binder resin made of a linear polymer having a carboxyl group content of 100 to 600 in acid equivalent and a weight average molecular weight of 20,000 to 500,000, 5 to 75 mass % of a photopolymerizable monomer having at least one terminal ethylenically unsaturated group, and 0.01 to 30 mass % of a photopolymerization initiator containing a specific compound. Summary of the Invention [Problem to be solved by the invention]

[0005] In JP 2008-94803 A, it is believed that a photopolymerization initiator having a specific structure is contained in the photosensitive resin layer in order to improve the dispersion stability of the photopolymerization initiator in the developer. However, in addition to the photopolymerization initiator, components with poor dispersion stability are present in the developer, and such components can cause the generation of scum (aggregates).

[0006] According to one embodiment of the present invention, there is provided a photosensitive transfer material that suppresses the generation of scum (aggregates) even when development is performed for a long period of time. Also, according to other embodiments of the present invention, there are provided a method for manufacturing a resin pattern, a method for manufacturing circuit wiring, and a method for manufacturing a touch panel using the photosensitive transfer material. [Means for solving the problem]

[0007] The present disclosure includes the following aspects. <1> A temporary support and a photosensitive resin layer disposed on the temporary support were included, and the photosensitive resin layer was immersed in 1 liter of a 30°C aqueous solution of 1% by mass of sodium carbonate at a concentration of 0.1 m. 2 A photosensitive transfer material, wherein the haze of a solution obtained by dissolving the photosensitive transfer material is 60% or less. <2> The thickness of the photosensitive resin layer is 10 μm or less; <1> The photosensitive transfer material according to claim 1. <3> the photosensitive resin layer contains a polymerizable compound and an alkali-soluble resin, and the ratio of the content of the polymerizable compound to the content of the alkali-soluble resin is 0.85 or less by mass; <1> or <2> The photosensitive transfer material according to claim 1. <4> the photosensitive resin layer contains an alkali-soluble resin, and the alkali-soluble resin has an acid value of 120 mg / KOH or more; <1> ~ <3> 10. The photosensitive transfer material according to any one of the above items. <5> the photosensitive resin layer contains an alkali-soluble resin, and the alkali-soluble resin contains a structural unit derived from styrene; <1> ~ <4> 10. The photosensitive transfer material according to any one of the above items. <6> The content of structural units derived from styrene is 40% by mass or more based on the total mass of the alkali-soluble resin. <5> The photosensitive transfer material according to claim 1. <7> the photosensitive resin layer contains a polymerizable compound having an acid group; <1> ~ <6> 10. The photosensitive transfer material according to any one of the above items. <8> a thermoplastic resin layer is further provided between the temporary support and the photosensitive resin layer; <1> ~ <7> 10. The photosensitive transfer material according to any one of the above items. <9> <1> ~ <8> a step of laminating a surface of the photosensitive resin layer in the photosensitive transfer material described in any one of the above that is not facing the temporary support to a substrate; a step of patternwise exposing the photosensitive resin layer in the photosensitive transfer material after the laminating step; and a step of developing the photosensitive resin layer after the patternwise exposing step to form a resin pattern. <10> <1> ~ <8> a step of laminating a surface of the photosensitive resin layer in the photosensitive transfer material described in any one of the above that does not face the temporary support to a substrate; a step of pattern-exposing the photosensitive resin layer in the photosensitive transfer material after the laminating step; a step of developing the photosensitive resin layer after the pattern-exposing step to form a resin pattern; and a step of etching the substrate in an area where the resin pattern is not arranged. <11> <1> ~ <8> a step of laminating a surface of the photosensitive resin layer in the photosensitive transfer material described in any one of the above that is not facing the temporary support to a substrate; a step of pattern-exposing the photosensitive resin layer in the photosensitive transfer material after the laminating step; a step of developing the photosensitive resin layer after the pattern-exposing step to form a resin pattern; and a step of etching the substrate in an area where the resin pattern is not arranged. [Effects of the Invention]

[0008] According to one embodiment of the present invention, a photosensitive transfer material can be provided that suppresses the generation of scum (aggregates) even when development is performed for a long period of time. Also, according to other embodiments of the present invention, a method for manufacturing a resin pattern, a method for manufacturing circuit wiring, and a method for manufacturing a touch panel using the above photosensitive transfer material can be provided. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 is a schematic diagram showing an example of the configuration of a photosensitive transfer material. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present disclosure will be described below with reference to the accompanying drawings, in which reference numerals may be omitted.

[0011] In the description of groups (atomic groups) in this specification, when a notation does not specify whether the group is substituted or unsubstituted, it encompasses both unsubstituted and substituted groups. For example, the notation "alkyl group" encompasses not only alkyl groups without a substituent (unsubstituted alkyl groups) but also alkyl groups with a substituent (substituted alkyl groups). In this specification, "(meth)acrylic acid" refers to both or either one of acrylic acid and methacrylic acid, and "(meth)acrylate" refers to both or either one of acrylate and methacrylate. In addition, chemical structural formulas in this specification may be written as simplified structural formulas in which hydrogen atoms are omitted.

[0012] In this specification, when a component contains multiple substances, the amount (content, etc.) of each component means the total amount (total content, etc.) of those multiple substances, unless otherwise specified. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In this specification, "% by mass" and "% by weight" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning.

[0013] In this specification, the term "process" does not only refer to an independent process, but also includes a process that cannot be clearly distinguished from other processes as long as it achieves a desired purpose. In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. In addition, light used for exposure generally includes the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, and extreme ultraviolet light. (Extreme ultraviolet lithography (EUV) light) and actinic rays (active energy rays) such as X-rays.

[0014] In this specification, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) are the same as those of TSKgel GMHxL, TSKgel G4000HxL, TSKgel The compound in a THF (tetrahydrofuran) solvent was detected with a differential refractometer using a gel permeation chromatography (GPC) analyzer equipped with a G2000HxL column (both are product names manufactured by Tosoh Corporation), and the molecular weight was calculated using polystyrene as a standard substance. As used herein, a combination of two or more preferred embodiments is a more preferred embodiment.

[0015] [Photosensitive transfer material] The photosensitive transfer material according to the present disclosure comprises a temporary support and a photosensitive resin layer disposed on the temporary support, and is formed by dissolving 0.1 m of the photosensitive resin layer in 1 liter of a 30°C aqueous solution of 1% by mass of sodium carbonate. 2 The haze of the solution obtained by dissolving the photosensitive transfer material is 60% or less.

[0016] When development is carried out for a long time, scum (aggregates) may form and adhere to the development equipment and the product. Components that form scum (aggregates) include polymerizable compounds and photopolymerization initiators contained in the photosensitive resin layer. When these components aggregate in the developer, the haze of the developer increases.

[0017] The photosensitive transfer material according to the present disclosure is dissolved in 0.1 ml of water in 1 liter of a 30°C aqueous solution of 1% by mass of sodium carbonate. 2 The haze of the solution obtained by dissolving the photosensitive transfer material is 60% or less, so that the developer has low haze even after development processing. By using the photosensitive transfer material according to the present disclosure, the generation of scum (aggregates) can be suppressed even when development processing is carried out for a long period of time.

[0018] The photosensitive transfer material according to the present disclosure will be described in detail below.

[0019] The photosensitive transfer material according to the present disclosure comprises a temporary support and a photosensitive resin layer disposed on the temporary support. The photosensitive resin layer may be disposed directly on the temporary support without any other layer interposed therebetween, or may be disposed via another layer. Furthermore, another layer may be disposed on the surface of the photosensitive resin layer opposite the surface facing the temporary support. Examples of layers other than the temporary support and the photosensitive resin layer include a thermoplastic resin layer, an intermediate layer, and a cover film.

[0020] Fig. 1 shows a schematic diagram of an example of the layer structure of a photosensitive transfer material according to the present disclosure. The photosensitive transfer material 100 shown in Fig. 1 includes a temporary support 10, a thermoplastic resin layer 12, an intermediate layer 14, a photosensitive resin layer 16, and a cover film 18 laminated in this order.

[0021] The photosensitive transfer material according to the present disclosure is dissolved in 1 L (liter) of a 1% by mass aqueous solution of sodium carbonate at 30°C. 2 The haze of the solution obtained by dissolving the photosensitive transfer material is 60% or less. The haze is measured, for example, by the following method.

[0022] First, prepare a 1% by mass aqueous solution of sodium carbonate and adjust the liquid temperature to 30°C. Add 0.02m 2 The photosensitive transfer material is placed in the solution. Stir for 4 hours at 30°C, taking care not to introduce air bubbles. After stirring, the insoluble temporary support is removed and the haze of the solution in which the photosensitive transfer material has dissolved is measured. Haze is measured using a haze meter (product name "NDH4000", manufactured by Nippon Denshoku Industries Co., Ltd.) with a liquid measurement unit and a dedicated liquid measurement cell with an optical path length of 20 mm. If the photosensitive transfer material contains a cover film, peel it off and then place the photosensitive transfer material in a 1% by mass aqueous sodium carbonate solution.

[0023] The haze of the solution obtained by the above method is preferably 30% or less, more preferably 10% or less, even more preferably 5% or less, and particularly preferably 1% or less, from the viewpoint of further suppressing the generation of scum (aggregates) when development processing is carried out for a long period of time.

[0024] <Temporary support> The photosensitive transfer material according to the present disclosure includes a temporary support. The temporary support is a peelable support that supports the photosensitive resin layer or the laminate including the photosensitive resin layer.

[0025] The temporary support preferably has optical transparency from the viewpoint of enabling exposure of the photosensitive resin layer through the temporary support when the photosensitive resin layer is subjected to patternwise exposure. In this specification, "having optical transparency" means that the transmittance of light of the wavelength used for patternwise exposure is 50% or more.

[0026] From the viewpoint of improving the exposure sensitivity of the photosensitive resin layer, the temporary support preferably has a transmittance of 60% or more, more preferably 70% or more, for light of the wavelength used for pattern exposure (preferably a wavelength of 365 nm).

[0027] The transmittance of a layer included in a photosensitive transfer material is the ratio of the intensity of light that passes through the layer and is emitted to the intensity of light that is incident when light is incident in a direction perpendicular to the main surface of the layer (i.e., in the thickness direction). The transmittance is measured using an "MCPD Series" product manufactured by Otsuka Electronics Co., Ltd.

[0028] The temporary support may be a single layer or a laminate of two or more layers.

[0029] Examples of the substrate constituting the temporary support include glass, resin film, and paper. From the viewpoints of strength, flexibility, and light transmittance, the substrate constituting the temporary support is preferably a resin film.

[0030] Examples of the resin film include a polyethylene terephthalate (PET) film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Of these, the resin film is preferably a PET film, and more preferably a biaxially stretched PET film.

[0031] The thickness of the temporary support is not particularly limited, and may be appropriately selected depending on the material from the viewpoints of the strength as a support, the flexibility required for bonding to the circuit wiring formation substrate, and the light transmittance required in the initial exposure step.

[0032] The thickness of the temporary support is preferably 5 μm to 100 μm, and from the viewpoint of ease of handling and versatility, more preferably 10 μm to 50 μm.

[0033] [Photosensitive resin layer] The photosensitive transfer material according to the present disclosure includes a photosensitive resin layer. The photosensitive resin layer is preferably a negative photosensitive resin layer in which the solubility of the exposed portion in a developer solution 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, and may be a positive photosensitive resin layer in which the solubility of the exposed portion in a developer solution is improved by exposure, and the exposed portion is removed by development.

[0034] The photosensitive resin layer can be obtained, for example, by applying a photosensitive resin composition and drying it.

[0035] The photosensitive resin layer preferably contains a polymer A, a polymerizable compound B, and a photopolymerization initiator. The photosensitive resin layer preferably contains 10% by mass to 90% by mass of polymer A, 5% by mass to 70% by mass of polymerizable compound B, and 0.01% by mass to 20% by mass of the photopolymerization initiator, relative to the total mass of the photosensitive resin layer. Each component will be explained below in order.

[0036] <Ingredients> (Polymer A) The polymer A is preferably an alkali-soluble resin. An alkali-soluble resin refers to a polymer that is easily soluble in an alkaline substance. In this specification, "alkali-soluble" means that the solubility in 100 g of a 1% by mass aqueous solution of sodium carbonate at 22°C is 0.1 g or more.

[0037] The acid value of polymer A is preferably 120 mgKOH / g or more, more preferably 150 mgKOH / g or more, and even more preferably 180 mgKOH / g or more, from the viewpoint of further suppressing the generation of scum (aggregates) when development processing is carried out for a long period of time. The alkali-soluble resin acts as a dispersant in the developer. When the acid value of the alkali-soluble resin is 120 mgKOH / g or more, it is highly effective in dispersing components that are not soluble in the developer, and it is thought that the generation of scum (aggregates) can be suppressed.

[0038] There is no particular upper limit to the acid value of polymer A. From the viewpoint of resolution, the acid value of polymer A is preferably 220 mgKOH / g or less, and more preferably 200 mgKOH / g or less.

[0039] The acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of sample.

[0040] In this specification, the unit of acid value is expressed as mgKOH / g. The acid value can be calculated, for example, from the average content of acid groups in the compound.

[0041] The acid value of polymer A may be adjusted by changing the type of structural unit constituting polymer A and the content of structural units containing an acid group.

[0042] The weight-average molecular weight of polymer A is preferably 5,000 to 500,000. A weight-average molecular weight of 500,000 or less is preferred because it improves resolution and developability. The weight-average molecular weight of polymer A is more preferably 100,000 or less, even more preferably 60,000 or less, and particularly preferably 50,000 or less. On the other hand, a weight-average molecular weight of 5,000 or more is preferred because it allows for control of the properties of the developed aggregates and the properties of the unexposed film, such as edge fusing and cut-chip resistance, when formed into a photosensitive resin laminate. The weight-average molecular weight of polymer A is more preferably 10,000 or more, even more preferably 20,000 or more, and particularly preferably 30,000 or more. Edge fusing refers to the degree to which the photosensitive resin layer easily protrudes from the edge of a roll when the photosensitive resin laminate is wound into a roll. The cut chip property refers to the degree to which chips fly off when an unexposed film is cut with a cutter. If these chips adhere to the upper surface of the photosensitive resin laminate, they will be transferred to a mask in a subsequent exposure step, causing defective products.

[0043] The dispersity of polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0. In the present disclosure, the molecular weight is a value measured using gel permeation chromatography. The dispersity is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight).

[0044] From the viewpoint of suppressing line width thickening and resolution degradation caused by shifts in the focal position during exposure, polymer A preferably contains a structural unit derived from a monomer having an aromatic hydrocarbon group. Examples of aromatic hydrocarbon groups include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group. The content of structural units derived from monomers having an aromatic hydrocarbon group in polymer A is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, particularly preferably 45% by mass or more, and most preferably 50% by mass or more, based on the total mass of polymer A. The upper limit of this content is not particularly limited. The content is preferably 95% by mass or less, more preferably 85% by mass or less, based on the total mass of polymer A. When multiple types of polymer A are contained, the content of structural units derived from monomers having an aromatic hydrocarbon group is determined as a weight average value.

[0045] Examples of the monomer having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer). Among these, the monomer having an aromatic hydrocarbon group is preferably a monomer having an aralkyl group or styrene, and more preferably styrene.

[0046] When the monomer having an aromatic hydrocarbon group is styrene, the content of structural units derived from styrene is preferably 40% by mass or more, more preferably 40% by mass to 80% by mass, even more preferably 45% by mass to 70% by mass, and particularly preferably 50% by mass to 55% by mass, based on the total mass of polymer A.

[0047] The aralkyl group includes a substituted or unsubstituted phenylalkyl group (excluding a benzyl group) and a substituted or unsubstituted benzyl group. The aralkyl group is preferably a substituted or unsubstituted benzyl group.

[0048] An example of a monomer having a phenylalkyl group is phenylethyl (meth)acrylate.

[0049] Examples of the monomer having a benzyl group include (meth)acrylates having a benzyl group and vinyl monomers having a benzyl group. Examples of the (meth)acrylates having a benzyl group include benzyl (meth)acrylate and chlorobenzyl (meth)acrylate. Examples of the vinyl monomer having a benzyl group include vinylbenzyl chloride and vinylbenzyl alcohol. Among them, the monomer having a benzyl group is preferably benzyl (meth)acrylate. When the monomer having an aromatic hydrocarbon group is benzyl (meth)acrylate, the content of the structural unit derived from benzyl (meth)acrylate is preferably 50% by mass to 95% by mass, more preferably 60% by mass to 90% by mass, even more preferably 70% by mass to 90% by mass, and particularly preferably 75% by mass to 90% by mass, based on the total mass of polymer A.

[0050] The polymer A containing a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably a polymer containing a structural unit derived from a monomer having an aromatic hydrocarbon group and a structural unit derived from at least one monomer selected from the group consisting of a first monomer described below and a second monomer described below.

[0051] Polymer A that does not contain a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably a polymer that contains a structural unit derived from at least one monomer selected from the group consisting of a first monomer and a second monomer, and more preferably a polymer that contains a structural unit derived from at least one first monomer and at least one second monomer.

[0052] The first monomer is a monomer having an anionic group and at least one polymerizable unsaturated group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. Among these, the first monomer is preferably (meth)acrylic acid.

[0053] The content of the structural units derived from the first monomer in polymer A is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and even more preferably 15% by mass to 30% by mass, relative to the total mass of polymer A.

[0054] In this specification, "(meth)acrylic acid" means acrylic acid or methacrylic acid, "(meth)acryloyl group" means acryloyl group or methacryloyl group, and "(meth)acrylate" means "acrylate" or "methacrylate".

[0055] The second monomer is a monomer that does not have an anionic group and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; vinyl esters such as vinyl acetate; and (meth)acrylonitrile. Among these, the second monomer is preferably methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or n-butyl (meth)acrylate, with methyl (meth)acrylate being particularly preferred.

[0056] The content of the structural units derived from the second monomer in polymer A is preferably 5% by mass to 60% by mass, more preferably 15% by mass to 50% by mass, and even more preferably 20% by mass to 45% by mass, relative to the total mass of polymer A.

[0057] From the viewpoint of suppressing line width thickening and resolution degradation caused by shifts in the focal position during exposure, polymer A preferably contains a structural unit derived from at least one monomer selected from the group consisting of a monomer having an aralkyl group and styrene. Specifically, polymer A is preferably a copolymer containing a structural unit derived from styrene, a structural unit derived from methyl methacrylate, and a structural unit derived from methacrylic acid.

[0058] In a first embodiment, polymer A preferably contains 25% to 40% by mass of structural units derived from a monomer having an aromatic hydrocarbon group, 20% to 35% by mass of structural units derived from a first monomer, and 30% to 45% by mass of structural units derived from a second monomer. In a second embodiment, polymer A preferably contains 70% to 90% by mass of structural units derived from a monomer having an aromatic hydrocarbon group, and 10% to 25% by mass of structural units derived from the first monomer. In a third embodiment, polymer A preferably contains 40% to 60% by mass of structural units derived from a monomer having an aromatic hydrocarbon group, 20% to 35% by mass of structural units derived from the first monomer, and 10% to 25% by mass of structural units derived from the second monomer.

[0059] The polymer A may have a branched structure or an alicyclic structure in the side chain. The branched structure or the alicyclic structure can be introduced into the side chain of the polymer A by using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain.

[0060] Examples of the monomer containing a group having a branched structure in the side chain include i-propyl (meth)acrylate, i-butyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, i-amyl (meth)acrylate, t-amyl (meth)acrylate, sec-iso-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and t-octyl (meth)acrylate. Among these, the monomer containing a group having a branched structure in the side chain is preferably i-propyl (meth)acrylate, i-butyl (meth)acrylate, or t-butyl (meth)acrylate, more preferably i-propyl (meth)acrylate or t-butyl (meth)acrylate.

[0061] Examples of the monomer containing a group having an alicyclic structure in the side chain include (meth)acrylates having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. Specifically, examples of monomers containing a group having an alicyclic structure in the side chain include (bicyclo[2.2.1]heptyl-2)(meth)acrylate, (meth)acrylate-1-adamantyl, (meth)acrylate-2-adamantyl, (meth)acrylate-3-methyl-1-adamantyl, (meth)acrylate-3,5-dimethyl-1-adamantyl, (meth)acrylate-3-ethyladamantyl, (meth)acrylate-3-methyl-5-ethyl-1-adamantyl, (meth)acrylate-3,5,8-triethyl-1-adamantyl, (meth)acrylate-3,5-dimethyl-8-ethyl-1-adamantyl, (meth)acrylate-2-methyl-2-adamantyl, (meth)acrylate-2-ethyl-2-adamantyl, (meth)acrylate ) 3-hydroxy-1-adamantyl acrylate, octahydro-4,7-menthanoinden-5-yl (meth)acrylate, octahydro-4,7-menthanoinden-1-ylmethyl (meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl (meth)acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, fenchyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, and cyclohexyl (meth)acrylate. Among these, the monomer containing a group having an alicyclic structure in the side chain is preferably cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fenchyl (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecane (meth)acrylate, and particularly preferably cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate.

[0062] The photosensitive resin layer may contain one type of polymer A alone or two or more types. When two or more types of polymer A are contained, the photosensitive resin layer preferably contains two types of polymer A containing structural units derived from a monomer having an aromatic hydrocarbon group. The photosensitive resin layer also preferably contains a polymer A1 containing structural units derived from a monomer having an aromatic hydrocarbon group, and a polymer A2 not containing structural units derived from a monomer having an aromatic hydrocarbon group. In the latter case, the content of polymer A1 is preferably 50% by mass or more, more preferably 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more, based on the total mass of polymer A.

[0063] The synthesis of polymer A is preferably carried out by adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to a solution obtained by diluting one or more of the above monomers with a solvent such as acetone, methyl ethyl ketone, or isopropanol, and stirring the mixture while heating. After the reaction is complete, further solvent may be added to adjust the concentration to the desired level. Polymerization methods include bulk polymerization, suspension polymerization, and emulsion polymerization, in addition to solution polymerization.

[0064] The glass transition temperature Tg of the polymer A is preferably 30°C to 135°C. By incorporating a polymer A having a Tg of 135°C or less into the photosensitive resin layer, it is possible to suppress line width thickening and resolution degradation when the focus position is shifted during exposure. The Tg of the polymer A is more preferably 130°C or less, even more preferably 120°C or less, and particularly preferably 110°C or less. Furthermore, incorporating a polymer A having a Tg of 30°C or more into the photosensitive resin layer is preferable from the viewpoint of improving edge fuse resistance. The Tg of the polymer A is more preferably 40°C or more, even more preferably 50°C or more, particularly preferably 60°C or more, and most preferably 70°C or more.

[0065] The content of polymer A is preferably in the range of 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, and even more preferably 40% by mass to 60% by mass, relative to the total mass of the photosensitive resin layer. It is preferable that the content of polymer A relative to the total mass of the photosensitive resin layer is 90% by mass or less, since this allows for control of the development time. On the other hand, it is preferable that the content of polymer A relative to the total mass of the photosensitive resin layer is 10% by mass or more, since this improves edge fuse resistance.

[0066] (Polymerizable compound B) The photosensitive resin layer contains a polymerizable compound B having a polymerizable group. In this specification, the term "polymerizable compound" refers to a compound that is polymerized by the action of a polymerization initiator described below, and is different from the polymer A described above.

[0067] The polymerizable group contained in the polymerizable compound B is not particularly limited as long as it is a group that participates in a polymerization reaction, and examples thereof include ethylenically unsaturated groups such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group; and cationically polymerizable groups such as an epoxy group and an oxetane group.

[0068] The polymerizable group is preferably an ethylenically unsaturated group, more preferably an acryloyl group or a methacryloyl group.

[0069] As the polymerizable compound B, a compound having one or more ethylenically unsaturated groups (i.e., an ethylenically unsaturated compound) is preferred, and a compound having two or more ethylenically unsaturated groups in one molecule (i.e., a polyfunctional ethylenically unsaturated compound) is more preferred, in that the photosensitivity of the photosensitive resin layer is superior.

[0070] In terms of achieving better resolution and releasability, the number of ethylenically unsaturated groups that the ethylenically unsaturated compound has in one molecule is preferably 6 or less, more preferably 3 or less, and even more preferably 2 or less.

[0071] The photosensitive resin layer preferably contains a bifunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule, or a trifunctional ethylenically unsaturated compound having three ethylenically unsaturated groups, in that the photosensitive resin layer has a better balance of photosensitivity, resolution, and releasability, and more preferably contains a bifunctional ethylenically unsaturated compound.

[0072] From the viewpoint of excellent releasability, the content of the bifunctional ethylenically unsaturated compound is preferably 60% by mass or more, and more preferably 70% by mass or more, based on the total mass of the polymerizable compound B. The upper limit of the content of the bifunctional ethylenically unsaturated compound is not particularly limited and may be 100% by mass. That is, all of the polymerizable compound B contained in the photosensitive resin layer may be a bifunctional ethylenically unsaturated compound.

[0073] The ethylenically unsaturated compound is preferably a (meth)acrylate compound.

[0074] -Polymerizable compound B1- The photosensitive resin layer preferably contains a polymerizable compound B1 having at least one aromatic ring and two ethylenically unsaturated groups in one molecule.

[0075] Examples of the aromatic ring contained in the polymerizable compound B1 include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, and an anthracene ring; aromatic heterocycles such as a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring, and a pyridine ring; and condensed rings thereof. The aromatic ring contained in the polymerizable compound B1 is preferably an aromatic hydrocarbon ring, more preferably a benzene ring. The aromatic ring may have a substituent.

[0076] The polymerizable compound B1 preferably has a bisphenol skeleton from the viewpoint of suppressing swelling of the photosensitive resin layer due to a developer and improving resolution.

[0077] Examples of the bisphenol skeleton include a bisphenol A skeleton derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), a bisphenol F skeleton derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and a bisphenol B skeleton derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane). Of these, the bisphenol skeleton is preferably a bisphenol A skeleton.

[0078] Examples of the polymerizable compound B1 having a bisphenol skeleton include a compound having a bisphenol skeleton and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol skeleton.

[0079] The bisphenol skeleton and the polymerizable group may be bonded directly or via one or more alkyleneoxy groups. The alkyleneoxy group bonded to the bisphenol skeleton is preferably an ethyleneoxy group or a propyleneoxy group, and more preferably an ethyleneoxy group. The number of alkyleneoxy groups added to the bisphenol skeleton is not particularly limited. The number of alkyleneoxy groups added per molecule is preferably 4 to 16, and more preferably 6 to 14.

[0080] The polymerizable compound B1 having a bisphenol skeleton is described in paragraphs 0072 to 0080 of JP-A-2016-224162, the contents of which are incorporated herein by reference.

[0081] The polymerizable compound B1 is preferably a bifunctional ethylenically unsaturated compound having a bisphenol A skeleton, and more preferably 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane.

[0082] Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), and 2,2-bis(4-(methacryloxydodecaethoxy)phenyl)propane. Examples of suitable ethoxylated bisphenol A diacrylates include 2,2-bis(4-(methacryloxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.), and ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0083] The polymerizable compound B1 includes a compound represented by the following general formula (I). [ka] In the formula, R 1 and R 2 each independently represent a hydrogen atom or a methyl group, A is C2H4, B is C3H6, n1 and n3 each independently represent an integer of 1 to 39, and n1 + n3 is an integer of 2 to 40, n2 and n4 each independently represent an integer of 0 to 29, and n2 + n4 is an integer of 0 to 30, and the arrangement of the -(AO)- and -(BO)- repeating units may be random or block. In the case of a block, either -(AO)- or -(BO)- may be on the bisphenol group side.

[0084] n1+n2+n3+n4 is preferably 2 to 20, more preferably 2 to 16, and even more preferably 4 to 12. Furthermore, n2+n4 is preferably 0 to 10, more preferably 0 to 4, even more preferably 0 to 2, and particularly preferably 0.

[0085] The photosensitive resin layer may contain one type of polymerizable compound B1 alone or two or more types of polymerizable compound B1.

[0086] In the photosensitive resin layer, the content of polymerizable compound B1 is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 55% by mass or more, and particularly preferably 60% by mass or more, based on the total mass of polymerizable compound B, from the viewpoint of superior resolution. There is no particular upper limit for the content of polymerizable compound B1. In terms of releasability, the content of polymerizable compound B1 is preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, and particularly preferably 85% by mass or less, based on the total mass of polymerizable compound B.

[0087] -Polymerizable compound B2- The photosensitive resin layer preferably contains a polymerizable compound B2 having an acid group, which disperses components that are insoluble in the developer, thereby preventing the formation of scum (aggregates).

[0088] Examples of the acid group include a carboxy group, a phenolic hydroxyl group, a sulfonic acid group, and a phosphoric acid group.

[0089] Examples of polymerizable compounds containing a carboxy group include unsaturated fatty acids such as acrylic acid, methacrylic acid, phthalic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, and cinnamon acid, and polyfunctional acrylate compounds modified with a carboxy group. Examples of polyfunctional acrylate compounds modified with a carboxy group include succinic acid-modified pentaerythritol triacrylate, succinic acid-modified trimethylolpropane triacrylate, succinic acid-modified pentaerythritol tetraacrylate, succinic acid-modified dipentaerythritol pentaacrylate, succinic acid-modified dipentaerythritol hexaacrylate, adipic acid-modified pentaerythritol triacrylate, adipic acid-modified trimethylolpropane triacrylate, adipic acid-modified pentaerythritol tetraacrylate, adipic acid-modified dipentaerythritol pentaacrylate, and adipic acid-modified dipentaerythritol tetraacrylate. The carboxy-modified polyfunctional acrylate compound may be a commercially available product, such as Aronix M-510, Aronix M-520, Aronix TO-2349, and Aronix TO-2359 (all manufactured by Toagosei Co., Ltd.).

[0090] Examples of the polymerizable compound containing a phenolic hydroxyl group include p-hydroxystyrene, 3,4-dihydroxystyrene, 3,5-dihydroxystyrene, 2,4,6-trihydroxystyrene, (p-hydroxy)benzyl acrylate, salicylic acid-modified pentaerythritol triacrylate, salicylic acid-modified trimethylolpropane triacrylate, salicylic acid-modified pentaerythritol tetraacrylate, salicylic acid-modified dipentaerythritol pentaacrylate, and salicylic acid-modified dipentaerythritol hexaacrylate.

[0091] Examples of polymerizable compounds containing a sulfonic acid group include vinyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, and butyl sulfonic acid-modified acrylamide.

[0092] Examples of polymerizable compounds containing a phosphate group include vinyl phosphate, styrene phosphate, and butyl phosphate-modified acrylamide.

[0093] Among these, the polymerizable compound B2 having an acid group is preferably a polymerizable compound having a carboxy group, from the viewpoint of further dispersing the components that are insoluble in the developer.

[0094] The photosensitive resin layer may contain one type of polymerizable compound B2 alone or two or more types of polymerizable compound B2.

[0095] In order to further disperse the components that are insoluble in the developer, the content of the polymerizable compound B2 in the photosensitive resin layer is preferably 10% by mass to 40% by mass, more preferably 15% by mass to 35% by mass, and even more preferably 20% by mass to 30% by mass, relative to the total mass of the polymerizable compound B.

[0096] The photosensitive resin layer may contain a polymerizable compound B other than the polymerizable compound B1. The photosensitive resin layer may also contain a polymerizable compound B other than the polymerizable compound B2. The polymerizable compound B other than the polymerizable compound B1 and the polymerizable compound B2 is not particularly limited and can be appropriately selected from known compounds. For example, the polymerizable compound B other than the polymerizable compound B1 and the polymerizable compound B2 includes a compound having one ethylenically unsaturated group in one molecule (i.e., a monofunctional ethylenically unsaturated compound), a bifunctional ethylenically unsaturated compound having no aromatic ring, and a trifunctional or higher ethylenically unsaturated compound.

[0097] Examples of monofunctional ethylenically unsaturated compounds include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate.

[0098] Examples of bifunctional ethylenically unsaturated compounds having no aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate.

[0099] Examples of alkylene glycol di(meth)acrylates include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate.

[0100] Examples of polyalkylene glycol di(meth)acrylates include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate.

[0101] Examples of urethane di(meth)acrylates include propylene oxide-modified urethane di(meth)acrylates and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates. Commercially available products include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0102] Examples of tri- or higher functional ethylenically unsaturated compounds include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, and the like. Examples thereof include acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide modified products thereof.

[0103] Here, "(tri / tetra / penta / hexa)(meth)acrylate" is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate.

[0104] The photosensitive resin layer preferably contains a polymerizable compound B1 and a tri- or higher functional ethylenically unsaturated compound, more preferably a polymerizable compound B1 and two or more tri- or higher functional ethylenically unsaturated compounds. In this case, the mass ratio of the polymerizable compound B1 to the tri- or higher functional ethylenically unsaturated compounds (total mass of the polymerizable compound B1:total mass of the tri- or higher functional ethylenically unsaturated compounds) is preferably 1:1 to 5:1, more preferably 1.2:1 to 4:1, and even more preferably 1.5:1 to 3:1.

[0105] Examples of alkylene oxide-modified trifunctional or higher ethylenically unsaturated compounds include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20, manufactured by Nippon Kayaku Co., Ltd.; A-9300-1CL, manufactured by Shin-Nakamura Chemical Co., Ltd.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040, manufactured by Nippon Kayaku Co., Ltd.; ATM-35E and A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.; EBECRYL (registered trademark) 135, manufactured by Daicel-Allnex Corporation), ethoxylated glycerin triacrylate (A-GLY-9E, manufactured by Shin-Nakamura Chemical Co., Ltd.), ARONIX (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), ARONIX M-520 (manufactured by Toagosei Co., Ltd.), and ARONIX M-510 (manufactured by Toagosei Co., Ltd.).

[0106] The photosensitive resin layer may contain one type of polymerizable compound B alone or two or more types thereof.

[0107] The content of the polymerizable compound B is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and even more preferably 20% by mass to 50% by mass, based on the total mass of the photosensitive resin layer.

[0108] The weight average molecular weight (Mw) of the polymerizable compound B is preferably from 200 to 3,000, more preferably from 280 to 2,200, and even more preferably from 300 to 2,200.

[0109] The ratio of the content of polymerizable compound B to the content of polymer A (preferably alkali-soluble resin) is preferably 0.85 or less by mass, more preferably 0.5 to 0.85, even more preferably 0.6 to 0.85, and particularly preferably 0.75 to 0.85. At this ratio, polymerizable compound B, which is insoluble in the developer, becomes oil droplets, and the alkali-soluble resin acts as a dispersant to prevent the oil droplets from coalescing, thereby preventing the formation of scum (aggregates).

[0110] (optional ingredient) The photosensitive resin layer may contain components other than the polymer A and the polymerizable compound B.

[0111] -Photopolymerization initiator- The photosensitive resin layer preferably contains a photopolymerization initiator.

[0112] A photopolymerization initiator is a compound that has the effect of initiating polymerization of a polymerizable compound by actinic rays such as ultraviolet rays, visible light, X-rays, etc. The photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used.

[0113] Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator. Among them, the photopolymerization initiator is preferably a photoradical polymerization initiator.

[0114] Examples of the photoradical polymerization initiator include a photopolymerization initiator having an oxime ester skeleton, a photopolymerization initiator having an α-aminoalkylphenone skeleton, a photopolymerization initiator having an α-hydroxyalkylphenone skeleton, a photopolymerization initiator having an acylphosphine oxide skeleton, and a photopolymerization initiator having an N-phenylglycine skeleton.

[0115] From the viewpoints of photosensitivity, visibility of exposed and unexposed areas, and resolution, the photosensitive resin layer preferably contains, as a photoradical polymerization initiator, at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof. Note that the two 2,4,5-triarylimidazole skeletons in the 2,4,5-triarylimidazole dimers and derivatives thereof may be the same or different.

[0116] Examples of derivatives of 2,4,5-triarylimidazole dimers include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0117] The photoradical polymerization initiator may be a polymerization initiator described in paragraphs 0031 to 0042 of JP-A No. 2011-95716 and paragraphs 0064 to 0081 of JP-A No. 2015-14783.

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

[0119] Commercially available photoradical polymerization initiators include, for example, 2,4-bis(trichloromethyl)-6-[2-(4-methylphenyl)ethenyl]-1,3,5-triazine (trade name: TAZ-110, manufactured by Midori Chemical Industry Co., Ltd.), (trade name: TAZ-111, manufactured by Midori Chemical Industry Co., Ltd.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime) (trade name: Irgacure® OXE-01, manufactured by BASF Japan Ltd.), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (trade name: Irgacure® OXE-01, manufactured by BASF Japan Ltd.), and OXE-02, manufactured by BASF Japan Ltd.), Irgacure OXE-03 (manufactured by BASF Japan Ltd.), Irgacure OXE-04 (manufactured by BASF Japan Ltd.), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins BV), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907, manufactured by IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (trade name: Omnirad 127, manufactured by IGM Resins BV), BV), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (trade name: Omnirad 369, IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, IGM Resins BV), 1-hydroxycyclohexyl phenyl ketone (trade name: Omnirad 184, IGM Resins BV), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651, IGM Resins BV), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, IGM Resins BV).Examples of photopolymerization initiators include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, manufactured by IGM Resins BV), oxime ester-based photopolymerization initiators (trade name: Lunar 6, manufactured by DKSH Japan Co., Ltd.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (trade name: B-CIM, manufactured by Hampford Chemical Industry Co., Ltd.), and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.).

[0120] A photocationic polymerization initiator (photoacid generator) is a compound that generates an acid when exposed to actinic rays. There are no particular limitations on the photocationic polymerization initiator, but it is preferably a compound that responds to actinic rays with a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid. Even if a compound is not directly sensitive to actinic rays with a wavelength of 300 nm or more, it can be preferably used in combination with a sensitizer as long as it responds to actinic rays with a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer.

[0121] The cationic photopolymerization initiator is preferably a cationic photopolymerization initiator that generates an acid having a pKa of 4 or less, more preferably a cationic photopolymerization initiator that generates an acid having a pKa of 3 or less, and particularly preferably a cationic photopolymerization initiator that generates an acid having a pKa of 2 or less. The lower limit of the pKa is not particularly limited, and is preferably, for example, −10.0.

[0122] Examples of the photocationic polymerization initiator include an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator.

[0123] Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.

[0124] The ionic photocationic polymerization initiator may be an ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of JP-A No. 2014-85643.

[0125] Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triazine compounds, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. The trichloromethyl-s-triazine compounds, diazomethane compounds, and imide sulfonate compounds may be compounds described in paragraphs 0083 to 0088 of JP 2011-221494 A. The oxime sulfonate compounds may be compounds described in paragraphs 0084 to 0088 of WO 2018 / 179640 A.

[0126] The photosensitive resin layer may contain one type of photopolymerization initiator alone or two or more types of photopolymerization initiators.

[0127] The content of the photopolymerization initiator is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, relative to the total mass of the photosensitive resin layer. The upper limit of the content of the photopolymerization initiator is not particularly limited. The content of the photopolymerization initiator is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the photosensitive resin layer.

[0128] -Dye- From the viewpoints of the visibility of exposed and unexposed areas, the pattern visibility after development, and resolution, the photosensitive resin layer preferably contains a dye (hereinafter simply referred to as "dye N") that has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 nm to 780 nm during color development and whose maximum absorption wavelength changes in response to an acid, a base, or a radical. When dye N is contained, adhesion to adjacent layers (for example, a temporary support and an intermediate layer) is improved, resulting in better resolution, although the detailed mechanism is unknown.

[0129] In this specification, the expression "the maximum absorption wavelength of a dye changes in response to an acid, a base, or a radical" may mean any of an embodiment in which a dye in a colored state is decolorized by an acid, a base, or a radical, an embodiment in which a dye in a decolorized state develops color by an acid, a base, or a radical, and an embodiment in which a dye in a colored state changes to a colored state of another hue.

[0130] Specifically, dye N may be a compound that changes from a decolorized state to develop a color upon exposure, or may be a compound that changes from a colored state to decolorize upon exposure. In this case, dye N may be a dye whose color-developing or decolorizing state changes when an acid, base, or radical is generated in the photosensitive resin layer upon exposure, or a dye whose color-developing or decolorizing state changes when the state (e.g., pH) in the photosensitive resin layer changes due to an acid, base, or radical. Dye N may also be a dye whose color-developing or decolorizing state changes upon direct exposure to an acid, base, or radical as a stimulus, without being exposed to light.

[0131] Among these, from the viewpoints of the visibility of exposed and unexposed areas and resolution, dye N is preferably a dye whose maximum absorption wavelength changes in response to an acid or a radical, and more preferably a dye whose maximum absorption wavelength changes in response to a radical.

[0132] From the viewpoints of the visibility of exposed and unexposed areas and resolution, the photosensitive resin layer preferably contains both a dye whose maximum absorption wavelength changes in response to radicals as dye N, and a photoradical polymerization initiator.

[0133] From the viewpoint of visibility of exposed and unexposed areas, dye N is preferably a dye that develops color in response to an acid, a base, or a radical.

[0134] An example of the color-developing mechanism of dye N is an embodiment in which a photoradical polymerization initiator, a cationic photopolymerization initiator (photoacid generator), or a photobase generator is added to a photosensitive resin layer, and color is developed by a radical, acid, or base generated from the photoradical polymerization initiator, the cationic photopolymerization initiator, or the photobase generator after exposure.

[0135] From the viewpoint of visibility of exposed and unexposed areas, dye N preferably has a maximum absorption wavelength of 550 nm or more in the wavelength range of 400 nm to 780 nm upon color development, more preferably 550 to 700 nm, and even more preferably 550 to 650 nm.

[0136] Furthermore, dye N may have only one or two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm when it develops color. When dye N has two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm when it develops color, it is sufficient that the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths is 450 nm or longer.

[0137] The maximum absorption wavelength of dye N can be obtained by measuring the transmission spectrum of a solution containing dye N (liquid temperature 25°C) in the range of 400 nm to 780 nm using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) in an atmospheric environment and detecting the wavelength at which the light intensity is minimum (i.e., the maximum absorption wavelength).

[0138] Examples of the dye that develops or loses color upon exposure include leuco compounds. Examples of the dye that loses color upon exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes. Among these, dye N is preferably a leuco compound from the viewpoint of visibility of exposed and unexposed areas.

[0139] Examples of leuco compounds include leuco compounds having a triarylmethane skeleton (triarylmethane-based dyes), leuco compounds having a spiropyran skeleton (spiropyran-based dyes), leuco compounds having a fluoran skeleton (fluoran-based dyes), leuco compounds having a diarylmethane skeleton (diarylmethane-based dyes), leuco compounds having a rhodamine lactam skeleton (rhodamine lactam-based dyes), leuco compounds having an indolylphthalide skeleton (indolylphthalide-based dyes), and leuco compounds having a leucoauramine skeleton (leucoauramine-based dyes).

[0140] Among these, the leuco compound is preferably a triarylmethane dye or a fluoran dye, and more preferably a leuco compound having a triphenylmethane skeleton (triphenylmethane dye) or a fluoran dye.

[0141] From the viewpoint of visibility of exposed and unexposed areas, the leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring. The lactone ring, sultine ring, or sultone ring of the leuco compound changes from a closed state to a ring-open state and develops color, or changes from a ring-open state to a closed state and loses color, upon reaction with a radical generated from a photoradical polymerization initiator or an acid generated from a photocationic polymerization initiator. The leuco compound is preferably a compound having a lactone ring, a sultine ring, or a sultone ring that develops color upon ring-opening by a radical or an acid, and more preferably a compound having a lactone ring that develops color upon ring-opening by a radical or an acid.

[0142] Examples of the dye N include the following dyes and leuco compounds. The dyes used include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, quinaldine red, rose bengal, metanil yellow, thymolsulfophthalein, xylenol blue, methyl orange, paramethyl red, Congo red, benzopurpurin 4B, α-naphthyl red, Nile blue 2B, Nile blue A, methyl violet, malachite green, parafuchsin, Victoria Pure Blue-naphthalenesulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Co., Ltd.), Oil Pink #312 (manufactured by Orient Chemical Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Co., Ltd.), and Oil Scarlet #308 (manufactured by Orient Chemical Co., Ltd.). Co., Ltd.), Oil Red OG (Orient Chemical Industries 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-pN,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0143] Examples of leuco compounds include p,p',p"-hexamethyltriaminotriphenylmethane (leuco crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl leucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(Np-tolyl-N-ethyl)aminofluoran, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluoran, 3,6-dimethoxyfluoran, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluoran, and 3-(N-cyclohexyl-N-methylamino)- 6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-xylidinofluoran, 3-(N,N-diethylamino)-6-methyl-7-chlorofluoran, 3-(N,N-diethylamino)-6-methoxy-7-aminofluoran, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluoran, 3-(N,N-diethylamino)-7-chlorofluoran, 3-(N,N-di 3-(N,N-Diethylamino)-7-benzylaminofluoran, 3-(N,N-Diethylamino)-7,8-benzofluoran, 3-(N,N-Dibutylamino)-6-methyl-7-anilinofluoran, 3-(N,N-Dibutylamino)-6-methyl-7-xylidinofluoran, 3-Piperidino-6-methyl-7-anilinofluoran, 3-Pyrrolidino-6-methyl-7-anilinofluoran, 3,3-Bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-Bis(1-n-butyl-2- 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-phthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthen-3-one.

[0144] From the viewpoints of the visibility of exposed and unexposed areas, the pattern visibility after development, and resolution, dye N is preferably a dye whose maximum absorption wavelength changes in response to radicals, and more preferably a dye that develops color in response to radicals.

[0145] Dye N is preferably leuco crystal violet, crystal violet lactone, brilliant green, or Victoria Pure Blue-naphthalene sulfonate.

[0146] The photosensitive resin layer may contain one type of dye N alone or two or more types thereof.

[0147] From the viewpoints of the visibility of exposed and unexposed areas, the pattern visibility after development, and resolution, the content of dye N is preferably 0.1 mass % or more, more preferably 0.1 mass % to 10 mass %, even more preferably 0.1 mass % to 5 mass %, and particularly preferably 0.1 mass % to 1 mass %, relative to the total mass of the photosensitive resin layer.

[0148] The content of dye N means the content of dye when all of the dye N contained in the photosensitive resin layer is in a color-developing state. Hereinafter, a method for quantifying the content of dye N will be described using a dye that develops color by radicals as an example.

[0149] Solutions were prepared by dissolving 0.001 g and 0.01 g of dye in 100 mL of methyl ethyl ketone. A photoradical polymerization initiator (Irgacure OXE01, manufactured by BASF Japan) was added to each solution, and radicals were generated by irradiating the solution with 365 nm light, causing all dyes to develop color. The absorbance of each solution was then measured at 25°C using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) under atmospheric conditions, and a calibration curve was created.

[0150] Next, the absorbance of the solution in which all the dye has developed is measured in the same manner as above, except that 3 g of the photosensitive resin layer is dissolved in methyl ethyl ketone instead of the dye.The content of the dye contained in the photosensitive resin layer is calculated based on the absorbance of the obtained solution containing the photosensitive resin layer and a calibration curve.

[0151] -Surfactants- From the viewpoint of thickness uniformity, the photosensitive resin layer preferably contains a surfactant.

[0152] Examples of surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. Of these, nonionic surfactants are preferred.

[0153] Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based nonionic surfactants, and fluorine-based nonionic surfactants.

[0154] From the viewpoint of improving resolution, the photosensitive resin layer preferably contains a fluorine-based nonionic surfactant, which is believed to be because the inclusion of a fluorine-based nonionic surfactant in the photosensitive resin layer inhibits penetration of the etching solution into the photosensitive resin layer, thereby reducing side etching.

[0155] Commercially available fluorine-based nonionic surfactants include, for example, Megafac F-551, F-552, and F-554 (all manufactured by DIC Corporation).

[0156] Commercially available fluorine-based surfactants include, for example, Megafac 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, and F-568. , F-575, F-780, EXP, MFS-330, MFS-578, MFS-579, MFS-586, MFS-587, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (all manufactured by DIC Corporation), Florard 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 AGC Inc.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA), Futergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (all manufactured by NEOS Corporation), etc. Examples include:

[0157] Furthermore, as the fluorosurfactant, an acrylic compound having a molecular structure with a functional group containing a fluorine atom, which cleaves the functional group containing the fluorine atom when heated, and the fluorine atom volatilizes, can also be suitably used. Examples of such a fluorosurfactant include the Megafac DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016), for example, Megafac DS-21. As the fluorine-based surfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. Furthermore, a block polymer can also be used as the fluorine-based surfactant. Furthermore, as the fluorine-based surfactant, a fluorine-containing polymer compound containing a structural unit derived from a (meth)acrylate compound having a fluorine atom and a structural unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups) can also be preferably used. As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used, such as Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0158] From the viewpoint of improving environmental friendliness, it is preferable that the fluorine-based surfactant be a surfactant derived from an alternative material to compounds having a linear perfluoroalkyl group having seven or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS).

[0159] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, Pluronic 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 Nippon Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), Paionin D-6112, D-6112-W, D-6315 (all manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (all manufactured by Nissin Chemical Industry Co., Ltd.), and the like.

[0160] Silicone surfactants include linear polymers consisting of siloxane bonds and side chain polymers. Examples include modified siloxane polymers in which organic groups have been introduced into the chain or terminals. Specific examples of silicone 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 (all manufactured by Toray Dow Corning Co., Ltd.), as well as X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, and KF- 945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (all manufactured by Shin-Etsu Silicones Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), BYK307, BYK323, BYK330 (all manufactured by BYK-Chemie), and the like.

[0161] The surfactant may be a surfactant described in paragraphs 0120 to 0125 of International Publication No. 2018 / 179640, a surfactant described in paragraph 0017 of Japanese Patent No. 4502784, and a surfactant described in paragraphs 0060 to 0071 of Japanese Patent Laid-Open No. 2009-237362.

[0162] The photosensitive resin layer may contain one type of surfactant alone or two or more types of surfactants.

[0163] The content of the surfactant is preferably 0.001% by mass to 10% by mass, and more preferably 0.01% by mass to 3% by mass, relative to the total mass of the photosensitive resin layer.

[0164] -Additives- In addition to the above components, the photosensitive resin layer may contain known additives as needed.

[0165] Examples of the additives include radical polymerization inhibitors, sensitizers, plasticizers, heterocyclic compounds, benzotriazoles, carboxybenzotriazoles, resins other than polymer A, and solvents. The photosensitive resin layer may contain one type of each additive alone, or two or more types.

[0166] The photosensitive resin layer may contain a radical polymerization inhibitor.

[0167] Examples of the radical polymerization inhibitor include the thermal polymerization inhibitors described in paragraph 0018 of Japanese Patent No. 4502784. Examples of the radical polymerization inhibitor include phenothiazine, phenoxazine, 4-methoxyphenol, naphthylamine, cuprous chloride, N-nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. Among these, the radical polymerization inhibitor is preferably phenothiazine, phenoxazine, 4-methoxyphenol, or N-nitrosophenylhydroxyamine aluminum salt.

[0168] Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.

[0169] Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole, 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole, and 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole. Examples of commercially available carboxybenzotriazoles include CBT-1 (manufactured by Johoku Chemical Industry Co., Ltd.).

[0170] The total content of the radical polymerization inhibitor, benzotriazoles, and carboxybenzotriazoles is preferably 0.01% by mass to 3% by mass, and more preferably 0.05% by mass to 1% by mass, relative to the total mass of the photosensitive resin layer. When the content is 0.01% by mass or more, the storage stability of the photosensitive resin composition is excellent. On the other hand, when the content is 3% by mass or less, sensitivity can be maintained and decolorization of the dye can be suppressed.

[0171] The photosensitive resin layer may contain a sensitizer.

[0172] The sensitizer is not particularly limited, and known sensitizers, dyes, and pigments can be used. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

[0173] The photosensitive resin layer may contain one type of sensitizer alone or two or more types of sensitizers.

[0174] When the photosensitive resin layer contains a sensitizer, the content of the sensitizer can be appropriately selected depending on the purpose. From the viewpoints of improving sensitivity to a light source and improving the curing rate by balancing the polymerization rate and chain transfer, the content of the sensitizer is preferably 0.01% by mass to 5% by mass, and more preferably 0.05% by mass to 1% by mass, relative to the total mass of the photosensitive resin layer.

[0175] The photosensitive resin layer may contain at least one selected from the group consisting of plasticizers and heterocyclic compounds.

[0176] Examples of the plasticizer and heterocyclic compound include the compounds described in paragraphs 0097 to 0103 and 0111 to 0118 of WO 2018 / 179640.

[0177] The photosensitive resin layer may contain a resin other than the polymer A.

[0178] Examples of resins other than polymer A include acrylic resins, styrene-acrylic copolymers (with the content of structural units derived from styrene being 40% by mass or less), polyurethanes, polyvinyl alcohols, polyvinyl formals, polyamides, polyesters, epoxy resins, polyacetals, polyhydroxystyrenes, polyimides, polybenzoxazoles, polysiloxanes, polyethyleneimines, polyallylamine, and polyalkylene glycols.

[0179] The photosensitive resin layer may contain a solvent. When a photosensitive resin layer is formed by drying a photosensitive resin composition containing a solvent, the solvent may remain in the photosensitive resin layer.

[0180] The photosensitive resin layer may further contain known additives such as metal oxide particles, antioxidants, rust inhibitors, chain transfer agents, dispersants, acid multipliers, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic suspending agents.

[0181] Additives that may be contained in the photosensitive resin layer are described in paragraphs 0165 to 0184 of JP-A No. 2014-85643, the contents of which are incorporated herein by reference.

[0182] <Physical properties etc.> The thickness of the photosensitive resin layer is preferably 10 μm or less, more preferably 5 μm or less, even more preferably 3 μm or less, and particularly preferably 2 μm or less. By reducing the thickness of the photosensitive resin layer, the amount of components contained in the photosensitive resin layer that are not dissolved in the developer can be reduced, thereby suppressing the generation of scum (aggregates). The lower limit of the thickness of the photosensitive resin layer is, for example, 0.5 μm.

[0183] The thickness of each layer of the photosensitive transfer material is calculated by observing a cross section of the photosensitive transfer material in a direction perpendicular to the main surface with a scanning electron microscope (SEM), measuring the thickness of each layer at 10 or more points based on the obtained observation image, and calculating the average value.

[0184] To obtain better adhesion, the transmittance of the photosensitive resin layer at a wavelength of 365 nm is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more. The upper limit of the transmittance of the photosensitive resin layer at a wavelength of 365 nm is not particularly limited, but is preferably 99.9%.

[0185] <Formation method> The method for forming the photosensitive resin layer is not particularly limited as long as it is a method that can form a layer containing the above components.

[0186] Examples of methods for forming the photosensitive resin layer include a method in which a photosensitive resin composition containing a polymer A, a polymerizable compound B, and a solvent is prepared, the photosensitive resin composition is applied to the surface of a temporary support or the like, and the coating film of the photosensitive resin composition is dried to form the layer.

[0187] The photosensitive resin composition used to form the photosensitive resin layer may be, for example, a composition containing a polymer A, a polymerizable compound B, the optional components described above, and a solvent.

[0188] The photosensitive resin composition preferably contains a solvent in order to adjust the viscosity of the photosensitive resin composition and facilitate the formation of the photosensitive resin layer.

[0189] (solvent) The solvent contained in the photosensitive resin composition is not particularly limited as long as it can dissolve or disperse the polymer A, the polymerizable compound B, and the above-mentioned optional components, and any known solvent can be used.

[0190] Examples of the solvent include alkylene glycol ethers, alkylene glycol ether acetates, alcohols (e.g., methanol and ethanol), ketones (e.g., acetone and methyl ethyl ketone), aromatic hydrocarbons (e.g., toluene), aprotic polar solvents (e.g., N,N-dimethylformamide), cyclic ethers (e.g., tetrahydrofuran), esters, amides, lactones, and mixed solvents containing two or more of these.

[0191] When preparing a photosensitive transfer material having a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer, the photosensitive resin composition preferably contains at least one selected from the group consisting of alkylene glycol ethers and alkylene glycol ether acetates. Among these, the solvent is more preferably a mixed solvent containing at least one selected from the group consisting of alkylene glycol ethers and alkylene glycol ether acetate solvents and at least one selected from the group consisting of ketones and cyclic ethers, and even more preferably a mixed solvent containing at least one selected from the group consisting of alkylene glycol ethers and alkylene glycol ether acetates, a ketone, and a cyclic ether.

[0192] Examples of alkylene glycol ethers include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers, and dipropylene glycol dialkyl ethers.

[0193] Examples of alkylene 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.

[0194] The solvent may be a solvent described in paragraphs 0092 to 0094 of WO 2018 / 179640 and a solvent described in paragraph 0014 of JP 2018-177889 A, the contents of which are incorporated herein by reference.

[0195] The photosensitive resin composition may contain one type of solvent alone or two or more types of solvents. The content of the solvent in the photosensitive resin composition is preferably 50 to 1,900 parts by mass, and more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content in the photosensitive resin composition.

[0196] The method for preparing the photosensitive resin composition is not particularly limited, and examples thereof include a method in which solutions of the components are dissolved in the above-mentioned solvents in advance, and the resulting solutions are mixed in a predetermined ratio to prepare the photosensitive resin composition.

[0197] The photosensitive resin composition is preferably filtered using a filter with a pore size of 0.2 μm to 30 μm before forming the photosensitive resin layer.

[0198] The method for applying the photosensitive resin composition is not particularly limited, and may be any known method, such as slit coating, spin coating, curtain coating, or inkjet coating.

[0199] The photosensitive resin layer may also be formed by applying a photosensitive resin composition onto a cover film, which will be described later, and drying the composition.

[0200] <Impurities, etc.> The photosensitive resin layer may contain a predetermined amount of impurities. Examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Among these, halide ions, sodium ions, and potassium ions are likely to be mixed in as impurities, so the following contents are preferred.

[0201] The content of impurities in the photosensitive resin layer is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less, by mass. The content of impurities in the photosensitive resin layer can be 1 ppb or more, or 0.1 ppm or more, by mass.

[0202] Methods for controlling the impurity content within the above range include selecting raw materials for the photosensitive resin layer that have a low impurity content, preventing impurities from being mixed in when the photosensitive resin layer is formed, and removing impurities by washing when the photosensitive resin layer is formed. By using these methods, the impurity content can be controlled within the above range.

[0203] Impurities can be quantitatively determined by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0204] The content of specific compounds, such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane, in the photosensitive resin layer is preferably low. The content of specific compounds in the photosensitive resin layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less, by mass. The lower limit of the content is preferably 10 ppb, more preferably 100 ppb, by mass. The content of specific compounds can be reduced by the same method as for the above-mentioned impurities. The content of specific compounds can also be quantified by known measurement methods.

[0205] The water content in the photosensitive resin layer is preferably 0.01% by mass to 1.0% by mass, and more preferably 0.05% by mass to 0.5% by mass, from the viewpoint of improving reliability and lamination properties.

[0206] [Thermoplastic resin layer] The photosensitive transfer material according to the present disclosure preferably includes a thermoplastic resin layer between the temporary support and the photosensitive resin layer. When the thermoplastic resin layer is disposed between the temporary support and the photosensitive resin layer, conformability to the substrate in the bonding step is improved, the inclusion of air bubbles between the substrate and the photosensitive transfer material is suppressed, and adhesion to an adjacent layer (for example, the temporary support) is improved.

[0207] <Ingredients> (alkali-soluble resin) The thermoplastic resin layer contains an alkali-soluble resin as the thermoplastic resin.

[0208] In this specification, "alkali-soluble" means that the solubility in 100 g of a 1% by mass aqueous solution of sodium carbonate at 22°C is 0.1 g or more.

[0209] Examples of alkali-soluble resins include acrylic resins, polystyrene, styrene-acrylic copolymers, polyurethanes, polyvinyl alcohols, polyvinyl formals, polyamides, polyesters, epoxy resins, polyacetals, polyhydroxystyrenes, polyimides, polybenzoxazoles, polysiloxanes, polyethyleneimines, polyallylamine, and polyalkylene glycols.

[0210] As the alkali-soluble resin, an acrylic resin is preferred from the viewpoint of developability and adhesion to adjacent layers.

[0211] Here, the acrylic resin means a resin having at least one type of structural unit selected from the group consisting of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid esters, and structural units derived from (meth)acrylic acid amides.

[0212] The acrylic resin preferably contains a total content of constituent units derived from (meth)acrylic acid, constituent units derived from (meth)acrylic acid ester, and constituent units derived from (meth)acrylic acid amide of 50% by mass or more relative to the total mass of the acrylic resin.

[0213] In particular, the total content of the structural units derived from (meth)acrylic acid and the structural units derived from (meth)acrylic acid esters is preferably 30% by mass to 100% by mass, and more preferably 50% by mass to 100% by mass, relative to the total mass of the acrylic resin.

[0214] The alkali-soluble resin is preferably a polymer having an acid group, such as a carboxy group, a sulfo group, a phosphate group, or a phosphonate group, with a carboxy group being preferred.

[0215] The upper limit of the acid value of the alkali-soluble resin is not particularly limited, but the acid value of the alkali-soluble resin is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less.

[0216] The carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited, and can be appropriately selected from known resins.

[0217] Examples of carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or more include alkali-soluble resins that are carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or more among the polymers described in paragraph 0025 of JP-A No. 2011-95716, carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or more among the polymers described in paragraphs 0033 to 0052 of JP-A No. 2010-237589, and carboxyl group-containing acrylic resins having an acid value of 60 mgKOH / g or more among the binder polymers described in paragraphs 0053 to 0068 of JP-A No. 2016-224162.

[0218] The content of the structural unit having a carboxy group in the carboxy group-containing acrylic resin is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and even more preferably 12% by mass to 30% by mass, relative to the total mass of the acrylic resin.

[0219] From the viewpoints of developability and adhesion to adjacent layers, the alkali-soluble resin is particularly preferably an acrylic resin having a structural unit derived from (meth)acrylic acid.

[0220] The alkali-soluble resin may have a reactive group, which may be an addition-polymerizable group, such as an ethylenically unsaturated group, a polycondensable group such as a hydroxy group or a carboxy group, or a polyaddition-reactive group such as an epoxy group or a (blocked) isocyanate group.

[0221] The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably from 10,000 to 100,000, and even more preferably from 20,000 to 50,000.

[0222] The thermoplastic resin layer may contain one kind of alkali-soluble resin alone or two or more kinds of alkali-soluble resins. From the viewpoints of developability and adhesion to adjacent layers, the content of the alkali-soluble resin is preferably 10% by mass to 99% by mass, more preferably 20% by mass to 90% by mass, even more preferably 40% by mass to 80% by mass, and particularly preferably 50% by mass to 70% by mass, relative to the total mass of the thermoplastic resin layer.

[0223] (dye) The thermoplastic resin layer preferably contains a dye (also simply referred to as "dye B") whose maximum absorption wavelength during color development is 450 nm or longer in the wavelength range of 400 nm to 780 nm and whose maximum absorption wavelength changes in response to an acid, a base, or a radical. Preferred aspects of dye B are the same as those of dye N, except for the points described below.

[0224] From the viewpoints of visibility of exposed and unexposed areas and resolution, dye B is preferably a dye whose maximum absorption wavelength changes in response to an acid or radical, and more preferably a dye whose maximum absorption wavelength changes in response to an acid.

[0225] From the viewpoints of visibility and resolution of exposed and unexposed areas, the thermoplastic layer preferably contains both a dye whose maximum absorption wavelength changes in response to an acid as dye B, and a compound that generates an acid when exposed to light, as described below.

[0226] The thermoplastic resin layer may contain one type of dye B alone or two or more types thereof.

[0227] From the viewpoint of visibility of exposed and unexposed areas, the content of dye B is preferably 0.2 mass% or more, more preferably 0.2 mass% to 6 mass%, even more preferably 0.2 mass% to 5 mass%, and particularly preferably 0.25 mass% to 3.0 mass%, relative to the total mass of the thermoplastic resin layer.

[0228] Here, the content of dye B means the content of dye when all of the dye B contained in the thermoplastic resin layer is in a color-developing state. A method for quantifying the content of dye B will be described below using a dye that develops color by radicals as an example.

[0229] Solutions were prepared by dissolving 0.001 g and 0.01 g of dye in 100 mL of methyl ethyl ketone. A photoradical polymerization initiator (Irgacure OXE01, manufactured by BASF Japan) was added to each solution, and radicals were generated by irradiating with 365 nm light, causing all dyes to develop color. The absorbance of each solution was then measured at 25°C using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) under atmospheric conditions, and a calibration curve was created.

[0230] Next, the absorbance of the solution in which all the dye has developed is measured in the same manner as above, except that 0.1 g of the thermoplastic resin layer is dissolved in methyl ethyl ketone instead of the dye. The amount of the dye contained in the thermoplastic resin layer is calculated based on the absorbance of the obtained solution containing the thermoplastic resin layer and a calibration curve.

[0231] (Compounds that generate acids, bases, or radicals when exposed to light) The thermoplastic resin layer may contain a compound that generates an acid, a base or a radical when exposed to light (also simply referred to as "compound C").

[0232] Compound C is preferably a compound that generates an acid, a base, or a radical when exposed to actinic rays such as ultraviolet light and visible light.

[0233] Compound C may be a known photoacid generator, photobase generator, or photoradical polymerization initiator (photoradical generator). Of these, compound C is preferably a photoacid generator.

[0234] -Photoacid generator- From the viewpoint of resolution, the thermoplastic resin layer preferably contains a photoacid generator. Examples of the photoacid generator include the cationic photopolymerization initiators that may be contained in the photosensitive resin layer described above, and preferred embodiments are also the same except for the points described below.

[0235] From the viewpoints of sensitivity and resolution, the photoacid generator is preferably at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds, and from the viewpoints of sensitivity, resolution, and adhesion, it is more preferably an oxime sulfonate compound. The photoacid generator is also preferably a photoacid generator having the following structure:

[0236] [ka]

[0237] -Photoradical polymerization initiator- The thermoplastic resin layer may contain a photoradical polymerization initiator. Examples of the photoradical polymerization initiator include the photoradical polymerization initiators that may be contained in the photosensitive resin layer described above, and the preferred embodiments are also the same.

[0238] -Photobase generator- The thermoplastic resin layer may contain a photobase generator. The photobase generator is not particularly limited as long as it is a known photobase generator, and examples thereof include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)- Examples include 1-benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt(III) tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2,6-dimethyl-3,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine, and 2,6-dimethyl-3,5-diacetyl-4-(2,4-dinitrophenyl)-1,4-dihydropyridine.

[0239] The thermoplastic resin layer may contain one type of compound C alone, or two or more types thereof.

[0240] The content of compound C is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoints of visibility and resolution of exposed and unexposed areas.

[0241] (plasticizer) The thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion to adjacent layers, and developability.

[0242] The plasticizer preferably has a smaller molecular weight (weight average molecular weight (Mw) in the case of an oligomer or polymer) than the alkali-soluble resin. The molecular weight (weight average molecular weight (Mw)) of the plasticizer is preferably 200 to 2,000.

[0243] The plasticizer is not particularly limited as long as it is a compound that is compatible with the alkali-soluble resin and exhibits plasticity. From the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, more preferably a polyalkylene glycol compound. The alkyleneoxy group contained in the plasticizer more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.

[0244] From the viewpoints of resolution and storage stability, the plasticizer preferably contains a (meth)acrylate compound. From the viewpoints of compatibility, resolution, and adhesion to adjacent layers, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound.

[0245] Examples of the (meth)acrylate compound used as the plasticizer include the (meth)acrylate compounds described above as the polymerizable compound B contained in the photosensitive resin layer.

[0246] In the photosensitive transfer material, when a thermoplastic resin layer and a photosensitive resin layer are laminated in direct contact with each other, it is preferable that the thermoplastic resin layer and the photosensitive resin layer contain the same (meth)acrylate compound. When the thermoplastic resin layer and the photosensitive resin layer each contain the same (meth)acrylate compound, component diffusion between the layers is suppressed, and storage stability is improved.

[0247] When the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, it is preferable that the (meth)acrylate compound does not polymerize even in the exposed area after exposure, from the viewpoint of adhesion to adjacent layers.

[0248] Furthermore, from the viewpoints of resolution, adhesion to adjacent layers, and developability, the (meth)acrylate compound used as a plasticizer is preferably a polyfunctional (meth)acrylate compound having two or more (meth)acryloyl groups in one molecule.

[0249] Furthermore, the (meth)acrylate compound used as the plasticizer is preferably a (meth)acrylate compound having an acid group or a urethane (meth)acrylate compound.

[0250] The thermoplastic resin layer may contain one type of plasticizer alone or two or more types of plasticizers.

[0251] From the viewpoints of resolution, adhesion to adjacent layers, and developability, the content of the plasticizer is preferably 1% by mass to 70% by mass, more preferably 10% by mass to 60% by mass, and particularly preferably 20% by mass to 50% by mass, relative to the total mass of the thermoplastic resin layer.

[0252] (surfactant) From the viewpoint of thickness uniformity, the thermoplastic resin layer preferably contains a surfactant. Examples of the surfactant include the surfactants that may be contained in the photosensitive resin layer described above, and preferred embodiments are also the same.

[0253] The thermoplastic resin layer may contain one type of surfactant alone or two or more types of surfactants.

[0254] The content of the surfactant is preferably 0.001% by mass to 10% by mass, and more preferably 0.01% by mass to 3% by mass, relative to the total mass of the thermoplastic resin layer.

[0255] (sensitizer) The thermoplastic resin layer may contain a sensitizer. The sensitizer is not particularly limited, and examples thereof include the sensitizers that may be contained in the photosensitive resin layer described above.

[0256] The thermoplastic resin layer may contain one type of sensitizer alone or two or more types of sensitizers.

[0257] The content of the sensitizer can be selected appropriately depending on the purpose, but from the viewpoint of improving sensitivity to the light source and visibility of exposed and unexposed areas, it is preferably in the range of 0.01% by mass to 5% by mass, and more preferably in the range of 0.05% by mass to 1% by mass, relative to the total mass of the thermoplastic resin layer.

[0258] (additives, etc.) The thermoplastic resin layer may contain known additives in addition to the above components, as necessary. The thermoplastic resin layer is described in paragraphs

[0189] to

[0193] of JP 2014-85643 A, the contents of which are incorporated herein by reference.

[0259] <Physical properties etc.> The thickness of the thermoplastic resin layer is not particularly limited, but from the viewpoint of adhesion with adjacent layers, it is preferably 1 μm or more, more preferably 2 μm or more. The upper limit of the thickness of the thermoplastic resin layer is not particularly limited. From the viewpoint of developability and resolution, the thickness of the thermoplastic resin layer is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less.

[0260] <Formation method> The method for forming the thermoplastic resin layer is not particularly limited as long as it is a method that can form a layer containing the above components.

[0261] Examples of methods for forming the thermoplastic resin layer include a method in which a thermoplastic resin composition containing the above-mentioned components and a solvent is prepared, the thermoplastic resin composition is applied to the surface of a temporary support or the like, and the coating film of the thermoplastic resin composition is dried to form the layer.

[0262] The thermoplastic resin composition preferably contains a solvent in order to adjust the viscosity of the thermoplastic resin composition and facilitate the formation of the thermoplastic resin layer.

[0263] (solvent) The solvent contained in the thermoplastic resin composition is not particularly limited as long as it can dissolve or disperse the above components contained in the thermoplastic resin layer.

[0264] Examples of the solvent contained in the thermoplastic resin composition include the solvents that may be contained in the photosensitive resin composition described above, and the preferred embodiments are also the same.

[0265] The solvent contained in the thermoplastic resin composition may be one type alone or two or more types.

[0266] The content of the solvent in the thermoplastic resin composition is preferably 50 to 1,900 parts by mass, and more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content in the thermoplastic resin composition.

[0267] The preparation of the thermoplastic resin composition and the formation of the thermoplastic resin layer may be carried out in accordance with the above-mentioned method for preparing the photosensitive resin composition and the method for forming the photosensitive resin layer.

[0268] For example, a solution is prepared in advance by dissolving each component contained in the thermoplastic resin layer in the above-mentioned solvent, and the obtained solution is mixed in a predetermined ratio to prepare a thermoplastic resin composition.The obtained thermoplastic resin composition is then applied to the surface of a temporary support, and the coating of the thermoplastic resin composition is dried to form a thermoplastic resin layer.

[0269] Alternatively, after forming a photosensitive resin layer and an intermediate layer on a cover film described below, a thermoplastic resin layer may be formed on the surface of the intermediate layer.

[0270] [Middle class] The photosensitive transfer material preferably includes an intermediate layer between the thermoplastic resin layer and the photosensitive resin layer, which can prevent components from mixing when multiple layers are applied and during storage after application.

[0271] The intermediate layer is preferably a water-soluble layer from the viewpoints of developability and suppressing mixing of components when applying a plurality of layers and during storage after application.

[0272] In this specification, "water-soluble" means that the solubility in 100 g of water at a liquid temperature of 22°C and a pH of 7.0 is 0.1 g or more.

[0273] An example of the intermediate layer is an oxygen-blocking layer having an oxygen-blocking function, which is described as a "separation layer" in JP-A-5-72724. When the intermediate layer is an oxygen-blocking layer, the sensitivity during exposure is improved, the time load of the exposure machine is reduced, and productivity is improved.

[0274] The oxygen-blocking layer used as the intermediate layer may be appropriately selected from known layers described in the above publications, etc. Among them, the intermediate layer is preferably an oxygen-blocking layer that exhibits low oxygen permeability and disperses or dissolves in water or an alkaline aqueous solution (a 1% by mass aqueous solution of sodium carbonate at 22°C).

[0275] The intermediate layer preferably contains a resin. Examples of resins contained in the intermediate layer include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamides, and copolymers thereof.

[0276] The resin contained in the intermediate layer is preferably a water-soluble resin. Furthermore, from the viewpoint of suppressing mixing of components between multiple layers, it is preferable that the resin contained in the intermediate layer is a resin different from both the polymer A contained in the photosensitive resin layer and the thermoplastic resin (alkali-soluble resin) contained in the thermoplastic resin layer.

[0277] From the viewpoints of oxygen barrier properties and suppressing mixing of components when multiple layers are applied and during storage after application, the intermediate layer preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone.

[0278] The intermediate layer may contain one kind of the above resin alone, or may contain two or more kinds of them.

[0279] The resin content in the intermediate layer is not particularly limited, but from the viewpoint of oxygen barrier properties and suppressing mixing of components when applying multiple layers and during storage after application, it is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, even more preferably 80% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass, relative to the total mass of the intermediate layer.

[0280] The intermediate layer may also contain additives such as surfactants, if necessary.

[0281] The thickness of the intermediate layer is not particularly limited, but is preferably 0.1 μm to 5 μm, and more preferably 0.5 μm to 3 μm.

[0282] When the thickness of the intermediate layer is within the above range, the oxygen barrier property is not reduced, and mixing of components can be suppressed when multiple layers are applied and during storage after application. Furthermore, when the thickness of the intermediate layer is within the above range, an increase in the time required to remove the intermediate layer during development can be suppressed.

[0283] The method for forming the intermediate layer is not particularly limited, and examples thereof include a method of preparing an intermediate layer composition containing the above-mentioned resin and any additives, applying it to the surface of the thermoplastic resin layer or the photosensitive resin layer, and drying the coating of the intermediate layer composition to form the intermediate layer.

[0284] The intermediate layer composition preferably contains a solvent to adjust the viscosity of the intermediate layer composition and facilitate the formation of the intermediate layer.

[0285] The solvent contained in the intermediate layer composition is not particularly limited as long as it can dissolve or disperse the above resin, and is preferably at least one selected from the group consisting of water and water-miscible organic solvents, and more preferably water or a mixed solvent of water and a water-miscible organic solvent.

[0286] Examples of water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, with alcohols having 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred.

[0287] [Cover film] The photosensitive transfer material preferably includes a cover film in contact with the surface of the photosensitive resin layer that does not face the temporary support. Hereinafter, in this specification, the surface of the photosensitive resin layer facing the temporary support is also referred to as the "first surface", and the surface opposite to the first surface is also referred to as the "second surface".

[0288] Examples of materials for the cover film include resin films and paper, and from the viewpoints of strength and flexibility, resin films are preferred.

[0289] Examples of the resin film include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among these, the resin film is preferably a polyethylene film, a polypropylene film, or a polyethylene terephthalate film.

[0290] The thickness of the cover film is not particularly limited, but is preferably 5 μm to 100 μm, and more preferably 10 μm to 50 μm.

[0291] The arithmetic mean roughness Ra of the surface of the cover film in contact with the photosensitive resin layer (hereinafter also referred to simply as "surface of the cover film") is preferably 0.3 μm or less, more preferably 0.1 μm or less, and even more preferably 0.05 μm or less, from the viewpoint of superior resolution. By ensuring that the Ra value of the surface of the cover film is within the above range, it is believed that the uniformity of the layer thickness of the photosensitive resin layer and the formed resin pattern is improved.

[0292] The lower limit of the Ra value of the surface of the cover film is not particularly limited, but the Ra value of the surface of the cover film is preferably 0.001 μm or more.

[0293] The Ra value of the surface of the cover film is measured by the following method. Using a 3D optical profiler (New View7300, manufactured by Zygo), the surface of the cover film is measured under the following conditions to obtain the surface profile of the optical film. The measurement and analysis software used is the Microscope Application of MetroPro ver. 8.3.2. Next, the Surface Map screen is displayed in the analysis software, and histogram data is obtained on the Surface Map screen. The arithmetic mean roughness is calculated from the obtained histogram data, and the Ra value of the cover film surface is obtained. When a cover film is attached to the photosensitive transfer material, the cover film is peeled off from the photosensitive transfer material, and the Ra value of the surface on the peeled side is measured.

[0294] The photosensitive transfer material may include layers other than the above-mentioned layers (hereinafter also referred to as "other layers"), such as a contrast enhancement layer. The contrast enhancement layer is described in paragraph 0134 of WO 2018 / 179640. The other layers are described in paragraphs 0194 to 0196 of JP 2014-85643 A. The contents of these publications are incorporated herein by reference.

[0295] [Method for producing photosensitive transfer material] The method for producing the photosensitive transfer material according to the present disclosure is not particularly limited, and known production methods, for example, known methods for forming each layer, can be used.

[0296] Hereinafter, a method for producing a photosensitive transfer material according to the present disclosure will be described with reference to Fig. 1. However, the photosensitive transfer material according to the present disclosure is not limited to the configuration shown in Fig. 1.

[0297] Fig. 1 is a schematic diagram showing an example of the configuration of a photosensitive transfer material according to the present disclosure. The photosensitive transfer material 100 shown in Fig. 1 has a configuration in which a temporary support 10, a thermoplastic resin layer 12, an intermediate layer 14, a photosensitive resin layer 16, and a cover film 18 are laminated in this order.

[0298] Examples of a method for manufacturing the photosensitive transfer material 100 include a process of applying a thermoplastic resin composition to the surface of the temporary support 10 and then drying the coating of the thermoplastic resin composition to form a thermoplastic resin layer 12; a process of applying an intermediate layer composition to the surface of the thermoplastic resin layer 12 and then drying the coating of the intermediate layer composition to form an intermediate layer 14; a process of applying a photosensitive resin composition to the surface of the intermediate layer 14 and then drying the coating of the photosensitive resin composition to form a photosensitive resin layer 16; and a process of pressing a cover film 18 onto the photosensitive resin layer 16.

[0299] When the photosensitive resin layer is provided directly on the temporary support, the photosensitive resin composition is applied to the surface of the temporary support.

[0300] In the method for producing a photosensitive transfer material according to the present disclosure, when a photosensitive resin composition (or a thermoplastic resin composition when a thermoplastic resin layer is laminated) is applied to the surface of a temporary support, the temporary support is virtually divided into two regions at the center in the thickness direction, and the photosensitive resin composition is applied to the side of the region with the fewer foreign matter particles. As a result, when the region on the temporary support closer to the photosensitive resin layer than the center in the thickness direction is defined as the first region, and the region on the opposite side of the photosensitive resin layer than the center in the thickness direction is defined as the second region, a photosensitive transfer material can be produced in which the number of foreign matter particles contained in the first region is fewer than the number of foreign matter particles contained in the second region.

[0301] The present inventors have found that when the temporary support is virtually divided into two regions at the center in the thickness direction, the surface on the side of the region with fewer foreign objects is the surface that is not in contact with the casting drum during the production of the temporary support. Therefore, in the production method of the present disclosure, it is preferable to apply a photosensitive resin composition (or a thermoplastic resin composition, if a thermoplastic resin layer is to be laminated) to the surface that is not in contact with the casting drum during the production of the temporary support.

[0302] In the above-mentioned manufacturing method, it is preferable to use a thermoplastic resin composition containing at least one solvent selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, an intermediate layer composition containing at least one solvent selected from the group consisting of water and water-miscible organic solvents, and a photosensitive resin composition containing polymer A, polymerizable compound B, and at least one solvent selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. This can prevent mixing of the components contained in the thermoplastic resin layer 12 and the components contained in the intermediate layer 14 during application of the intermediate layer composition to the surface of the thermoplastic resin layer 12 and / or during storage of a laminate having a coating film of the intermediate layer composition. Furthermore, this can prevent mixing of the components contained in the intermediate layer 14 and the components contained in the photosensitive resin layer 16 during application of the photosensitive resin composition to the surface of the intermediate layer 14 and / or during storage of a laminate having a coating film of the photosensitive resin composition.

[0303] A method for producing a photosensitive transfer material according to the present disclosure preferably includes a step of providing a cover film 18 in contact with the second surface of the photosensitive resin layer 16, thereby producing a photosensitive transfer material 100 comprising a temporary support 10, a thermoplastic resin layer 12, an intermediate layer 14, a photosensitive resin layer 16, and a cover film 18.

[0304] After producing the photosensitive transfer material 100, the photosensitive transfer material 100 may be wound up to produce and store a roll of the photosensitive transfer material. The roll of the photosensitive transfer material can be provided in its original form for the step of laminating the photosensitive transfer material to a substrate in a roll-to-roll system, which will be described later.

[0305] [Method for manufacturing a resin pattern and a circuit wiring] The method for producing a resin pattern is not particularly limited as long as it is a method for producing a resin pattern using the above-mentioned photosensitive transfer material.

[0306] The method for producing a resin pattern preferably includes, in this order, a step of bonding the surface of the photosensitive resin layer in the photosensitive transfer material that is not facing the temporary support (i.e., the second surface) to a substrate (hereinafter also referred to as the "bonding step"); a step of patternwise exposing the photosensitive resin layer (hereinafter also referred to as the "exposure step"); and a step of developing the photosensitive resin layer after the patternwise exposing step to form a resin pattern (hereinafter also referred to as the "development step").

[0307] The method for producing the circuit wiring is not particularly limited as long as it is a method for producing the circuit wiring using the above-mentioned photosensitive transfer material.

[0308] It is preferable that the method for manufacturing circuit wiring is a method including the above-mentioned laminating step, the above-mentioned exposure step, the above-mentioned development step, and a step of etching the substrate in areas where the resin pattern is not arranged (hereinafter also referred to as the "etching step").

[0309] Each step included in the method for manufacturing a resin pattern and the method for manufacturing a circuit wiring will be described below. Unless otherwise specified, the content described for each step included in the method for manufacturing a resin pattern also applies to each step included in the method for manufacturing a circuit wiring.

[0310] [Laminating process] The method for producing the resin pattern preferably includes a lamination step. In the lamination step, it is preferable to bring a substrate (or the conductive layer, if provided on the surface of the substrate) into contact with the second surface of the photosensitive resin layer, and to press the photosensitive transfer material and the substrate together. In this embodiment, the adhesion between the second surface of the photosensitive resin layer and the substrate is improved, so that the patterned photosensitive resin layer after exposure and development can be suitably used as an etching resist when etching.

[0311] When the photosensitive transfer material has a cover film, the cover film may be removed from the surface of the photosensitive resin layer before lamination.

[0312] Furthermore, in the case where the photosensitive transfer material further comprises a layer other than the cover film on the second surface of the photosensitive resin layer (for example, at least one layer selected from the group consisting of a high refractive index layer and a low refractive index layer), the lamination step is carried out in such a manner that the second surface of the photosensitive resin layer and the substrate are laminated via that layer.

[0313] The method for pressing the substrate and the photosensitive transfer material together is not particularly limited, and known transfer methods and lamination methods can be used.

[0314] The photosensitive transfer material is preferably bonded to the substrate by placing the substrate on the second surface side of the photosensitive resin layer and applying pressure and heat using a roll or other means. For bonding, known laminators such as a laminator, a vacuum laminator, and an auto-cut laminator, which can further increase productivity, can be used.

[0315] The method for producing a resin pattern and the method for producing a circuit wiring, which include the lamination step, are preferably carried out by a roll-to-roll method.

[0316] The roll-to-roll method will be described below. The roll-to-roll method is a method in which a substrate that can be wound up and unwound is used as the substrate, and includes a step of unwinding the substrate or a structure including the substrate (also referred to as an "unwinding step") before any of the steps included in the method for manufacturing a resin pattern or the method for manufacturing circuit wiring, and a step of winding up the substrate or a structure including the substrate (also referred to as a "winding step") after any of the steps, and at least any of the steps (preferably all of the steps, or all of the steps other than the heating step) are performed while the substrate or the structure including the substrate is being transported.

[0317] The unwinding method in the unwinding step and the winding method in the winding step are not particularly limited, and any known method may be used in a manufacturing method that employs a roll-to-roll system.

[0318] <Substrate> A known substrate can be used as the substrate used in forming a resin pattern using the photosensitive transfer material according to the present disclosure. The substrate is preferably a substrate having a conductive layer, more preferably a substrate having a conductive layer on the surface of a base material.

[0319] The substrate may have any layer other than the conductive layer, if necessary.

[0320] Examples of the base material that constitutes the substrate include glass, silicon, and resin films. The substrate is preferably transparent. In this specification, "transparent" means that the transmittance of light with a wavelength of 400 nm to 700 nm is 80% or more. The refractive index of the substrate is preferably 1.50 to 1.52.

[0321] Examples of transparent glass substrates include tempered glass, such as Gorilla Glass from Corning Inc. Furthermore, materials described in JP-A-2010-86684, JP-A-2010-152809, and JP-A-2010-257492 can be used as the transparent glass substrate.

[0322] When a resin film is used as the substrate, the substrate is preferably a resin film with small optical distortion and / or high transparency, such as polyethylene terephthalate (PET) film, polyethylene naphthalate film, polycarbonate film, triacetyl cellulose film, and cycloolefin polymer film.

[0323] When manufacturing by a roll-to-roll method, the substrate is preferably a resin film. When manufacturing circuit wiring for a touch panel by a roll-to-roll method, the substrate is preferably a resin sheet.

[0324] The conductive layer of the substrate may be a conductive layer used for general circuit wiring or touch panel wiring.

[0325] From the viewpoints of electrical conductivity and fine line formability, the conductive layer is preferably at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, more preferably a metal layer, and even more preferably a copper layer or a silver layer.

[0326] The substrate may have one conductive layer or two or more conductive layers. When the substrate has two or more conductive layers, the substrate preferably has conductive layers made of two or more different materials.

[0327] Materials for the conductive layer include metals and conductive metal oxides.

[0328] Metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au.

[0329] Examples of conductive metal oxides include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO2. In this specification, "conductive" refers to a material having a volume resistivity of 1×10 6 The volume resistivity of conductive metal oxides is less than 1×10 4 It is preferably less than Ωcm.

[0330] When a resin pattern is produced using a substrate having a plurality of conductive layers, at least one of the plurality of conductive layers preferably contains a conductive metal oxide.

[0331] The conductive layer is preferably an electrode pattern corresponding to a sensor of a visual recognition section used in a capacitive touch panel or wiring of a peripheral extraction section.

[0332] [Exposure process] The method for producing a resin pattern preferably includes, after the laminating step, a step of pattern-exposing the photosensitive resin layer (exposure step).

[0333] The detailed arrangement and specific size of the pattern in the pattern exposure are not particularly limited. At least a part of the pattern (preferably the electrode pattern and / or lead wiring portion of the touch panel) preferably includes thin lines having a width of 20 μm or less, more preferably thin lines having a width of 10 μm or less. This can improve the display quality of a display device (e.g., a touch panel) equipped with an input device having circuit wiring manufactured by the circuit wiring manufacturing method, and reduce the area occupied by the lead wiring.

[0334] The light source used for exposure is not particularly limited as long as it irradiates light with a wavelength (e.g., 365 nm or 405 nm) that can expose the photosensitive resin layer, and can be appropriately selected and used. Examples of light sources include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (light emitting diodes).

[0335] The exposure dose was 5 mJ / cm 2 ~200mJ / cm 2 and preferably 10 mJ / cm 2 ~100mJ / cm 2 It is more preferable that:

[0336] In the exposure process, pattern exposure may be performed after peeling the temporary support from the photosensitive resin layer, or pattern exposure may be performed via the temporary support and then peeling the temporary support. When exposing after peeling the temporary support, exposure may be performed by bringing the mask and the photosensitive resin layer into contact, or by bringing the mask and the photosensitive resin layer into close proximity without contact. When exposing without peeling the temporary support, exposure may be performed by bringing the mask and the temporary support into contact, or by bringing the mask and the temporary support into close proximity without contact. To prevent mask contamination 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, it is preferable to perform pattern exposure without peeling the temporary support. The exposure method can be appropriately selected from contact exposure in the case of contact exposure, and proximity exposure, lens-based or mirror-based projection exposure, or direct exposure using an exposure laser, etc. in the case of non-contact exposure. In the case of lens-based or mirror-based projection exposure, an exposure machine with an appropriate lens numerical aperture (NA) can be used depending on the required resolution and depth of focus. In the case of the direct exposure method, the photosensitive resin layer may be directly exposed, or the photosensitive resin layer may be subjected to reduced projection exposure via a lens. The exposure may be performed not only under atmospheric pressure but also under reduced pressure or vacuum. Furthermore, the exposure may be performed by interposing a liquid such as water between the light source and the photosensitive resin layer.

[0337] [Development process] The method for producing a resin pattern preferably includes, after the exposure step, a step of developing the exposed photosensitive resin layer to form a resin pattern (development step).

[0338] When the photosensitive transfer material has a thermoplastic resin and an intermediate layer, the thermoplastic resin layer and the intermediate layer in the non-exposed area are removed together with the photosensitive resin layer in the non-exposed area in the development step. In addition, the thermoplastic resin layer and the intermediate layer in the exposed area may also be removed in the development step by dissolving or dispersing in the developer.

[0339] The exposed photosensitive resin layer can be developed using a developer.

[0340] The developer is not particularly limited as long as it can remove the non-image areas (non-exposed areas) of the photosensitive resin layer, and known developers such as those described in JP-A No. 5-72724 can be used.

[0341] The developer is preferably an alkaline aqueous solution containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol / L to 5 mol / L. The developer may contain at least one selected from the group consisting of water-soluble organic solvents and surfactants. The developer is also preferably the developer described in paragraph 0194 of WO 2015 / 093271.

[0342] The development method is not particularly limited, and may be any of puddle development, shower development, shower and spin development, and dip development. Shower development is a development treatment in which a developer is sprayed onto the exposed photosensitive resin layer by showering, thereby removing the unexposed areas.

[0343] After the development step, it is preferable to remove development residues by spraying a cleaning agent by showering and scrubbing with a brush.

[0344] The temperature of the developer is not particularly limited, but is preferably 20°C to 40°C.

[0345] [Etching process] The method for manufacturing circuit wiring preferably includes a step (etching step) of etching the substrate in areas where the resin patterns are not arranged in a laminate in which the resin patterns manufactured by the manufacturing method including the laminating step, the exposing step, and the developing step are laminated in this order.

[0346] In the etching step, the resin pattern formed from the photosensitive resin layer is used as an etching resist to etch the substrate.

[0347] As the etching method, known methods can be applied, for example, the method described in paragraphs 0209 to 0210 of JP 2017-120435 A, the method described in paragraphs 0048 to 0054 of JP 2010-152155 A, a wet etching method in which the substrate is immersed in an etching solution, and a dry etching method such as plasma etching can be mentioned.

[0348] The etching solution used in the wet etching may be an acidic or alkaline etching solution that is appropriately selected depending on the target to be etched.

[0349] Examples of acidic etching solutions include aqueous solutions of an acidic component selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, and aqueous solutions of a mixture of an acidic component and a salt selected from ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component may be a combination of multiple acidic components.

[0350] Examples of alkaline etching solutions include aqueous solutions of alkaline components selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide), as well as aqueous solutions of mixtures of alkaline components and salts (e.g., potassium permanganate). The alkaline component may be a combination of multiple alkaline components.

[0351] [Removal process] In the method for manufacturing circuit wiring, it is preferable to carry out a step of removing the remaining resin pattern (removal step).

[0352] The removal step is not particularly limited and can be carried out as needed, but is preferably carried out after the etching step.

[0353] The method for removing the remaining resin pattern is not particularly limited, but includes a method of removing it by chemical treatment, and a method of removing it using a remover is preferred as a method of removing the remaining resin pattern.

[0354] A method for removing the photosensitive resin layer includes immersing the substrate with the remaining resin pattern in a stirring removal liquid, the liquid temperature of which is preferably 30°C to 80°C, more preferably 50°C to 80°C, for 1 minute to 30 minutes.

[0355] Examples of the removal solution include a removal solution obtained by dissolving an inorganic or organic alkaline component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixture thereof. Examples of the inorganic alkaline component include sodium hydroxide and potassium hydroxide. Examples of the organic alkaline component include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

[0356] Alternatively, the remaining resin pattern may be removed by a known method such as a spray method, a shower method, or a puddle method using a remover.

[0357] [Other steps] The method for manufacturing a circuit wiring may include any other steps (other steps) in addition to the steps described above, such as, but not limited to, the following steps.

[0358] Furthermore, examples of the exposure step, development step, and other steps that can be applied to the method for manufacturing circuit wiring include the steps described in paragraphs 0035 to 0051 of JP-A No. 2006-23696.

[0359] <Cover film peeling process> When the photosensitive transfer material has a cover film, the method for producing a resin pattern preferably includes a step of peeling the cover film from the photosensitive transfer material. The method for peeling the cover film is not particularly limited, and known methods can be applied.

[0360] <Step of reducing visible light reflectance> The method for manufacturing circuit wiring may include a step of performing a treatment to reduce the visible light reflectance of a part or all of the conductive layers provided on the substrate.

[0361] An example of a treatment for reducing the visible light reflectance is oxidation treatment. When the substrate has a conductive layer containing copper, the copper is oxidized to form copper oxide, and the conductive layer is blackened, thereby reducing the visible light reflectance of the conductive layer.

[0362] Treatments for reducing visible light reflectance are described in paragraphs 0017 to 0025 of JP 2014-150118 A and paragraphs 0041, 0042, 0048, and 0058 of JP 2013-206315 A, and the contents of these publications are incorporated herein by reference.

[0363] <Step of forming an insulating film, step of forming a new conductive layer on the surface of the insulating film> The method for manufacturing a circuit wiring 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. By these steps, a second electrode pattern insulated from the first electrode pattern can be formed.

[0364] The step of forming the insulating film is not particularly limited, and may include a known method for forming a permanent film. Alternatively, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having insulating properties.

[0365] The step of forming a new conductive layer on the insulating film is not particularly limited, and for example, a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.

[0366] A preferred method for manufacturing circuit wiring involves using a substrate having multiple conductive layers on both surfaces of a base material, and sequentially or simultaneously forming circuits on the conductive layers formed on both surfaces of the base material. This configuration allows the formation of touch panel circuit wiring in which a first conductive pattern is formed on one surface of the base material and a second conductive pattern is formed on the other surface. It is also preferred to form such touch panel circuit wiring from both surfaces of the base material using a roll-to-roll process.

[0367] [Circuit wiring applications] The circuit wiring manufactured by the circuit wiring manufacturing method can be applied to various devices. Examples of devices equipped with the circuit wiring manufactured by the above manufacturing method include input devices, preferably touch panels, and more preferably capacitive touch panels. Furthermore, the input devices can be applied to display devices such as organic electroluminescence (EL) display devices and liquid crystal display devices.

[0368] [Touch panel manufacturing method] The method for producing a touch panel is not particularly limited as long as it is a method for producing a touch panel using the above-mentioned photosensitive transfer material.

[0369] It is preferable that the method for manufacturing a touch panel includes the above-mentioned bonding step, the above-mentioned exposure step, the above-mentioned development step, and a step of etching the substrate in areas where the resin pattern is not arranged (hereinafter also referred to as the "etching step").

[0370] Specific aspects of each step in the method for manufacturing a touch panel, and the order in which each step is performed, are as described above in the section "Method for manufacturing circuit wiring," and the same applies to preferred aspects. The method for manufacturing a touch panel may refer to known methods for manufacturing a touch panel, except that the touch panel wiring is formed by the above method. The method for manufacturing a touch panel may also include any other steps (other steps) in addition to the above steps.

[0371] The touch panel manufacturing method described above produces a touch panel having at least touch panel wiring. The touch panel preferably has a transparent substrate, electrodes, and an insulating layer or a protective layer.

[0372] Examples of detection methods for touch panels include known methods such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, an optical method, etc. Among these, the capacitance method is preferred as the detection method for touch panels. [Example]

[0373] The following examples further illustrate the embodiments of the present invention. The materials, amounts used, proportions, processing details, and processing procedures shown in the following examples can be changed as appropriate without departing from the spirit of the embodiments of the present invention. Therefore, the scope of the embodiments of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[0374] <Preparation of Photosensitive Resin Composition> The components used to prepare the photosensitive resin composition are as follows: [Polymer A (alkali-soluble resin)] Polymer A-3 was synthesized according to the following method: In the synthesis method of polymer A-3, the following abbreviations represent the following compounds, respectively. St: Styrene (Fujifilm Wako Pure Chemical Industries, Ltd.) MAA: methacrylic acid (Fujifilm Wako Pure Chemical Industries, Ltd.) MMA: Methyl methacrylate (Fujifilm Wako Pure Chemical Industries, Ltd.) V-601: 2,2'-azobis(isobutyrate) dimethyl (Fujifilm Wako Pure Chemical Industries, Ltd., polymerization initiator) PGMEA: Propylene glycol monomethyl ether acetate

[0375] PGMEA (116.5 parts) was placed in a three-neck flask and heated to 90°C under a nitrogen atmosphere. While maintaining the liquid temperature in the three-neck flask at 90°C ± 2°C, a mixture of St (52.0 parts), MMA (19.0 parts), MAA (29.0 parts), V-601 (4.0 parts), and PGMEA (116.5 parts) was added dropwise to the three-neck flask over 2 hours. After the addition was completed, the mixture was stirred for 2 hours while maintaining the liquid temperature at 90°C ± 2°C, yielding a composition containing 30.0% by mass of polymer A. The acid value of polymer A was 189 mgKOH / g, the weight-average molecular weight was 60,000, and the glass transition temperature was 131°C.

[0376] <Polymers A-1, A-2, A-4 and A-5> Polymers A-1, A-2, A-4, and A-5 were synthesized in the same manner as polymer A-3, except that the types and amounts of monomers used in polymer synthesis were changed as shown in Table 1 below, to obtain compositions containing 30.0% by mass of the polymer. In Table 1, BnMA means benzyl methacrylate (manufactured by Mitsubishi Gas Chemical Company, Inc.). Table 1 also shows the weight average molecular weight (Mw), acid value and glass transition temperature (Tg) of the obtained polymer.

[0377] [Table 1]

[0378] [Polymerizable compound B] Polymerizable compound B-1: NK Ester BPE-500 (2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd.) Polymerizable compound B-2: NK Ester BPE-200 (2,2-bis(4-(methacryloxydiethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd.) Polymerizable compound B-3: NK Ester A-TMPT (trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) Polymerizable compound B-4: Aronix TO-2349 (compound having the following structure, manufactured by Toagosei Co., Ltd.)

[0379] [ka]

[0380] [Photopolymerization initiator] B-CIM (photoradical polymerization initiator, 2-(2-chlorophenyl)-4,5-diphenylimidazole dimer, manufactured by Hampford)

[0381] [Sensitizer] SB-PI 701 (4,4'-bis(diethylamino)benzophenone, manufactured by Sanyo Trading Co., Ltd.)

[0382] [Dye N] Dye N-1: LCV (Leuco Crystal Violet, manufactured by Tokyo Chemical Industry Co., Ltd., color developed by radicals) Dye N-2: Brilliant Green (Tokyo Chemical Industry Co., Ltd.)

[0383] [Rust inhibitor] A mixture of 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole (1:1 mass ratio)

[0384] [Antioxidants] Irganox 245 (ethylene bis(oxyethylene) bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate), manufactured by BASF)

[0385] [Polymerization inhibitor] N-nitrosophenylhydroxylamine aluminum salt (Fujifilm Wako Pure Chemical Industries, Ltd.)

[0386] A photosensitive resin composition was prepared by mixing the following components. ·Polymer A-1 (solid content 30.0%): 53.27 parts ·Polymerizable compound B-1: 22.50 parts ·Polymerizable compound B-2: 10.00 parts ·Polymerizable compound B-3: 10.00 parts Photopolymerization initiator: 3.00 parts Sensitizer: 0.30 parts ·Dye N-1: 0.60 parts ·Dye N-2: 0.02 parts Rust inhibitor: 0.10 parts Antioxidant: 0.20 parts Polymerization inhibitor: 0.01 parts Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.): 100.00 parts PGMEA (Showa Denko): 50.00 parts Methanol (Mitsubishi Gas Chemical Co., Ltd.): 10.00 parts

[0387] <Preparation of photosensitive transfer material> [Example 1] A 30 μm thick PET film was prepared as a temporary support. A photosensitive resin composition was applied to the surface of the temporary support using a slit nozzle so that the coating width was 1.0 m and the layer thickness after drying was 5 μm. The coating of the photosensitive resin composition was dried at 80°C for 40 seconds to form a photosensitive resin layer, and a photosensitive transfer material was obtained.

[0388] [Examples 2 to 13, Comparative Examples 1 and 2] A photosensitive transfer material was obtained in the same manner as in Example 1, except that the thickness of the photosensitive resin layer, and the types and amounts of polymer A and polymerizable compound B contained in the photosensitive resin layer were changed to the values ​​shown in Tables 2 and 3.

[0389] In Tables 2 and 3, the "styrene content" of "polymer A" indicates the content of structural units derived from styrene relative to the total mass of polymer A contained in the photosensitive resin layer. The "content" of "polymer A" indicates the content of polymer A relative to the total mass of the photosensitive resin layer. For polymerizable compound B, the content (mass %) of each polymerizable compound relative to the total mass of the photosensitive resin layer is shown. Furthermore, the "M / B ratio" indicates the ratio of the content of polymerizable compound B to the content of polymer A.

[0390] <Preparation of Intermediate Layer Composition> An intermediate layer composition was prepared by mixing the following ingredients: Ion-exchanged water: 38.12 parts Methanol (manufactured by Mitsubishi Gas Chemical Co., Ltd.): 57.17 parts Kuraray Poval PVA-205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.): 3.22 parts Polyvinylpyrrolidone K-30 (Nippon Shokubai Co., Ltd.): 1.49 parts Megafac F-444 (fluorine-based nonionic surfactant, manufactured by DIC): 0.0 015 part

[0391] <Preparation of Thermoplastic Resin Composition> A thermoplastic resin composition was prepared by mixing the following components. Copolymer of benzyl methacrylate, methacrylic acid and acrylic acid (solid concentration 30.0%, Mw 30000, acid value 153 mg KOH / g): 42.85 parts NK Ester A-DCP (tricyclodecane dimethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.): 4.63 parts 8UX-015A (multifunctional urethane acrylate compound, manufactured by Taisei Fine Chemical Co., Ltd.): 2.31 parts Aronix TO-2349 (manufactured by Toagosei): 0.77 parts 0.32 parts of a compound with the structure shown below (photoacid generator, a compound synthesized according to the method described in paragraph 0227 of JP-A-2013-47765):

[0392] [ka]

[0393] Compound with the structure shown below (acid-sensitive pigment): 0.08 parts

[0394] [ka]

[0395] Megafac F552 (DIC): 0.03 parts Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.): 39.50 parts PGMEA (Showa Denko): 9.51 parts

[0396] <Preparation of photosensitive transfer material> [Example 14] A 30 μm thick PET film was prepared as a temporary support. A thermoplastic resin composition was applied to the surface of the temporary support using a slit nozzle so that the coating width was 1.0 m and the layer thickness after drying was 3.0 μm. The formed coating film of the thermoplastic resin composition was dried at 80°C for 40 seconds to form a thermoplastic resin layer. An intermediate layer composition was applied to the surface of the formed thermoplastic resin layer using a slit nozzle so that the coating width was 1.0 m and the layer thickness after drying was 1.2 μm. The coating film of the intermediate layer composition was dried at 80°C for 40 seconds to form an intermediate layer. A photosensitive resin composition was applied to the surface of the formed intermediate layer using a slit nozzle so that the coating width was 1.0 m and the layer thickness after drying was 2 μm. The coating film of the photosensitive resin composition was dried at 80°C for 40 seconds to form a photosensitive resin layer, and a photosensitive transfer material was obtained.

[0397] The photosensitive transfer materials obtained in the examples and comparative examples were used to measure haze and evaluate resolution, cushioning properties, and scum generation. The measurement and evaluation methods are as follows. The evaluation results are shown in Tables 2 and 3.

[0398] <Haze> From the photosensitive transfer materials obtained in the examples and comparative examples, 0.02 m 2 A measurement sample of 0.02 m was obtained by dissolving 0.02 m in 200 mL of a 1 mass % sodium carbonate aqueous solution. 2 The measurement sample was added and stirred at 30°C for 4 hours, taking care not to introduce air bubbles. After stirring, the haze of the solution in which the measurement sample had been dissolved was measured. The haze was measured using a haze meter (product name "NDH4000", manufactured by Nippon Denshoku Industries Co., Ltd.) with a liquid measurement unit and a dedicated liquid measurement cell with an optical path length of 20 mm.

[0399] <resolution> First, a copper layer having a thickness of 200 nm was formed on a polyethylene terephthalate (PET) film having a thickness of 100 μm by sputtering, thereby preparing a PET substrate with a copper layer. After unwinding the photosensitive transfer material in roll form, the photosensitive transfer material and the PET substrate with the copper layer were laminated together so that the photosensitive resin layer and the copper layer were in contact with each other. The lamination process was carried out under the conditions of a roll temperature of 120°C, a linear pressure of 1.0 MPa, and a linear speed of 0.5 m / min. The photosensitive resin layer was exposed to light from the temporary support side of the resulting laminate through a photomask using an ultra-high pressure mercury lamp (dominant exposure wavelength: 365 nm). The photomask used for exposure had a line and space pattern in which the ratio of the width of the transmission area to the width of the light-shielding area (duty ratio) was 1:1 and the line width (and space width) varied in 1 μm increments from 1 μm to 20 μm. The exposure dose to the photosensitive resin layer was adjusted so that the line width of the resin pattern formed by exposure to irradiation light that passed through an area of ​​the photomask where the line width and space width of the line and space pattern were 20 μm would be 20 μm. After peeling off the temporary support from the exposed laminate, the laminate was subjected to shower development for 30 seconds using a 1.0% by mass aqueous solution of sodium carbonate at a liquid temperature of 25°C. The unexposed photosensitive resin layer was removed from the laminate, and a resin pattern having the above-mentioned stepwise line-and-space pattern was produced on the surface of the copper layer. In the example in which an intermediate layer and a thermoplastic resin layer were laminated, the intermediate layer and the thermoplastic resin layer were also removed by this development step.

[0400] The formed resin pattern was observed for each line width using a scanning electron microscope (product name "S-4800", manufactured by Hitachi High-Technologies Corporation) to check for the presence or absence of residues of the photosensitive resin layer in the pattern shape and space areas. The smallest line width of the resin pattern in which the cured photosensitive resin layer did not peel off in the line areas and no residues of the photosensitive resin layer were present was determined as the resolution. The evaluation criteria were as follows: 3 or higher is a level that is acceptable for practical use. 5: The resolution is 4 μm or less. 4: Resolution is 5 μm or 6 μm. 3: Resolution is 7 μm or 8 μm. 2: The resolution is 9 μm or 10 μm. 1: Resolution is 11 μm or greater.

[0401] <Cushioning> First, a 200-nm-thick copper layer was formed on a 100-μm-thick polyethylene terephthalate (PET) film by sputtering to prepare a copper-layered PET substrate. The copper-layered PET substrate was then etched to produce a substrate with a step consisting of a line-and-space copper pattern 200 nm high and 1,000 μm wide. After unwinding a roll of photosensitive transfer material, the photosensitive transfer material and the substrate were bonded together so that the photosensitive resin layer and the copper layer were in contact with each other to obtain a laminate. The bonding process was carried out under atmospheric pressure, with a linear pressure of 1.0 MPa and a linear speed of 4 m / min, while changing the roll temperature in 5°C increments. The lowest temperature at which bonding to the step was possible without introducing air bubbles (hereinafter referred to as the "bubble-free lamination temperature") was used as an index of cushioning. The lower the temperature at which bonding without introducing air bubbles was possible, the better the cushioning. The evaluation criteria were as follows: 3 or higher is considered acceptable for practical use. 5: The temperature at which bubble-free lamination is possible is 70°C or below. 4: The temperature at which bubble-free lamination is possible is between 75°C and 85°C. 3: The temperature at which bubble-free lamination is possible is between 90°C and 100°C. 2: The temperature at which bubble-free lamination is possible is 105°C or higher and 115°C or lower. 1: The temperature at which bubble-free lamination is possible is 120°C or higher.

[0402] <Scum generation> From the photosensitive transfer materials obtained in the examples and comparative examples, 0.5 m 2 The evaluation sample was obtained by adding 0.5 ml of 1 L of 1 mass % sodium carbonate aqueous solution. 2The evaluation sample was dissolved in the solution. The solution containing the dissolved evaluation sample was circulated for 3 hours while being sprayed at a pressure of 0.15 MPa. After 3 hours, 200 mL of the solution was collected and filtered using a polypropylene membrane filter (HDCII Pall) with a pore size of 0.45 μm. After filtration, the filter used for filtration was vacuum dried at 80°C to evaporate the water. The mass of the filtration residue was calculated from the mass of the filter before and after filtration. The remaining solution was allowed to stand in a room at 25°C for 24 hours. After 24 hours, the formation of aggregates (scum) in the tank containing the remaining solution was visually observed. The evaluation criteria are as follows: 3 or higher is a level that is acceptable for practical use. 6: The mass of the filtration residue was less than 1 mg, and no scum (aggregates) was observed in the tank. 5: The mass of the filtration residue was 1 mg or more and less than 2 mg, and no scum (aggregates) was observed in the tank. 4: The mass of the filtration residue was 1 mg or more and less than 2 mg, but scum (aggregates) was observed in the tank. 3: The mass of the filtration residue is 2 mg or more and less than 5 mg. 2: The mass of the filtration residue is 5 mg or more and less than 10 mg. 1: The mass of the filtration residue was 10 mg or more, or a large amount of solid scum (aggregates) was observed in the tank.

[0403] [Table 2]

[0404] [Table 3]

[0405] As shown in Tables 2 and 3, in Examples 1 to 14, 0.1 ml of sodium carbonate was added to 1 liter of a 30°C aqueous solution of 1% by mass of sodium carbonate. 2 It was found that the haze of the solution obtained by dissolving the photosensitive transfer material was 60% or less, and therefore the generation of scum (aggregates) was low.

[0406] On the other hand, as shown in Table 3, in Comparative Examples 1 and 2, the haze of the above solutions was 100% and 68.2%, respectively, indicating that a large amount of scum (aggregates) was generated.

[0407] In Example 3, the acid value of the alkali-soluble resin contained in the photosensitive resin layer is 120 mg / KOH or more, so compared to Example 1, there is less generation of scum (aggregates) and the resolution is excellent.

[0408] In Example 3, the ratio of the polymerizable compound content to the alkali-soluble resin content in the photosensitive resin layer is 0.85 or less by mass, and therefore, less scum (aggregates) is generated compared to Example 13.

[0409] In Example 8, the alkali-soluble resin contained in the photosensitive resin layer contains a structural unit derived from styrene, and therefore, compared to Example 7, less scum (aggregates) is generated.

[0410] In Example 10, the thickness of the photosensitive resin layer is 10 μm or less, and therefore, compared to Example 9, the generation of scum (aggregates) is small.

[0411] Since Example 11 contains a polymerizable compound having an acid group, compared to Example 8, less scum (aggregates) are generated.

[0412] The photosensitive transfer material according to the present disclosure can be suitably used in various applications requiring precision microfabrication by photolithography. After patterning the photosensitive resin layer, the photosensitive resin layer may be used as a coating for etching, or electroforming based on electroplating may be performed. The cured film obtained by patterning may also be used as a permanent film. The cured film may be used, for example, as an interlayer insulating film, a wiring protective film, or a wiring protective film having an index matching layer. The photosensitive transfer material according to the present disclosure can also be suitably used as a material for forming various wiring such as semiconductor packages, printed circuit boards, and sensor substrates, as well as a material for forming touch panels, electromagnetic wave shielding materials, conductive films such as film heaters, liquid crystal sealants, micromachines, and structures in the microelectronics field.

[0413] The disclosure of Japanese Patent Application No. 2020-079534, filed on April 28, 2020, is incorporated herein by reference in its entirety. In addition, all documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually indicated to be incorporated by reference.

Claims

1. A temporary support and a photosensitive resin layer disposed on the temporary support, 0.1 ml of 1% by mass sodium carbonate in 1 liter of aqueous solution at 30°C ２ the haze of the solution obtained by dissolving the photosensitive transfer material is 60% or less, the photosensitive resin layer is a negative type and contains a polymerizable compound and an alkali-soluble resin; The alkali-soluble resin has an acid value of 120 mg KOH / g or more, The thickness of the photosensitive resin layer is 12 μm or less, The polymerizable compound includes a polymerizable compound having an acid group. Photosensitive transfer material.

2. 2. The photosensitive transfer material according to claim 1, wherein the photosensitive resin layer has a thickness of 10 [mu]m or less.

3. 3. The photosensitive transfer material according to claim 1, wherein the ratio of the content of the polymerizable compound to the content of the alkali-soluble resin is 0.85 or less on a mass basis.

4. 4. The photosensitive transfer material according to claim 1, wherein the alkali-soluble resin contains a structural unit derived from styrene.

5. 5. The photosensitive transfer material according to claim 4, wherein the content of the structural unit derived from styrene is 40% by mass or more based on the total mass of the alkali-soluble resin.

6. 6. The photosensitive transfer material according to claim 1, further comprising a thermoplastic resin layer between the temporary support and the photosensitive resin layer.

7. a step of laminating a surface of the photosensitive resin layer in the photosensitive transfer material according to any one of claims 1 to 6, the surface not facing the temporary support, to a substrate; a step of pattern-exposing the photosensitive resin layer in the photosensitive transfer material after the laminating step; and developing the photosensitive resin layer after the pattern exposure step to form a resin pattern.

8. a step of laminating a surface of the photosensitive resin layer in the photosensitive transfer material according to any one of claims 1 to 6, the surface not facing the temporary support, to a substrate; a step of pattern-exposing the photosensitive resin layer in the photosensitive transfer material after the laminating step; a step of developing the photosensitive resin layer after the pattern exposure step to form a resin pattern; and etching the substrate in the area where the resin pattern is not disposed.

9. a step of laminating a surface of the photosensitive resin layer in the photosensitive transfer material according to any one of claims 1 to 6, the surface not facing the temporary support, to a substrate; a step of pattern-exposing the photosensitive resin layer in the photosensitive transfer material after the laminating step; a step of developing the photosensitive resin layer after the pattern exposure step to form a resin pattern; and etching the substrate in an area where the resin pattern is not disposed.

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