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

Abstract

The present application provides a photosensitive transfer material and applications thereof, the photosensitive transfer material has a temporary support body and a photosensitive resin layer arranged on the temporary support body, the turbidity of a solution obtained by dissolving 0.1 m 2 of the photosensitive transfer material in 1 liter of a 30°C aqueous solution of 1 mass% sodium carbonate is 60% or less.

Description

TECHNICAL FIELD

[0001] The present application relates to a photosensitive transfer material, a method for manufacturing a resin pattern, a method for manufacturing a circuit wiring, and a method for manufacturing a touch panel BACKGROUND

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

[0003] Generally, when forming a patterned layer, the number of processes for obtaining a desired pattern shape is small, and therefore a method of disposing a layer (photosensitive layer) of a photosensitive resin composition on a substrate using a photosensitive transfer material and performing development after exposing the photosensitive layer through a mask having a desired pattern is widely adopted.

[0004] For example, in Japanese Patent Application Publication No. 2008-94803, a photosensitive resin laminate is described, which is provided with a photosensitive resin layer composed of a photosensitive resin composition on a support layer, the photosensitive resin composition containing 20 to 90 mass% of a binder resin composed of a linear polymer having a carboxyl group content of 100 to 600 in acid equivalents 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 olefinic unsaturated group, and 0.01 to 30 mass% of a photopolymerization initiator containing a specific compound. SUMMARY

[0005] Technical Problem to be Solved by the Invention

[0006] In Japanese Patent Application Publication No. 2008-94803, in order to improve the dispersion stability of the photopolymerization initiator in the developing solution, a photopolymerization initiator having a specific structure is considered to be contained in the photosensitive resin layer. However, in the developing solution, in addition to the photopolymerization initiator, there are components having poor dispersion stability, and these components can become a cause of the generation of scum (agglomerates).

[0007] According to an embodiment of the present application, a photosensitive transfer material is provided, in which the generation of scum (agglomerates) can be suppressed even when the developing process is performed for a long time. Furthermore, according to another embodiment of the present application, a method for manufacturing a resin pattern, a method for manufacturing a circuit wiring, and a method for manufacturing a touch panel using the above-described photosensitive transfer material are provided.

[0008] Means for Solving the Technical Problem

[0009] The present application includes the following modes.

[0010] <1> A photosensitive transfer material comprising a temporary support and a photosensitive resin layer disposed on the temporary support,

[0011] The turbidity of a solution obtained by dissolving 0.1 m 2 of the photosensitive transfer material in 1 liter of a 1 mass% sodium carbonate aqueous solution at 30°C is 60% or less.

[0012] <2> The photosensitive transfer material according to <1>, wherein

[0013] The thickness of the photosensitive resin layer is 10 μm or less.

[0014] <3> The photosensitive transfer material according to <1> or <2>, wherein

[0015] The photosensitive resin layer contains a polymerizable compound and an alkali-soluble resin,

[0016] 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.

[0017] <4> The photosensitive transfer material according to any one of <1> to <3>, wherein

[0018] The photosensitive resin layer contains an alkali-soluble resin,

[0019] The acid value of the alkali-soluble resin is 120 mgKOH / g or more.

[0020] <5> The photosensitive transfer material according to any one of <1> to <4>, wherein

[0021] The photosensitive resin layer contains an alkali-soluble resin,

[0022] The alkali-soluble resin contains a structural unit derived from styrene.

[0023] <6> The photosensitive transfer material according to <5>, wherein

[0024] The content of the structural unit derived from styrene is 40 mass% or more with respect to the total mass of the alkali-soluble resin.

[0025] <7> The photosensitive transfer material according to any one of <1> to <6>, wherein

[0026] The photosensitive resin layer contains a polymerizable compound having an acid group.

[0027] <8> The photosensitive transfer material according to any one of <1> to <7>, further comprising a thermoplastic resin layer between the temporary support and the photosensitive resin layer.

[0028] <9> A method for manufacturing a resin pattern, comprising:

[0029] make <1> to <8> The process of bonding the side of the photosensitive resin layer in the photosensitive transfer material that is not opposite to the temporary support to the substrate, as described in any one of the above.

[0030] The process of exposing the photosensitive resin layer in the photosensitive transfer material to a pattern after the bonding process; and

[0031] The process of developing the photosensitive resin layer after the pattern exposure process to form a resin pattern.

[0032] <10> A method for manufacturing circuit wiring, comprising:

[0033] make <1> to <8> The process of bonding the side of the photosensitive resin layer in the photosensitive transfer material that is not opposite to the temporary support to the substrate, as described in any one of the above.

[0034] The process of exposing the photosensitive resin layer in the photosensitive transfer material to a pattern after the bonding process;

[0035] The process of developing the photosensitive resin layer after the pattern exposure process to form a resin pattern; and

[0036] The process of etching the substrate in areas where no resin pattern is configured.

[0037] <11> A method for manufacturing a touch panel, comprising:

[0038] make <1> to <8> The process of bonding the side of the photosensitive resin layer in the photosensitive transfer material that is not opposite to the temporary support to the substrate, as described in any one of the above.

[0039] The process of exposing the photosensitive resin layer in the photosensitive transfer material to a pattern after the bonding process;

[0040] The process of developing the photosensitive resin layer after the pattern exposure process to form a resin pattern; and

[0041] The process of etching the substrate in areas where no resin pattern is configured.

[0042] Invention Effects

[0043] According to one embodiment of the present invention, a photosensitive transfer material can be provided that suppresses the formation of scum (agglomerates) even during prolonged development processing. Furthermore, according to another embodiment of the present invention, a method for manufacturing a resin pattern using the above-described photosensitive transfer material, a method for manufacturing circuit wiring, and a method for manufacturing a touch panel can be provided. Attached Figure Description

[0044] Figure 1 This is a schematic diagram illustrating an example of the structure of a photosensitive transfer material. Detailed Implementation

[0045] The present invention will now be described. The description will be made with reference to the accompanying drawings, although symbols may sometimes be omitted.

[0046] In the designation of groups (atomic groups) in this specification, the designations without substitution and unsubstituted groups include groups without substituents, and also include groups with substituents. For example, the designation of "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups), but also alkyl groups with substituents (substituted alkyl groups).

[0047] In this specification, "(meth)acrylic acid" means either or both acrylic acid and methacrylic acid, and "(meth)acrylate" means either or both acrylate and methacrylate.

[0048] Furthermore, the chemical structural formulas in this specification are sometimes described as simplified structural formulas with hydrogen atoms omitted.

[0049] In this specification, where multiple substances are present in each component, unless otherwise specified, the amount (content, etc.) of each component refers to the total amount (total content, etc.) of these multiple substances.

[0050] In this specification, the numerical range indicated by “~” refers to the range encompassed by the values ​​recorded before and after “~” as the lower and upper limits.

[0051] In this specification, "mass%" and "weight%" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning.

[0052] In this specification, the term "process" includes not only independent processes, but also processes that achieve the intended purpose, even if they cannot be clearly distinguished from other processes.

[0053] In this specification, unless otherwise specified, "exposure" includes not only exposure using light, but also depiction using particle beams such as electron beams and ion beams. Furthermore, examples of light used in exposure include bright-line spectra from mercury lamps, far-ultraviolet light represented by excimer lasers, extreme ultraviolet (EUV) light, and active light rays (active energy rays) such as X-rays.

[0054] Unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in this invention are molecular weights calculated by using a gel permeation chromatography (GPC) analytical apparatus with columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation) and detecting compounds in THF (tetrahydrofuran) solvent using a differential refractometer, with polystyrene as a standard substance.

[0055] In this specification, a combination of two or more preferred methods is a more preferred method.

[0056] [Photosensitive transfer materials]

[0057] The photosensitive transfer material of the present invention comprises a temporary support and a photosensitive resin layer disposed on the temporary support.

[0058] Dissolve 0.1 mg of sodium carbonate in 1 liter of a 1% sodium carbonate aqueous solution at 30°C. 2 The turbidity of the solution obtained from the photosensitive transfer material is below 60%.

[0059] If the developing process is prolonged, scum (agglomerates) may sometimes form and adhere to the developing equipment and the product. Components that contribute to this scum (agglomerates) include polymeric compounds and photopolymerization initiators contained in the photosensitive resin layer. If these components aggregate in the developing solution, the turbidity of the developing solution increases.

[0060] In the photosensitive transfer material involved in this invention, 0.1 mg is dissolved in 1 liter of a 1% sodium carbonate aqueous solution at 30°C. 2 The turbidity of the solution obtained from the photosensitive transfer material is less than 60%, therefore the turbidity of the developing solution is also low during the developing process. By using the photosensitive transfer material according to the present invention, the formation of scum (agglomerates) can be suppressed even during long-term developing processes.

[0061] The photosensitive transfer material involved in this invention will be described in detail below.

[0062] The photosensitive transfer material of the present invention 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 other layers, or it may be disposed via other layers. Furthermore, other layers may be disposed on the side of the photosensitive resin layer opposite to the side facing the temporary support. Examples of other layers besides the temporary support and the photosensitive resin layer include, for example, a thermoplastic resin layer, an intermediate layer, and a cover film.

[0063] Figure 1 This is an example of the layer structure of the photosensitive transfer material involved in the present invention. Figure 1 The photosensitive transfer material 100 shown is sequentially stacked with a temporary support 10, a thermoplastic resin layer 12, an intermediate layer 14, a photosensitive resin layer 16, and a cover film 18.

[0064] In the photosensitive transfer material involved in this invention, 0.1 mg is dissolved in 1 L (liter) of a 1% by mass sodium carbonate aqueous solution at 30°C. 2 The turbidity of the solution obtained from the photosensitive transfer material is less than 60%. Turbidity can be measured, for example, by the following method.

[0065] First, prepare a 1% (w / w) sodium carbonate aqueous solution and adjust the temperature to 30°C. Add 0.02 mg of sodium carbonate solution to 200 mL of the sodium carbonate aqueous solution. 2 The photosensitive transfer material was stirred at 30°C for 4 hours while being careful to prevent air bubbles from being introduced. After stirring, the insoluble temporary support was removed, and the turbidity of the solution containing the photosensitive transfer material was measured. A turbidimeter (product name "NDH4000", manufactured by NIPPON DENSHOKU INDUSTRIES Co., LTD.) was used, along with a liquid measurement unit and a dedicated liquid measurement cuvette with a 20mm optical path length. Additionally, in cases where the photosensitive transfer material contained a cover film, the material was added to a 1% (w / w) sodium carbonate aqueous solution after peeling.

[0066] From the viewpoint that the formation of scum (aggregates) can be further suppressed when the development process is carried out for a long time, the turbidity 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.

[0067] <Temporary support>

[0068] The photosensitive transfer material involved in this invention has a temporary support.

[0069] The temporary support is a support that supports the photosensitive resin layer or a laminate including the photosensitive resin layer and is peelable.

[0070] From the viewpoint that exposure of the photosensitive resin layer through the temporary support is possible during pattern exposure of the photosensitive resin layer, the temporary support preferably has light transmittance. Furthermore, in this specification, "having light transmittance" means that the transmittance of light of the wavelength used in pattern exposure is 50% or more.

[0071] From the viewpoint of improving the exposure sensitivity of the photosensitive resin layer, the temporary support preferably has a light transmittance of 60% or more for the wavelength (preferably 365 nm) used in pattern exposure, more preferably 70% or more.

[0072] Furthermore, the transmittance of a photosensitive transfer material layer is the ratio of the intensity of the emitted light to the intensity of the incident light when light is incident in a direction perpendicular to the main surface of the layer (i.e., the thickness direction). The transmittance was measured using the product name "MCPD Series" manufactured by OTSUKA ELECTRONICS Co., LTD.

[0073] The temporary support can be a single layer or a stack of two or more layers.

[0074] Examples of substrates that can be used to form a temporary support include glass, resin film, and paper. From the viewpoints of strength, flexibility, and light transmittance, a resin film is preferred as the substrate for forming the temporary support.

[0075] Examples of resin films include polyethylene terephthalate (PET) films, cellulose triacetate films, polystyrene films, and polycarbonate films. Among these, PET films are preferred, and biaxially stretched PET films are more preferred.

[0076] There are no particular limitations on the thickness of the temporary support. It can be selected appropriately based on the material, taking into account the strength of the support, the flexibility required for bonding with the substrate for circuit wiring, and the light transmittance required in the initial exposure process.

[0077] The thickness of the temporary support is preferably 5μm to 100μm, and more preferably 10μm to 50μm from the perspective of ease of operation and versatility.

[0078] [Photosensitive resin layer]

[0079] The photosensitive transfer material of the present invention comprises a photosensitive resin layer. The photosensitive resin layer is preferably a negative photosensitive resin layer in which the solubility of the exposed portion in the developer decreases upon exposure and the non-exposed portion is removed by development. However, the photosensitive resin layer is not limited to a negative photosensitive resin layer; it may also be a positive photosensitive resin layer in which the solubility of the exposed portion in the developer increases upon exposure and the exposed portion is removed by development.

[0080] A photosensitive resin layer is obtained, for example, by coating a photosensitive resin composition and allowing it to dry.

[0081] The photosensitive resin layer preferably contains polymer A, polymerizable compound B, and a photopolymerization initiator. The photosensitive resin layer preferably contains 10% to 90% by mass of polymer A, 5% to 70% by mass of polymerizable compound B, and 0.01% to 20% by mass of photopolymerization initiator relative to the total mass of the photosensitive resin layer. The components are described in order below.

[0082] <ingredients>

[0083] (Polymer A)

[0084] Polymer A is preferably an alkali-soluble resin. An alkali-soluble resin is a polymer that readily dissolves in alkali substances. Furthermore, in this specification, "alkali-soluble" means that the solubility of sodium carbonate in 100g of a 1% (by mass) aqueous solution is 0.1g or more at 22°C.

[0085] From the viewpoint of further suppressing the formation of scum (agglomerates) during prolonged developing processes, the acid value of polymer A is preferably 120 mg KOH / g or higher, more preferably 150 mg KOH / g or higher, and even more preferably 180 mg KOH / g or higher. The alkali-soluble resin acts as a dispersant in the developing solution. It is believed that if the acid value of the alkali-soluble resin is 120 mg KOH / g or higher, the dispersion effect of components insoluble in the developing solution is high, and the formation of scum (agglomerates) can be suppressed.

[0086] There is no particular upper limit to the acid value of polymer A. From a resolution point of view, the acid value of polymer A is preferably below 220 mg KOH / g, and more preferably below 200 mg KOH / g.

[0087] Additionally, the acid value is the mass of potassium hydroxide [mg] required to neutralize 1g of the sample.

[0088] In this specification, the unit of acid value is stated as mgKOH / g. Acid value can be calculated, for example, from the average content of acid groups in the compound.

[0089] The acid value of polymer A can be adjusted by using the types of structural units that make up polymer A and the content of structural units containing acid groups.

[0090] The weight-average molecular weight of polymer A is preferably 5,000 to 500,000. If the weight-average molecular weight is 500,000 or less, resolution and developability are improved, therefore it is preferred. 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, if the weight-average molecular weight is 5,000 or more, the properties of the developing aggregate and the properties of the unexposed film, such as edge melting and chipping, can be controlled when it is used as a photosensitive resin laminate, therefore it is preferred. 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 melting refers to the degree to which the photosensitive resin layer easily protrudes from the end face of the roller when it is wound into a roller shape as a photosensitive resin laminate. Chipping refers to the degree to which the chip easily scatters when the unexposed film is cut with a cutting machine. If the shavings adhere to the upper surface of the photosensitive resin laminate, they will be transferred to the mask in subsequent exposure processes, resulting in a defective product.

[0091] 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 this invention, the molecular weight is a value determined using gel permeation chromatography. Furthermore, the dispersity is the ratio of weight-average molecular weight to number-average molecular weight (weight-average molecular weight / number-average molecular weight).

[0092] From the viewpoint of suppressing the reduction in linewidth and resolution due to focus position shift during exposure, polymer A preferably contains structural units derived from monomers having aromatic hydrocarbon groups. Examples of aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The content of structural units derived from monomers having aromatic hydrocarbon groups in polymer A relative to the total mass of polymer A is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, particularly preferably 45% by mass or more, and most preferably 50% by mass or more. There is no particular limitation on the upper limit of the above content. Based on the total mass of polymer A, the above content is preferably 95% by mass or less, more preferably 85% by mass or less. Furthermore, in the case of multiple polymers A, the content of structural units derived from monomers having aromatic hydrocarbon groups is calculated as a weight average.

[0093] Examples of monomers having an aromatic hydrocarbon group include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimers, and styrene trimers). Among these, monomers having an aromatic hydrocarbon group are preferably monomers having an aralkyl group or styrene, and more preferably styrene.

[0094] 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% to 80% by mass, further preferably 45% to 70% by mass, and especially preferably 50% to 55% by mass, based on the total mass of polymer A.

[0095] Aryl groups include substituted or unsubstituted phenylalkyl groups (except benzyl groups) and substituted or unsubstituted benzyl groups. Aryl groups are preferably substituted or unsubstituted benzyl groups.

[0096] Ethyl phenyl (meth)acrylate is an example of a monomer containing a phenyl alkyl group.

[0097] Examples of benzyl monomers include benzyl (meth)acrylates and benzyl vinyl monomers. Examples of benzyl (meth)acrylates include benzyl (meth)acrylate and benzyl (meth)acrylate chloride. Examples of benzyl vinyl monomers include vinyl benzyl chloride and vinyl benzyl alcohol. Among these, benzyl (meth)acrylate is preferred. When the monomer having an aromatic hydrocarbon group is benzyl (meth)acrylate, the content of structural units derived from benzyl (meth)acrylate, based on the total mass of polymer A, is preferably 50% to 95% by mass, more preferably 60% to 90% by mass, further preferably 70% to 90% by mass, and particularly preferably 75% to 90% by mass.

[0098] Polymer A containing structural units derived from monomers having aromatic hydrocarbon groups is preferably a polymer containing structural units derived from monomers having aromatic hydrocarbon groups and structural units derived from at least one monomer selected from the first monomer and the second monomer described later.

[0099] Polymer A, which does not contain structural units derived from monomers having aromatic hydrocarbon groups, is preferably a polymer containing structural units derived from at least one monomer selected from the first monomer and the second monomer, and more preferably a polymer containing at least one structural unit derived from the first monomer and at least one structural unit derived from the second monomer.

[0100] The first monomer is a monomer having an anionic group and at least one polymerizable unsaturated group in its 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 half-ester. Among these, (meth)acrylic acid is preferred.

[0101] The content of structural units derived from the first monomer in polymer A relative to the total mass of polymer A is preferably 5% to 50% by mass, more preferably 10% to 40% by mass, and even more preferably 15% to 30% by mass.

[0102] In addition, in this specification, "(meth)acrylic acid" means acrylic acid or methacrylic acid, "(meth)acryloyl" means acryloyl or methacryloyl, and "(meth)acrylate" means "acrylate" or "methacrylate".

[0103] The second monomer is a monomer that does not have anionic groups and has at least one polymerizable unsaturated group in its molecule. Examples of the second monomer include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, vinyl esters such as vinyl acetate, and methacrylonitrile. The second monomer is preferably methyl methacrylate, 2-ethylhexyl methacrylate, or n-butyl methacrylate, and is particularly preferably methyl methacrylate.

[0104] The content of structural units derived from the second monomer in polymer A relative to the total mass of polymer A is preferably 5% to 60% by mass, more preferably 15% to 50% by mass, and even more preferably 20% to 45% by mass.

[0105] From the viewpoint of suppressing the decrease in linewidth and resolution due to focus position shift during exposure, polymer A preferably contains structural units derived from at least one monomer selected from monomers having an aryl group and styrene. Specifically, polymer A is preferably a copolymer containing structural units derived from styrene, structural units derived from methyl methacrylate, and structural units derived from methacrylic acid.

[0106] As a first embodiment, polymer A is preferably a polymer containing 25% to 40% by mass of structural units derived from monomers having aromatic hydrocarbon groups, 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. Furthermore, as a second embodiment, polymer A is preferably a polymer containing 70% to 90% by mass of structural units derived from monomers having aromatic hydrocarbon groups and 10% to 25% by mass of structural units derived from the first monomer. Furthermore, as a third embodiment, polymer A is preferably a polymer containing 40% to 60% by mass of structural units derived from monomers having aromatic hydrocarbon groups, 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.

[0107] Polymer A can have a branched structure or an alicyclic structure in its side chain. By using monomers containing groups with a branched structure in their side chain or monomers containing groups with an alicyclic structure in their side chain, a branched structure or an alicyclic structure can be introduced into the side chain of polymer A.

[0108] Examples of monomers containing branched groups on their side chains include isopropyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, isoamyl methacrylate, tert-amyl methacrylate, sec-isoamyl methacrylate, 2-octyl methacrylate, 3-octyl methacrylate, and tert-octyl methacrylate. Among these, isopropyl methacrylate, isobutyl methacrylate, or tert-butyl methacrylate are preferred monomers, and isopropyl methacrylate or tert-butyl methacrylate are more preferred.

[0109] Examples of monomers containing a group having an alicyclic structure on 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 on the side chain include (meth)acrylate (bicyclo[2.2.1]hept-2) ester, (meth)acrylate-1-adamantyl ester, (meth)acrylate-2-adamantyl ester, (meth)acrylate-3-methyl-1-adamantyl ester, (meth)acrylate-3,5-dimethyl-1-adamantyl ester, (meth)acrylate-3-ethyladamantyl ester, (meth)acrylate-3-methyl-5-ethyl-1-adamantyl ester, (meth)acrylate-3,5,8-triethyl-1-adamantyl ester, (meth)acrylate-3,5-dimethyl-8-ethyl-1-adamantyl ester, and (meth)acrylate-2-methyl-2-adamantyl ester. 2-Ethyl-2-adamantyl acrylate, 3-hydroxy-1-adamantyl acrylate, octahydro-4,7-benzyl-5-yl acrylate, octahydro-4,7-benzyl-1-yl methyl acrylate, 1-menthol acrylate, tricyclodecane acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptane acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptane acrylate, norbornyl acrylate, isobornyl acrylate, fenyl acrylate, 2,2,5-trimethylcyclohexyl acrylate and cyclohexyl acrylate. Among them, the monomers containing groups having alicyclic structures on the side chains are preferably cyclohexyl methacrylate, norbornyl methacrylate, isobornyl methacrylate, 1-adamantyl methacrylate, 2-adamantyl methacrylate, fentanyl methacrylate, 1-menthol methacrylate, and tricyclodecane methacrylate, and particularly preferably cyclohexyl methacrylate, norbornyl methacrylate, isobornyl methacrylate, 2-adamantyl methacrylate, or tricyclodecane methacrylate.

[0110] The photosensitive resin layer may contain only one polymer A or two or more polymers A. When containing two or more polymers A, the photosensitive resin layer preferably contains two polymers A that include structural units derived from monomers having aromatic hydrocarbon groups. Furthermore, the photosensitive resin layer preferably contains polymer A1, which includes structural units derived from monomers having aromatic hydrocarbon groups, and polymer A2, which does not include structural units derived from monomers having aromatic hydrocarbon groups. In the latter case, based on the total mass of polymers A, the content of polymer A1 is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more.

[0111] The synthesis of polymer A is preferably carried out as follows: Benzoyl peroxide, azoisobutyronitrile, or other free radical polymerization initiators are added to an appropriate amount of a solution of one or more of the monomers diluted with solvents such as acetone, methyl ethyl ketone, or isopropanol, while heating and stirring. After the reaction is complete, the solvent can be added to adjust the concentration to the desired level. In addition to solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization are also possible polymerization methods.

[0112] The glass transition temperature (Tg) of polymer A is preferably 30°C to 135°C. By including polymer A with a Tg of 135°C or lower in the photosensitive resin layer, the decrease in linewidth and resolution due to focus position shift during exposure can be suppressed. The Tg of polymer A is more preferably 130°C or lower, even more preferably 120°C or lower, and particularly preferably 110°C or lower. Furthermore, from the viewpoint of improving edge melt resistance, it is preferable to include polymer A with a Tg of 30°C or higher in the photosensitive resin layer. The Tg of polymer A is more preferably 40°C or higher, even more preferably 50°C or higher, particularly preferably 60°C or higher, and most preferably 70°C or higher.

[0113] The content of polymer A relative to the total mass of the photosensitive resin layer is preferably in the range of 10% to 90% by mass, more preferably 30% to 70% by mass, and even more preferably 40% to 60% by mass. If the content of polymer A relative to the total mass of the photosensitive resin layer is 90% by mass or less, the development time can be controlled, which is therefore preferable. On the other hand, if the content of polymer A relative to the total mass of the photosensitive resin layer is 10% by mass or more, the resistance to edge melting is improved, which is also preferable.

[0114] (Polymer compound B)

[0115] The photosensitive resin layer contains polymeric compound B, which has polymeric groups.

[0116] In this specification, "polymerizable compound" refers to a compound that is different from polymer A described above and polymerized by the polymerization initiator described below.

[0117] As for the polymerizable group in polymerizable compound B, there are no particular restrictions as long as it is a group related to the polymerization reaction. Examples include olefinic unsaturated groups such as vinyl, acryloyl, methacryloyl, styryl, and maleimide; and cationic polymerizable groups such as epoxy and oxetyl.

[0118] The polymerizable group is preferably an olefinic unsaturated group, more preferably an acryloyl group or a methacryloyl group.

[0119] As for polymerizable compound B, in terms of superior photosensitivity of the photosensitive resin layer, it is preferable to have one or more olefin unsaturated groups (i.e., olefin unsaturated compounds), and more preferably to have two or more olefin unsaturated groups in one molecule (i.e., polyfunctional olefin unsaturated compounds).

[0120] Furthermore, in terms of superior resolution and peelability, the number of olefinic unsaturated groups in one molecule of the olefinic unsaturated compound is preferably 6 or less, more preferably 3 or less, and even more preferably 2 or less.

[0121] In terms of superior balance between photosensitivity, resolution, and peelability of the photosensitive resin layer, the photosensitive resin layer preferably contains a difunctional olefin unsaturated compound having two olefin unsaturated groups in one molecule or a trifunctional olefin unsaturated compound having three olefin unsaturated groups, and more preferably contains a difunctional olefin unsaturated compound.

[0122] From the perspective of excellent peelability, the content of difunctional olefin unsaturated compounds is preferably 60% by mass or more, more preferably 70% by mass or more, relative to the total mass of polymeric compound B. There is no particular upper limit to the content of difunctional olefin unsaturated compounds, and it can be 100% by mass. That is, all polymeric compound B contained in the photosensitive resin layer can be difunctional olefin unsaturated compounds.

[0123] Furthermore, olefinic unsaturated compounds are preferably (meth)acrylate compounds.

[0124] -Polymerizing compound B1-

[0125] The photosensitive resin layer preferably contains a polymeric compound B1 having at least one aromatic ring and two olefinic unsaturated groups in one molecule.

[0126] Examples of aromatic rings in polymerizable compound B1 include aromatic hydrocarbon rings such as benzene rings, naphthalene rings, and anthracene rings; aromatic heterocycles such as thiophene rings, furan rings, pyrrole rings, imidazole rings, triazole rings, and pyridine rings; and their fused rings. The aromatic ring in polymerizable compound B1 is preferably an aromatic hydrocarbon ring, more preferably a benzene ring. Furthermore, the aforementioned aromatic ring may have substituents.

[0127] From the viewpoint of suppressing the swelling of the photosensitive resin layer caused by the developer and improving resolution, polymeric compound B1 preferably has a bisphenol backbone.

[0128] Examples of bisphenol skeletons include the bisphenol A skeleton derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), the bisphenol F skeleton derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and the bisphenol B skeleton derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane). The bisphenol A skeleton is preferred.

[0129] Examples of polymerizable compounds B1 having a bisphenol backbone include compounds having a bisphenol backbone and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol backbone.

[0130] The bisphenol backbone can be directly bonded to the polymerizable group, or it can be bonded through one or more alkene oxygen groups. The alkene oxygen groups bonded to the bisphenol backbone are preferably ethoxide or propoxide, more preferably ethoxide. There is no particular limitation on the number of additional alkene oxygen groups bonded to the bisphenol backbone. The number of additional alkene oxygen groups is preferably 4 to 16 per molecule, more preferably 6 to 14.

[0131] Regarding polymeric compound B1 having a bisphenol skeleton, it is described in paragraphs 0072 to 0080 of Japanese Patent Application Publication No. 2016-224162, the contents of which are incorporated herein by reference.

[0132] As the polymerizable compound B1, it is preferably a difunctional olefinic unsaturated compound having a bisphenol A backbone, more preferably 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane.

[0133] Examples of 2,2-bis(4-((methacryloyloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloyloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloyloxypentethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxydodecethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), and 2,2-bis(4-(methacryloyloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.). 2,2-bis(4-(methacryloyloxydiethoxy)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.).

[0134] As polymeric compounds, B1 can be represented by compounds represented by the following general formula (I).

[0135] [Chemical Formula 1]

[0136]

[0137] In the formula, R 1 and R 2 Each of the following groups independently represents a hydrogen atom or a methyl group: A is C2H4, B is C3H6, n1 and n3 are independent integers from 1 to 39, and n1+n3 is an integer from 2 to 40; n2 and n4 are independent integers from 0 to 29, and n2+n4 is an integer from 0 to 30; the repeating units of -(AO)- and -(BO)- can be arranged randomly or in blocks. In the case of blocks, either -(AO)- or -(BO)- can be a bisphenol group side.

[0138] 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.

[0139] The photosensitive resin layer may contain only one polymeric compound B1, or it may contain two or more compounds.

[0140] From the perspective of superior resolution, the content of polymeric compound B1 in the photosensitive resin layer relative to the total mass of polymeric compound B is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 55% by mass or more, and especially preferably 60% by mass or more. There is no particular upper limit to the content of polymeric compound B1. From the perspective of peelability, the content of polymeric compound B1 relative to the total mass of polymeric compound B is preferably 99% by mass or less, more preferably 95% by mass or less, further preferably 90% by mass or less, and especially preferably 85% by mass or less.

[0141] -Polymerizing compound B2-

[0142] The photosensitive resin layer preferably contains a polymeric compound B2 with acid groups. By using the polymeric compound B2 with acid groups to disperse components insoluble in the developer, the formation of scum (agglomerates) can be suppressed.

[0143] Examples of acid groups include carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups, and phosphate groups.

[0144] Examples of carboxyl-containing polymeric compounds include unsaturated fatty acids such as acrylic acid, methacrylic acid, phthalic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, and cinnamic acid, as well as carboxyl-modified polyfunctional acrylate compounds. Examples of carboxyl-modified polyfunctional acrylate compounds include, for instance, 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. Carboxyl-modified polyfunctional acrylate compounds are commercially available products. Commercially available products include ARONIX M-510, ARONIX M-520, ARONIX TO-2349 and ARONIX TO-2359 (all manufactured by TOAGOSEI CO., Ltd.).

[0145] Examples of polymeric compounds containing phenolic hydroxyl groups 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.

[0146] Examples of polymeric compounds containing sulfonic acid groups include vinyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, and butyl sulfonic acid-modified acrylamide.

[0147] Examples of polymeric compounds containing phosphoric acid groups include vinyl phosphoric acid, styrene phosphoric acid, and butyl phosphoric acid-modified acrylamide.

[0148] From the viewpoint of further dispersing components insoluble in the developer, polymeric compound B2 having an acid group is preferably a polymeric compound having a carboxyl group.

[0149] The photosensitive resin layer may contain only one polymeric compound B2, or it may contain two or more.

[0150] From the viewpoint of further dispersing the components insoluble in the developer, the content of polymeric compound B2 in the photosensitive resin layer relative to the total mass of polymeric compound B is preferably 10% to 40% by mass, more preferably 15% to 35% by mass, and even more preferably 20% to 30% by mass.

[0151] The photosensitive resin layer may contain polymeric compound B other than polymeric compound B1. Furthermore, the photosensitive resin layer may contain polymeric compound B other than polymeric compound B2.

[0152] There are no particular limitations on polymerizable compound B other than polymerizable compounds B1 and B2, and appropriate selections can be made from known compounds. Examples of polymerizable compounds B other than polymerizable compounds B1 and B2 include compounds having one olefin unsaturated group in one molecule (i.e., monofunctional olefin unsaturated compounds), difunctional olefin unsaturated compounds without an aromatic ring, and olefin unsaturated compounds with three or more functions.

[0153] Examples of monofunctional alkenyl unsaturated compounds include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl butylene glycol ester, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate.

[0154] Examples of difunctional olefinic unsaturated compounds that do not have an aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate.

[0155] Examples of alkylene glycol di(meth)acrylates include tricyclodecanediethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecanediethanol 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.

[0156] 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.

[0157] 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 examples 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.).

[0158] Examples of olefinic unsaturated compounds with three or more functions include pentaerythritol (tris / tetra / penta / hexa)methacrylate, pentaerythritol (tris / tetra)methacrylate, trimethylolpropane tri(meth)acrylate, bis(trimethylolpropane)tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanurate tri(meth)acrylate, glycerol tri(meth)acrylate, and their epoxide-modified derivatives.

[0159] Here, "(tri / tetra / penta / hexa)meth)acrylate" refers to the concept that includes tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate and hexa(meth)acrylate, and "(tri / tetra)meth)acrylate" refers to the concept that includes tri(meth)acrylate and tetra(meth)acrylate.

[0160] The photosensitive resin layer preferably contains a polymerizable compound B1 and an olefinically unsaturated compound with three or more functions, more preferably it contains a polymerizable compound B1 and two or more olefinically unsaturated compounds with three or more functions. In this case, the mass ratio of the polymerizable compound B1 to the olefinically unsaturated compound with three or more functions (total mass of polymerizable compound B1 : total mass of olefinically unsaturated compound with three or more functions) 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.

[0161] Examples of epoxide-modified olefinic compounds with three or more functions include caprolactone-modified (meth)acrylate compounds (KAYARAD DPCA-20, manufactured by Nippon Kayaku Co., Ltd.; A-9300-1CL, manufactured by Shin-Nakamura Chemical Co., Ltd.), epoxide-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 135, manufactured by DAICEL-ALLNEX LTD.), ethoxylated glycerol triacrylate (A-GLY-9E, manufactured by Shin-Nakamura Chemical Co., Ltd.), ARONIX TO-2349 (manufactured by TOAGOSEICO., Ltd.), and ARONIX... M-520 (manufactured by TOAGOSEI CO., Ltd.) and ARONIX M-510 (manufactured by TOAGOSEI CO., Ltd.).

[0162] The photosensitive resin layer may contain one polymeric compound B alone, or it may contain two or more compounds.

[0163] The content of polymeric compound B relative to the total mass of the photosensitive resin layer is preferably 10% to 70% by mass, more preferably 20% to 60% by mass, and even more preferably 20% to 50% by mass.

[0164] The weight-average molecular weight (Mw) of polymeric compound B is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.

[0165] The ratio of the content of polymeric compound B to the content of polymer A (preferably an 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 the above ratio, the polymeric compound B, which is insoluble in the developer, forms oil droplets, and the alkali-soluble resin acts as a dispersant, inhibiting the aggregation of oil droplets and suppressing the formation of scum (agglomerates).

[0166] (Any ingredients)

[0167] The photosensitive resin layer may contain components other than polymer A and polymeric compound B.

[0168] -Photopolymerization initiator-

[0169] The photosensitive resin layer preferably contains a photopolymerization initiator.

[0170] Photopolymerization initiators are compounds that can initiate the polymerization of polymerizable compounds using active light sources such as ultraviolet light, visible light, and X-rays. There are no particular limitations on photopolymerization initiators; any known photopolymerization initiator can be used.

[0171] Examples of photopolymerization initiators include photoradical polymerization initiators and photocationic polymerization initiators. Among them, photoradical polymerization initiators are preferred.

[0172] Examples of photoradical polymerization initiators include photopolymerization initiators with an oxime ester skeleton, photopolymerization initiators with an α-aminoalkylphenyl ketone skeleton, photopolymerization initiators with an α-hydroxyalkylphenyl ketone skeleton, photopolymerization initiators with an acylphosphine oxide skeleton, and photopolymerization initiators with an N-phenylglycine skeleton.

[0173] Furthermore, from the viewpoints of photosensitivity, visibility of the exposed and unexposed areas, and resolution, the photosensitive resin layer preferably contains at least one selected from 2,4,5-triarylimidazolium dimers and their derivatives as a photoradical polymerization initiator. Additionally, the two 2,4,5-triarylimidazolium skeletons in the 2,4,5-triarylimidazolium dimers and their derivatives may be the same or different.

[0174] Examples of derivatives of 2,4,5-triarylimidazolium dimers include 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazolium dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazolium dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazolium dimer.

[0175] The photoradical polymerization initiator can be the polymerization initiator described in paragraphs 0031 to 0042 of Japanese Patent Application Publication No. 2011-95716 and paragraphs 0064 to 0081 of Japanese Patent Application Publication No. 2015-14783.

[0176] Examples of photoradical polymerization initiators include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisole (p,p'-dimethoxybenzyl), and benzophenone.

[0177] Commercially available photoradical polymerization initiators include, for example, 2,4-bis(trichloromethyl)-6-[2-(4-methylphenyl)vinyl]-1,3,5-triazine (trade name: TAZ-110, manufactured by Midori Kagaku Co., Ltd.), (trade name: TAZ-111, manufactured by Midori Kagaku Co., Ltd.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.), and 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyl oxime) (trade name: Irgacure (registered trademark) OXE-01, BASF JAPAN). (manufactured by BASF JAPAN LTD.), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl] acetophenone-1-(O-acetyl oxime) (trade names: Irgacure 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-morpholino(memo of morpholino))phenyl]-1-butanone (trade names: Omnirad 379EG, manufactured by IGM Resins BV), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropyl-1-one (trade names: Omnirad 907, IGM Resins) (BV manufactured), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanoyl)benzyl]phenyl}-2-methylpropane-1-one (trade names: Omnirad 127, manufactured by IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (trade names: Omnirad 369, manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropane-1-one (trade names: Omnirad 1173, manufactured by IGM Resins BV), 1-hydroxycyclohexylphenyl ketone (trade names: Omnirad 184, manufactured by IGM Resins BV), 2,2-dimethoxy-1,2-diphenylethane-1-one (trade names: Omnirad 651, manufactured by IGM Resins) 2,4,6-Trimethylbenzoyl-diphenylphosphine oxide (trade names: Omnirad TPO H, IGM Resins BV), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade names: Omnirad 819, IGM Resins BV)(Manufactured), oxime ester-based photopolymerization initiators (trade names: Lunar 6, manufactured by DKSH MANAGEMENT LTD.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazolium dimer) (trade name: B-CIM, manufactured by Hampford), and 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer (trade name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.).

[0178] Photocationic polymerization initiators (photoacid generators) are compounds that generate acids under active light. There are no particular limitations on the photocationic polymerization initiator, but compounds that generate acids upon sensing active light with wavelengths of 300 nm or higher (preferably 300 nm to 450 nm) are preferred. Furthermore, compounds that do not directly sense active light with wavelengths of 300 nm or higher can be used; as long as they are compounds that generate acids upon sensing active light with wavelengths of 300 nm or higher by being used in conjunction with a sensitizer, they are preferably used in combination with the sensitizer.

[0179] Photocationic polymerization initiators are preferably those that generate acids with a pKa of 4 or less, more preferably those that generate acids with a pKa of 3 or less, and especially preferably those that generate acids with a pKa of 2 or less. There are no particular limitations on the lower limit of the pKa value; for example, -10.0 is preferred.

[0180] Examples of photocationic polymerization initiators include ionic and nonionic photocationic polymerization initiators.

[0181] Examples of ionic photocationic polymerization initiators include diaryliodonium salts, triarylsulfonium salts, and quaternary ammonium salts.

[0182] The ionic photocationic polymerization initiator can be the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of Japanese Patent Application Publication No. 2014-85643.

[0183] Examples of nonionic photocationic polymerization initiators include trichloromethyltriazine compounds, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. The trichloromethyltriazine compounds, diazomethane compounds, and imide sulfonate compounds can be those described in paragraphs 0083 to 0088 of Japanese Patent Application Publication No. 2011-221494. Furthermore, the oxime sulfonate compounds can be those described in paragraphs 0084 to 0088 of International Patent Application Publication No. 2018 / 179640.

[0184] The photosensitive resin layer may contain one type of photopolymerization initiator or two or more types.

[0185] There is no particular limitation on the content of the photopolymerization initiator, but it 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. There is no particular limitation on the upper limit of the content of the photopolymerization initiator. The content of the photopolymerization initiator relative to the total mass of the photosensitive resin layer is preferably 10% by mass or less, more preferably 5% by mass or less.

[0186] -pigment-

[0187] From the viewpoints of visibility of the exposed and unexposed areas, visibility of the developed pattern, and resolution, the photosensitive resin layer preferably contains a pigment (hereinafter also referred to as "pigment N") with a maximum absorption wavelength of 450 nm or higher in the wavelength range of 400 nm to 780 nm during color development, and whose maximum absorption wavelength changes with acid, alkali, or free radicals. While the detailed mechanism is not yet fully understood, the presence of pigment N improves adhesion to adjacent layers (e.g., temporary supports and intermediate layers), resulting in superior resolution.

[0188] In this specification, "the maximum absorption wavelength of the pigment changes due to acid, alkali or free radical" refers to any of the following methods: the pigment in the color developing state is decolorized by acid, alkali or free radical; the pigment in the decolorized state is color developed by acid, alkali or free radical; and the pigment in the color developing state changes to another color developing state.

[0189] Specifically, pigment N can be a compound that changes color from a decolorized state upon exposure, or a compound that changes color from a color-developed state upon exposure. In this case, it can be a pigment whose color-developing or decolorizing state changes upon exposure due to the generation of acids, bases, or free radicals within the photosensitive resin layer, or a pigment whose color-developing or decolorizing state changes upon changes in the state (e.g., pH) within the photosensitive resin layer due to acids, bases, or free radicals. Furthermore, pigment N can be a pigment whose color-developing or decolorizing state changes directly upon receiving acids, bases, or free radicals as stimuli without exposure.

[0190] From the viewpoint of visibility and resolution of the exposed and unexposed areas, pigment N is preferably a pigment whose maximum absorption wavelength is changed by acid or free radicals, and more preferably a pigment whose maximum absorption wavelength is changed by free radicals.

[0191] From the viewpoint of visibility and resolution of the exposed and unexposed areas, the photosensitive resin layer is preferably composed of both a pigment N containing a pigment that changes the maximum absorption wavelength through free radicals and a photoradical polymerization initiator.

[0192] Furthermore, from the viewpoint of visibility of both the exposed and unexposed areas, pigment N is preferably a pigment that develops color through acid, alkali, or free radicals.

[0193] Examples of color-developing mechanisms for pigment N include adding a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator), or a photoalkali generator to a photosensitive resin layer, and then developing color through free radicals, acids, or bases generated by the photoradical polymerization initiator, photocationic polymerization initiator, or photoalkali generator after exposure.

[0194] From the viewpoint of visibility of the exposed and unexposed portions, the maximum absorption wavelength of pigment N in the wavelength range of 400 nm to 780 nm during color development is preferably 550 nm or more, more preferably 550 to 700 nm, and even more preferably 550 nm to 650 nm.

[0195] Furthermore, pigment N may have only one maximum absorption wavelength in the wavelength range of 400nm to 780nm for color development, or it may have two or more. If pigment N has two or more maximum absorption wavelengths in the wavelength range of 400nm to 780nm for color development, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths should be 450nm or higher.

[0196] The maximum absorption wavelength of pigment N was obtained by measuring the transmission spectrum of a solution containing pigment N (liquid temperature 25°C) in the range of 400 nm to 780 nm using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) under atmospheric conditions and detecting the wavelength at which the light intensity becomes minimal (i.e., the maximum absorption wavelength).

[0197] Examples of pigments that develop or decolorize through exposure include colorless compounds. Examples of pigments that decolorize through exposure include colorless compounds, diarylmethane pigments, oxazine pigments, xanthones, iminonaphthoquinone pigments, azomethyl alkaloid pigments, and anthraquinone pigments. From the viewpoint of visibility of both the exposed and unexposed areas, pigment N is preferably a colorless compound.

[0198] Examples of colorless compounds include colorless compounds having a triarylmethane skeleton (triarylmethane pigments), colorless compounds having a spiropyran skeleton (spiropyran pigments), colorless compounds having a fluorane skeleton (fluorane pigments), colorless compounds having a diarylmethane skeleton (diarylmethane pigments), colorless compounds having a rhodamine lactam skeleton (rhodamine lactam pigments), colorless compounds having an indolephthalide skeleton (indolephthalide pigments), and colorless compounds having a colorless golden ammonia skeleton (colorless golden ammonia pigments).

[0199] The colorless compound is preferably a triarylmethane pigment or a fluorane pigment, more preferably a colorless compound (triphenylmethane pigment) or a fluorane pigment with a triphenylmethane skeleton.

[0200] From the viewpoint of visibility of both exposed and unexposed areas, colorless compounds preferably have lactone rings, sultine rings, or sulfonyl lactone rings. The lactone rings, sultine rings, or sulfonyl lactone rings of the colorless compound react with free radicals generated by a photoradical polymerization initiator or acids generated by a photocationic polymerization initiator, thereby changing from a closed-ring state to an open-ring state to develop color, or changing from an open-ring state to a closed-ring state to decolorize. Colorless compounds are preferably compounds that have lactone rings, sultine rings, or sulfonyl lactone rings and develop color through ring-opening by free radicals or acids; more preferably, compounds that have lactone rings and develop color through ring-opening by free radicals or acids.

[0201] Examples of pigments N include the following dyes and colorless compounds.

[0202] Examples of dyes include Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Vernix Red, Methyl Violet 2B, Quinazine Red, Rose Red, Formyl Yellow, Thimorpholine, Xylenol Blue, Methyl Orange, p-Methyl Red, Congo Red, Benzopurine 4B, α-Naphthalene Red, Naphthalene Blue 2B, Naphthalene Blue A, Methyl Violet, Malachite Green, Hydroquinone, Victoria Pure Blue - Alkyl Naphthalene Sulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue#603 (manufactured by ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Pink#312 (manufactured by ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Red 5B (manufactured by ORIENT CHEMICAL INDUSTRIES CO., LTD.), Oil Scarlet#308 (manufactured by ORIENT CHEMICAL INDUSTRIES CO., LTD.), and Oil Red OG (manufactured by ORIENT CHEMICAL INDUSTRIES CO., LTD.). Oil Red RR (manufactured by ORIENT CHEMICAL INDUSTRIES CO.,LTD), Oil Green#502 (manufactured by ORIENT CHEMICAL INDUSTRIES CO.,LTD), Spiron Red BEH Special (manufactured by Hodogaya Chemical Co.,Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulfonyl rhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanisto-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0203] Examples of colorless compounds include p,p',p”-hexamethyltriaminotriphenylmethane (colorless crystal violet), Pergascript Blue SRB (manufactured by Novartis International AG), crystal violet lactone, malachite green lactone, benzoyl colorless methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-p-formyldiamino)fluorane, 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, and 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-aniline. 3-(N,N-diethylamino)-6-methyl-7-aniline fluorane, 3-(N,N-diethylamino)-6-methyl-7-phenyl fluorane, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorane, 3-(N,N-diethylamino)-6-methoxy-7-aminofluorane, 3-(N,N-diethylamino)-7-(4-chloroaniline)fluorane, 3-(N,N-diethylamino)-7-chlorofluorane, 3-(N,N-di-di-... 3-(N,N-diethylamino)-7,8-benzofluorane, 3-(N,N-dibutylamino)-6-methyl-7-aniline fluorane, 3-(N,N-dibutylamino)-6-methyl-7-phenylfluorane, 3-hydropyridyl-6-methyl-7-aniline fluorane, 3-pyrrolidine-6-methyl-7-aniline fluorane, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(1- n-Butyl-2-methylindole-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-phthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)phthalide and 3',6'-bis(diphenylamine)spiroisobenzofuran-1(3H),9'-[9H]xepide-3-one.

[0204] From the viewpoint of visibility of the exposed and unexposed areas, visibility of the pattern after development, and resolution, pigment N is preferably a pigment that changes the maximum absorption wavelength by free radicals, and more preferably a pigment that develops color by free radicals.

[0205] Pigment N is preferably colorless crystal violet, crystal violet lactone, bright green, or Victoria blue alkyl naphthalene sulfonate.

[0206] The photosensitive resin layer may contain only one type of pigment N, or it may contain two or more types.

[0207] From the viewpoint of visibility of the exposed and unexposed areas, visibility of the developed pattern, and resolution, the content of pigment N relative to the total mass of the photosensitive resin layer is preferably 0.1% by mass or more, more preferably 0.1% by mass to 10% by mass, even more preferably 0.1% by mass to 5% by mass, and particularly preferably 0.1% by mass to 1% by mass.

[0208] The content of pigment N refers to the total amount of pigment N contained in the photosensitive resin layer when it reaches its colored state. The following explanation uses a pigment that develops color via free radicals as an example to illustrate the quantitative method for determining the content of pigment N.

[0209] Solutions were prepared by dissolving 0.001 g and 0.01 g of pigment in 100 mL of methyl ethyl ketone. A photoradical polymerization initiator (Irgacure OXE01, manufactured by BASF JAPAN LTD.) was added to each solution, and the solutions were irradiated with 365 nm light, thereby generating free radicals and bringing all the pigments to their colored state. Subsequently, under atmospheric conditions, the absorbance of each solution at a liquid temperature of 25 °C was measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), and calibration curves were constructed.

[0210] Next, instead of the pigment, 3g of the photosensitive resin layer was dissolved in methyl ethyl ketone. Then, the absorbance of the solution that caused the pigment to fully develop was measured using the same method as described above. The pigment content in the photosensitive resin layer was calculated from the absorbance of the solution containing the obtained photosensitive resin layer, based on the calibration curve.

[0211] -surfactant-

[0212] From the viewpoint of thickness uniformity, the photosensitive resin layer preferably contains a surfactant.

[0213] Examples of surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. Among these, nonionic surfactants are preferred.

[0214] Examples of nonionic surfactants include, for example, polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based nonionic surfactants, and fluorinated nonionic surfactants.

[0215] From the perspective of improving resolution, the photosensitive resin layer preferably contains a fluorinated nonionic surfactant. This is believed to be because by containing a fluorinated nonionic surfactant in the photosensitive resin layer, the penetration of the etching solution into the photosensitive resin layer is inhibited, thereby reducing sidewall etching.

[0216] Commercially available fluorinated nonionic surfactants include Megaface F-551, F-552, and F-554 (all manufactured by DIC CORPORATION).

[0217] Furthermore, commercially available fluorinated surfactants include, for example, Megaface F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, and F-563. 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 (the above are DIC) (manufactured by CORPORATION), Fluorad FC430, FC431, FC171 (all manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA SOLUTIONS INC.), Ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (the above are NEOS products), etc.

[0218] Furthermore, as fluorinated surfactants, acrylic compounds that have a molecular structure containing functional groups with fluorine atoms, and whose functional groups containing fluorine atoms are cleaved and the fluorine atoms volatilize when heated, are preferred. Examples of such fluorinated surfactants include the Megaface DS series manufactured by DIC CORPORATION (Kanisho Kogyo Nichijou (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), such as Megaface DS-21.

[0219] Furthermore, as a fluorinated surfactant, a polymer of a vinyl ether compound having fluorinated alkyl or fluorinated alkylene ether groups and a hydrophilic vinyl ether compound is preferred.

[0220] Furthermore, block polymers can also be used as fluorinated surfactants.

[0221] Furthermore, as a fluorinated surfactant, it is preferable to use a fluorinated polymer compound that contains structural units derived from (meth)acrylate compounds having fluorine atoms and structural units derived from (meth)acrylate compounds having 2 or more (preferably 5 or more) alkeneoxy groups (preferably ethoxide or propoxide).

[0222] Furthermore, as a fluorinated surfactant, it can also be used on fluorinated polymers with olefinically unsaturated groups on their side chains. Examples include Megaface RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC CORPORATION).

[0223] From the viewpoint of improving environmental adaptability, surfactants derived from perfluorooctane acid (PFOA) and perfluorooctane sulfonate (PFOS) or other compounds with straight-chain perfluoroalkyl groups having 7 or more carbon atoms are preferred as fluorinated surfactants.

[0224] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxy and propoxy esters (e.g., glycerol propoxy ester, glycerol ethoxy ester, etc.), polyoxyethylene lauryl ether, polyoxyethylene octadecyl ether, polyoxyethylene oil-based 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), Solsperse 20000 (all manufactured by The Lubrizol Corporation), NCW-101, NCW-1001, NCW-1002 (all manufactured by FUJIFILM Wako Pure Chemical). (manufactured by Corporation), PIONIN D-6112, D-6112-W, D-6315 (the above are manufactured by Takemoto Oil & Fat Co., Ltd.), OLFINE E1010, Surfynol104, 400, 440 (the above are manufactured by Nissin Chemical Co., Ltd.), etc.

[0225] Examples of silicone surfactants include linear polymers composed of siloxane bonds and modified siloxane polymers with organic groups introduced into the side chains or ends.

[0226] Specific examples of silicone-based surfactants include DOWSIL 8032 ADDITIVE, Toray SILICONE DC3PA, Toray SILICONE SH7PA, Toray SILICONE DC11PA, Toray SILICONE SH21PA, Toray SILICONE SH28PA, Toray SILICONE SH29PA, Toray SILICONE SH30PA, and Toray SILICONE SH8400 (the above are Dow Corning Toray). (manufactured by Shin-Etsu Silicone Co., Ltd.) and X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (manufactured by Shin-Etsu Silicone Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc.), BYK307, BYK323, BYK330 (manufactured by BYK Co., Ltd.), etc.

[0227] The surfactant may be the surfactant described in paragraphs 0120 to 0125 of International Publication No. 2018 / 179640, the surfactant described in paragraph 0017 of Japanese Patent No. 4502784, and the surfactant described in paragraphs 0060 to 0071 of Japanese Patent Application Publication No. 2009-237362.

[0228] The photosensitive resin layer may contain one surfactant or two or more surfactants.

[0229] The surfactant content relative to the total mass of the photosensitive resin layer is preferably 0.001% to 10% by mass, more preferably 0.01% to 3% by mass.

[0230] -additive-

[0231] In addition to the above-mentioned components, the photosensitive resin layer may contain known additives as needed.

[0232] Examples of additives include free radical polymerization inhibitors, sensitizers, plasticizers, heterocyclic compounds, benzotriazoles, carboxybenzotriazoles, resins other than polymer A, and solvents. The photosensitive resin layer may contain one or more of these additives.

[0233] The photosensitive resin layer may contain free radical polymerization inhibitors.

[0234] Examples of free radical polymerization inhibitors include the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784. Furthermore, examples of free radical polymerization inhibitors include phenothiazine, phenothiazine, 4-methoxyphenol, naphthylamine, cuprous chloride, aluminum salt of N-nitrosophenylhydroxylamine, and diphenylnitrosamine. Among these, phenothiazine, phenothiazine, 4-methoxyphenol, or aluminum salt of N-nitrosophenylhydroxylamine are preferred.

[0235] 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.

[0236] Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylene carboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylene carboxybenzotriazole, N-(N,N-di-2-ethylhexyl)aminoethylene carboxybenzotriazole, 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole, and 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole. Commercially available examples of carboxybenzotriazoles include CBT-1 (manufactured by JOHOKUCHEMICAL CO., LTD.).

[0237] The total content of the free radical polymerization inhibitor, benzotriazole, and carboxybenzotriazole relative to the total mass of the photosensitive resin layer is preferably 0.01% to 3% by mass, more preferably 0.05% to 1% by mass. If the above content is 0.01% by mass or more, the photosensitive resin composition exhibits excellent storage stability. On the other hand, if the above content is 3% by mass or less, sensitivity can be maintained and dye decolorization can be suppressed.

[0238] The photosensitive resin layer may contain sensitizers.

[0239] There are no particular limitations on the sensitizers used; known sensitizers, dyes, and pigments can be used. Examples of sensitizers include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthonesone compounds, thioxanthonesone compounds, acridinone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalenedicarboximide compounds, triarylamine compounds, and aminoacridine compounds.

[0240] The photosensitive resin layer may contain one type of sensitizer or two or more types.

[0241] When the photosensitive resin layer contains a sensitizer, the content of the sensitizer can be appropriately selected according to the purpose. From the viewpoint of improving the sensitivity to the light source and improving the curing speed based on the balance between polymerization rate and chain transfer, the content of the sensitizer relative to the total mass of the photosensitive resin layer is preferably 0.01% to 5% by mass, more preferably 0.05% to 1% by mass.

[0242] The photosensitive resin layer may contain at least one selected from plasticizers and heterocyclic compounds.

[0243] As plasticizers and heterocyclic compounds, examples include the compounds described in paragraphs 0097 to 0103 and 0111 to 0118 of International Publication No. 2018 / 179640.

[0244] The photosensitive resin layer may contain resins other than polymer A.

[0245] Examples of resins other than polymer A include acrylic resins, styrene-acrylic copolymers (however, the content of structural units derived from styrene is less than 40% by mass), polyurethanes, polyvinyl alcohol, polyvinyl formal, polyamides, polyesters, epoxy resins, polyacetals, polyhydroxystyrene, polyimides, polybenzoxazoles, polysiloxanes, polyethyleneimines, polyallylamines, and polyalkylene glycols.

[0246] The photosensitive resin layer may contain solvent. When a photosensitive resin composition containing solvent is dried to form a photosensitive resin layer, solvent may sometimes remain in the photosensitive resin layer.

[0247] Furthermore, the photosensitive resin layer may also contain known additives such as metal oxide particles, antioxidants, rust inhibitors, chain transfer agents, dispersants, acid proliferation agents, development promoters, conductive fibers, thermal free radical polymerization initiators, thermal acid-generating agents, ultraviolet absorbers, tackifiers, crosslinking agents, and organic or inorganic precipitation inhibitors.

[0248] The additives that may be contained in the photosensitive resin layer are described in paragraphs 0165 to 0184 of Japanese Patent Application Publication No. 2014-85643, the contents of which are incorporated into this specification.

[0249] <Physical properties, etc.>

[0250] 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. Reducing the thickness of the photosensitive resin layer decreases the amount of insoluble components contained in the developing solution, thereby suppressing the formation of scum (agglomerates). For example, the lower limit of the thickness of the photosensitive resin layer is 0.5 μm.

[0251] Regarding the thickness of each layer of the photosensitive transfer material, a cross-section perpendicular to the main surface of the photosensitive transfer material is observed using a scanning electron microscope (SEM). The thickness of each layer is measured at more than 10 points based on the obtained observation images, and the average value is used to calculate the thickness.

[0252] From the perspective of superior 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. There is no particular upper limit to the transmittance of the photosensitive resin layer at a wavelength of 365 nm, but 99.9% is preferred.

[0253] <Formation Method>

[0254] There are no particular limitations on the method of forming the photosensitive resin layer, which is capable of forming a layer containing the above-mentioned components.

[0255] As a method for forming a photosensitive resin layer, an example can be given by forming it by: preparing a photosensitive resin composition containing polymer A, polymeric compound B and solvent, coating the photosensitive resin composition onto the surface of a temporary support or the like, and drying the coating film of the photosensitive resin composition.

[0256] Examples of photosensitive resin compositions used in the formation of a photosensitive resin layer include compositions containing polymer A, polymeric compound B, any of the above-mentioned components, and a solvent.

[0257] The viscosity of the photosensitive resin composition is adjusted, and it is preferable to contain a solvent in order to facilitate the formation of the photosensitive resin layer.

[0258] (solvent)

[0259] As a solvent contained in the photosensitive resin composition, there are no particular restrictions as long as it can dissolve or disperse polymer A, polymeric compound B, and any of the above components, and known solvents can be used.

[0260] Examples of solvents 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 them.

[0261] In the fabrication of a photosensitive transfer material comprising 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 alkylene glycol ethers and alkylene glycol ether acetates. More preferably, the solvent contains a mixed solvent comprising at least one selected from alkylene glycol ethers and alkylene glycol ether acetate solvents and at least one selected from ketones and cyclic ethers; even more preferably, it contains a mixed solvent comprising at least one selected from alkylene glycol ethers and alkylene glycol ether acetates, ketones, and cyclic ethers.

[0262] 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.

[0263] 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.

[0264] The solvent may be any solvent described in paragraphs 0092 to 0094 of International Publication No. 2018 / 179640 and any solvent described in paragraph 0014 of Japanese Patent Application Publication No. 2018-177889, which are incorporated herein by reference.

[0265] The photosensitive resin composition may contain one solvent alone or two or more solvents.

[0266] The solvent content in the photosensitive resin composition is preferably 50 to 1,900 parts by weight, more preferably 100 to 900 parts by weight, relative to 100 parts by weight of the total solids in the photosensitive resin composition.

[0267] There are no particular limitations on the preparation method of the photosensitive resin composition. For example, a method for preparing the photosensitive resin composition can be described as follows: a solution in which each component is dissolved in the solvent is prepared in advance, and the solution is obtained by mixing them in a specified proportion.

[0268] Before forming the photosensitive resin layer, the photosensitive resin composition is preferably filtered using a filter with a pore size of 0.2 μm to 30 μm.

[0269] There are no particular limitations on the coating method of the photosensitive resin composition; it can be coated using known methods. Examples of coating methods include slit coating, spin coating, curtain coating, and inkjet coating.

[0270] Furthermore, the photosensitive resin layer can be formed by coating the photosensitive resin composition onto the cover film described later and allowing it to dry.

[0271] <Impurities, etc.>

[0272] The photosensitive resin layer may contain a specified amount of impurities. Examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and their ions. Among these, halide ions, sodium ions, and potassium ions are easily incorporated as impurities, and therefore are preferably set to the following contents.

[0273] The impurity content 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, based on mass. The impurity content in the photosensitive resin layer can be set to 1 ppb or more or 0.1 ppm or more, based on mass.

[0274] As a method to keep impurities within the aforementioned range, examples include selecting raw materials with low impurity content as the raw material for the photosensitive resin layer, preventing impurity contamination during the formation of the photosensitive resin layer, and removing impurities during the formation of the photosensitive resin layer. By using this method, the impurity content can be kept within the aforementioned range.

[0275] Impurities can be quantified using known methods such as ICP (Inductively Coupled Plasma) luminescence spectrophotometry, atomic absorption spectrometry, and ion chromatography.

[0276] The photosensitive resin layer preferably contains low levels of specific compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane. The content of these specific compounds in the photosensitive resin layer, on a mass basis, is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less. The lower limit of the content, on a mass basis, is preferably 10 ppb, more preferably 100 ppb. The content of these specific compounds can be suppressed using the same method as for the aforementioned impurities. Furthermore, the content of these specific compounds can be quantified using a known determination method.

[0277] From the viewpoint of improving reliability and lamination, the water content in the photosensitive resin layer is preferably 0.01% to 1.0% by mass, more preferably 0.05% to 0.5% by mass.

[0278] [Thermoplastic resin layer]

[0279] The photosensitive transfer material of the present invention preferably has a thermoplastic resin layer between the temporary support and the photosensitive resin layer. If a thermoplastic resin layer is disposed between the temporary support and the photosensitive resin layer, the substrate following performance during the bonding process is improved, the incorporation of air bubbles between the substrate and the photosensitive transfer material is suppressed, thereby improving the adhesion to adjacent layers (e.g., the temporary support).

[0280] <ingredients>

[0281] (Alkali-soluble resin)

[0282] The thermoplastic resin layer contains alkali-soluble resin as it is a thermoplastic resin.

[0283] In addition, in this specification, "alkali solubility" means that the solubility of sodium carbonate in 100g of a 1% by mass aqueous solution is greater than 0.1g at 22°C.

[0284] Examples of alkali-soluble resins include acrylic resins, polystyrene, styrene-acrylic copolymers, polyurethanes, polyvinyl alcohol, polyvinyl formal, polyamides, polyesters, epoxy resins, polyacetals, polyhydroxystyrene, polyimides, polybenzoxazoles, polysiloxanes, polyethyleneimines, polyallylamines, and polyalkylene glycols.

[0285] From the viewpoint of developability and adhesion to adjacent layers, acrylic resin is preferred as an alkali-soluble resin.

[0286] Here, acrylic resin refers to a resin having at least one structural unit selected from structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylate, and structural units derived from (meth)acrylamide.

[0287] As an acrylic resin, the total content of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylate, and structural units derived from (meth)acrylamide is preferably 50% by mass or more relative to the total mass of the acrylic resin.

[0288] The total content of structural units derived from (meth)acrylic acid and structural units derived from (meth)acrylate relative to the total mass of acrylic resin is preferably 30% to 100% by mass, more preferably 50% to 100% by mass.

[0289] Furthermore, the alkali-soluble resin is preferably a polymer containing acid groups. Examples of acid groups include carboxyl, sulfonyl, phosphate, and phosphonic acid groups, with carboxyl groups being preferred.

[0290] There is no particular upper limit to the acid value of alkali-soluble resins. Preferably, the acid value of alkali-soluble resins is below 200 mg KOH / g, more preferably below 150 mg KOH / g.

[0291] There are no particular restrictions on the use of carboxyl-containing acrylic resins with an acid value of 60 mg KOH / g or higher, and they can be appropriately selected from known resins.

[0292] Examples of carboxyl-containing acrylic resins with an acid value of 60 mg KOH / g or higher include alkali-soluble resins containing carboxyl-containing acrylic resins with an acid value of 60 mg KOH / g or higher in the polymer described in paragraph 0025 of Japanese Patent Application Publication No. 2011-95716, acrylic resins containing carboxyl-containing acrylic resins with an acid value of 60 mg KOH / g or higher in the polymer described in paragraphs 0033 to 0052 of Japanese Patent Application Publication No. 2010-237589, and acrylic resins containing carboxyl-containing acrylic resins with an acid value of 60 mg KOH / g or higher in the adhesive polymer described in paragraphs 0053 to 0068 of Japanese Patent Application Publication No. 2016-224162.

[0293] The content of carboxyl-containing structural units in the above-mentioned carboxyl-containing acrylic resin is preferably 5% to 50% by mass relative to the total mass of the acrylic resin, more preferably 10% to 40% by mass, and even more preferably 12% to 30% by mass.

[0294] From the viewpoint of developability and adhesion to adjacent layers, alkali-soluble resins are particularly preferred acrylic resins having structural units derived from (meth)acrylic acid.

[0295] Alkali-soluble resins can possess reactive groups. These reactive groups can be those capable of addition polymerization, such as olefinic unsaturated groups; condensation groups like hydroxyl and carboxyl groups; and addition polymerization reactive groups like epoxy and (terminated) isocyanate groups.

[0296] The weight-average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and even more preferably 20,000 to 50,000.

[0297] The thermoplastic resin layer may contain one type of alkali-soluble resin or two or more types.

[0298] From the viewpoint of developability and adhesion to adjacent layers, the content of alkali-soluble resin relative to the total mass of the thermoplastic resin layer is preferably 10% to 99% by mass, more preferably 20% to 90% by mass, even more preferably 40% to 80% by mass, and particularly preferably 50% to 70% by mass.

[0299] (pigment)

[0300] The thermoplastic resin layer preferably contains a pigment (also referred to as "pigment B") with a maximum absorption wavelength of 450 nm or higher in the wavelength range of 400 nm to 780 nm during color development, and whose maximum absorption wavelength can be altered by acid, alkali, or free radicals. The preferred method for pigment B is the same as that for pigment N, except for the aspects described later.

[0301] From the viewpoint of visibility and resolution of the exposed and unexposed areas, pigment B is preferably a pigment whose maximum absorption wavelength is changed by acid or free radicals, and more preferably a pigment whose maximum absorption wavelength is changed by acid.

[0302] From the viewpoint of visibility and resolution of the exposed and unexposed areas, the thermoplastic layer preferably contains both a pigment (as pigment B) whose maximum absorption wavelength is altered by acid and a compound that generates acid through light (described later).

[0303] The thermoplastic resin layer may contain one pigment B alone, or it may contain two or more pigments.

[0304] From the viewpoint of visibility of the exposed and unexposed areas, the content of pigment B relative to the total mass of the thermoplastic resin layer is preferably 0.2% by mass or more, more preferably 0.2% to 6% by mass, even more preferably 0.2% to 5% by mass, and particularly preferably 0.25% to 3.0% by mass.

[0305] Here, the content of pigment B refers to the total amount of pigment B contained in the thermoplastic resin layer when it reaches its colored state. The following explanation uses a pigment that develops color via free radicals as an example to illustrate the quantitative method for determining the content of pigment B.

[0306] Solutions were prepared by dissolving 0.001 g and 0.01 g of pigment in 100 mL of methyl ethyl ketone. A photoradical polymerization initiator (Irgacure OXE01, manufactured by BASF JAPAN LTD.) was added to each solution, and the solutions were irradiated with 365 nm light, thereby generating free radicals and bringing all the pigments to their colored state. Subsequently, under atmospheric conditions, the absorbance of each solution at a liquid temperature of 25 °C was measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), and calibration curves were constructed.

[0307] Next, instead of the pigment, 0.1 g of the thermoplastic resin layer was dissolved in methyl ethyl ketone. Otherwise, the absorbance of the solution that caused the pigment to fully develop color was measured using the same method as described above. The amount of pigment contained in the thermoplastic resin layer was calculated from the absorbance of the solution containing the obtained thermoplastic resin layer based on the calibration curve.

[0308] (Compounds that generate acids, bases, or free radicals through phototransformation)

[0309] The thermoplastic resin layer may contain compounds that generate acids, bases, or free radicals through light (also referred to as "Compound C").

[0310] As compound C, it is preferred to be a compound that generates an acid, base or free radical under active light such as ultraviolet and visible light.

[0311] Compound C can be a known photoacid generator, photoalkali generator, or photoradical polymerization initiator (photoradical generator). Among them, compound C is preferably a photoacid generator.

[0312] -Photogenerating Acid Agent-

[0313] From a resolution perspective, the thermoplastic resin layer preferably contains a photoacid-generating agent.

[0314] As photoacid generators, examples of photocationic polymerization initiators that can be contained in the aforementioned photosensitive resin layer are as follows, except for the aspects described later.

[0315] From the viewpoint of sensitivity and resolution, the photoacid generator is preferably at least one compound selected from onium salt compounds and oxime sulfonate compounds, and from the viewpoint of sensitivity, resolution and adhesion, oxime sulfonate compounds are more preferred.

[0316] Furthermore, photoacid generators preferably have the following structure.

[0317] [Chemical Formula 2]

[0318]

[0319] -Photoradical polymerization initiator-

[0320] The thermoplastic resin layer may contain a photoradical polymerization initiator.

[0321] As photoradical polymerization initiators, examples of photoradical polymerization initiators that can be contained in the aforementioned photosensitive resin layer are given, and the preferred method is also the same.

[0322] -Photo-alkali-producing agent-

[0323] The thermoplastic resin layer may contain photoalkali-generating agents.

[0324] As a photo-alkali-producing agent, there are no particular limitations as long as it is a well-known photo-alkali-producing agent. Examples include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamine, O-carbamoyl oxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinylethane, and (4-morpholinylbenzoyl) -1-Benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaminecobalt(III)tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-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.

[0325] The thermoplastic resin layer may contain one compound C alone, or it may contain two or more compounds.

[0326] From the viewpoint of visibility and resolution of both the exposed and unexposed areas, the content of compound C is preferably 0.1% to 10% by mass, more preferably 0.5% to 5% by mass, relative to the total mass of the thermoplastic resin layer.

[0327] (Plasticizer)

[0328] From the viewpoints of resolution, adhesion to adjacent layers, and developability, the thermoplastic resin layer preferably contains a plasticizer.

[0329] The plasticizer preferably has a smaller molecular weight than the alkali-soluble resin (in the case of oligomers or polymers, the weight-average molecular weight (Mw)). The molecular weight (weight-average molecular weight (Mw)) of the plasticizer is preferably 200 to 2,000.

[0330] There are no particular limitations on plasticizers as long as they are compounds that express plasticity and are miscible with alkali-soluble resins. From the viewpoint of imparting plasticity, plasticizers preferably have alkene groups in their molecules, and more preferably are polyalkylene glycol compounds. The alkene groups contained in the plasticizer are more preferably polyethoxy or polyacryloxy structures.

[0331] Furthermore, from the viewpoint of resolution and storage stability, the plasticizer preferably contains a (meth)acrylate compound. From the viewpoint of compatibility, resolution, and adhesion to adjacent layers, the alkali-soluble resin is more preferably an acrylic resin and the plasticizer contains a (meth)acrylate compound.

[0332] Examples of (meth)acrylate compounds used as plasticizers include the polymeric compound B described in the aforementioned photosensitive resin layer.

[0333] In photosensitive transfer materials, when a thermoplastic resin layer and a photosensitive resin layer are laminated in direct contact, it is preferable that both the thermoplastic resin layer and the photosensitive resin layer contain the same (meth)acrylate compound. If both the thermoplastic resin layer and the photosensitive resin layer contain the same (meth)acrylate compound, interlayer diffusion is suppressed, and storage stability is improved.

[0334] When the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, from the viewpoint of adhesion to adjacent layers, it is preferable that the (meth)acrylate compound does not polymerize in the exposed portion after exposure.

[0335] 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.

[0336] Furthermore, the (meth)acrylate compounds used as plasticizers are preferably (meth)acrylate compounds or urethane (meth)acrylate compounds having acid groups.

[0337] The thermoplastic resin layer may contain one type of plasticizer or two or more types.

[0338] From the viewpoints of resolution, adhesion to adjacent layers, and developability, the content of plasticizer relative to the total mass of the thermoplastic resin layer is preferably 1% to 70% by mass, more preferably 10% to 60% by mass, and particularly preferably 20% to 50% by mass.

[0339] (surfactant)

[0340] From the viewpoint of thickness uniformity, the thermoplastic resin layer preferably contains a surfactant. Examples of surfactants that can be contained in the aforementioned photosensitive resin layer are provided, and the preferred formulation is also the same.

[0341] The thermoplastic resin layer may contain one surfactant or two or more surfactants.

[0342] The surfactant content is preferably 0.001% to 10% by mass relative to the total mass of the thermoplastic resin layer, more preferably 0.01% to 3% by mass.

[0343] (Sensitizer)

[0344] The thermoplastic resin layer may contain a sensitizer. There are no particular limitations on the sensitizer, and examples of sensitizers that the aforementioned photosensitive resin layer may contain are provided.

[0345] The thermoplastic resin layer may contain one type of sensitizer or two or more types.

[0346] The content of the sensitizer can be appropriately selected according to the purpose. From the viewpoint of improving the sensitivity to the light source and the visibility of the exposed and unexposed parts, the content is preferably in the range of 0.01% to 5% by mass relative to the total mass of the thermoplastic resin layer, and more preferably in the range of 0.05% to 1% by mass.

[0347] (Additives, etc.)

[0348] In addition to the above-mentioned components, the thermoplastic resin layer may contain known additives as needed. Furthermore, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese Patent Application Publication No. 2014-85643, the contents of which are incorporated herein by reference.

[0349] <Physical properties, etc.>

[0350] There is no particular limitation on the thickness of the thermoplastic resin layer, but from the viewpoint of adhesion to adjacent layers, it is preferable to be 1 μm or more, more preferably 2 μm or more. There is no particular upper limit to the thickness of the thermoplastic resin layer. 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.

[0351] <Formation Method>

[0352] There are no particular limitations on the method of forming the thermoplastic resin layer, which is capable of forming a layer containing the above-mentioned components.

[0353] As a method for forming a thermoplastic resin layer, an example can be given by forming it by: preparing a thermoplastic resin composition containing the above-mentioned components and solvent, applying the thermoplastic resin composition to the surface of a temporary support or the like, and drying the coating film of the thermoplastic resin composition.

[0354] The viscosity of the thermoplastic resin composition is adjusted, and it is preferable to contain a solvent in order to facilitate the formation of a thermoplastic resin layer.

[0355] (solvent)

[0356] There are no particular limitations on the solvent contained in the thermoplastic resin composition, as long as it can dissolve or disperse the aforementioned components contained in the thermoplastic resin layer.

[0357] Examples of solvents that can be contained in the thermoplastic resin composition include those found in the above-mentioned photosensitive resin composition, and the preferred method is also the same.

[0358] The solvent contained in the thermoplastic resin composition may be a single type or two or more types.

[0359] The solvent content in the thermoplastic resin composition is preferably 50 to 1,900 parts by weight, more preferably 100 to 900 parts by weight, relative to 100 parts by weight of the total solids content in the thermoplastic resin composition.

[0360] The preparation of the thermoplastic resin composition and the formation of the thermoplastic resin layer can be carried out by following the above-described methods for preparing the photosensitive resin composition and forming the photosensitive resin layer.

[0361] For example, a solution is prepared in advance in which each component contained in the thermoplastic resin layer is dissolved in the above solvent, and the solution is mixed in a specified proportion to obtain a thermoplastic resin composition. After that, the obtained thermoplastic resin composition is coated on the surface of a temporary support, and the coating film of the thermoplastic resin composition is dried to form a thermoplastic resin layer.

[0362] Furthermore, after forming the photosensitive resin layer and the intermediate layer on the cover film described later, a thermoplastic resin layer can be formed on the surface of the intermediate layer.

[0363] [Middle Layer]

[0364] The photosensitive transfer material preferably has an intermediate layer between the thermoplastic resin layer and the photosensitive resin layer. By configuring the intermediate layer, the mixing of components can be suppressed when multiple layers are applied and during storage after coating.

[0365] From the viewpoint of developability and the inhibition of mixing of components during multi-layer coating and storage after coating, the intermediate layer is preferably a water-soluble layer.

[0366] In addition, in this specification, "water solubility" means that the solubility of 100g of water at pH 7.0 with a liquid temperature of 22°C is greater than 0.1g.

[0367] As an intermediate layer, an oxygen barrier layer with oxygen barrier function can be described as a "separation layer" in Japanese Patent Application Publication No. 5-72724. If the intermediate layer is an oxygen barrier layer, the sensitivity during exposure is improved, the time load of the exposure machine is reduced, and thus the productivity is increased.

[0368] The oxygen barrier layer used as the intermediate layer can be appropriately selected from the known layers described in the aforementioned publications, etc. Among them, the intermediate layer is preferably an oxygen barrier layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (a 1% by mass aqueous solution of sodium carbonate at 22°C).

[0369] The intermediate layer preferably contains resin.

[0370] Examples of resins contained in the intermediate layer include polyvinyl alcohol resins, polyvinylpyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamides and their copolymers.

[0371] Water-soluble resin is preferred as the resin contained in the intermediate layer.

[0372] Furthermore, from the viewpoint of suppressing the mixing of components between multiple layers, the resin contained in the intermediate layer is preferably a different resin from either polymer A contained in the photosensitive resin layer or thermoplastic resin (alkali-soluble resin) contained in the thermoplastic resin layer.

[0373] From the viewpoint of oxygen barrier properties and the inhibition of mixing of components during multi-layer coating and storage after coating, the intermediate layer preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone.

[0374] The intermediate layer may contain one of the above-mentioned resins alone, or it may contain two or more of them.

[0375] There is no particular limitation on the resin content in the intermediate layer. From the viewpoint of oxygen barrier properties and suppressing the mixing of components during multi-layer coating and storage after coating, it is preferably 50% to 100% by mass relative to the total mass of the intermediate layer, more preferably 70% to 100% by mass, even more preferably 80% to 100% by mass, and especially preferably 90% to 100% by mass.

[0376] Furthermore, the intermediate layer may contain additives such as surfactants, as needed.

[0377] There is no particular limitation on the thickness of the intermediate layer, but it is preferably 0.1 μm to 5 μm, and more preferably 0.5 μm to 3 μm.

[0378] If the thickness of the intermediate layer is within the above range, the oxygen barrier properties will not be reduced, and the mixing of components during multi-layer coating and post-coating storage can be suppressed. Furthermore, if the thickness of the intermediate layer is within the above range, the increase in intermediate layer removal time during development can be suppressed.

[0379] There are no particular limitations on the method of forming the intermediate layer. For example, a method can be described as preparing an intermediate layer composition containing the above-mentioned resin and any additives, coating it on the surface of a thermoplastic resin layer or a photosensitive resin layer, and drying the coating film of the intermediate layer composition to form the intermediate layer.

[0380] In order to adjust the viscosity of the intermediate layer composition to facilitate the formation of the intermediate layer, the intermediate layer composition preferably contains a solvent.

[0381] The solvent contained in the intermediate layer composition is not particularly limited as long as it can dissolve or disperse the resin, and is preferably selected from at least one of water and water-miscible organic solvents, more preferably water or a mixture of water and water-miscible organic solvents.

[0382] Examples of water-miscible organic solvents include alcohols with 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerol, with alcohols with 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred.

[0383] [Covering film]

[0384] The photosensitive transfer material preferably has a cover film that is in contact with the surface of the photosensitive resin layer that is not in contact with the temporary support.

[0385] In this specification, the surface of the photosensitive resin layer opposite to the temporary support will be referred to as the "first surface", and the surface opposite to the first surface will be referred to as the "second surface".

[0386] Examples of materials that constitute the covering film include resin film and paper. Among these, from the viewpoint of strength and flexibility, resin film is preferred as the material constituting the covering film.

[0387] Examples of resin films include polyethylene films, polypropylene films, polyethylene terephthalate films, cellulose triacetate films, polystyrene films, and polycarbonate films. Among these, polyethylene films, polypropylene films, or polyethylene terephthalate films are preferred.

[0388] There is no particular limitation on the thickness of the covering film, but it is preferred to be 5μm to 100μm, and more preferably 10μm to 50μm.

[0389] Furthermore, considering superior resolution, the arithmetic mean roughness Ra value of the surface of the cover film in contact with the photosensitive resin layer (hereinafter also referred to as "the 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. It is believed that when the Ra value of the surface of the cover film is within the above range, the uniformity of the thickness of the photosensitive resin layer and the formed resin pattern is improved.

[0390] There is no particular limitation on the lower limit of the Ra value of the cover film surface. Preferably, the Ra value of the cover film surface is 0.001 μm or higher.

[0391] The Ra value of the surface of the covering film was determined by the following method.

[0392] The surface profile of the cover film was obtained by measuring the surface of the optical film using a three-dimensional optical analyzer (New View 7300, manufactured by Zygo) under the following conditions. The measurement and analysis software used was MetroPro ver8.3.2's Microscope Application. Next, the Surface Map screen was displayed using the aforementioned analysis software, and histogram data was obtained from the Surface Map screen. The arithmetic mean roughness was calculated from the obtained histogram data to obtain the Ra value of the cover film surface.

[0393] With the cover film and photosensitive transfer material bonded together, the cover film can be peeled off from the photosensitive transfer material, and the Ra value of the peeled-off side surface can be measured.

[0394] Photosensitive transfer materials may have layers other than those described above (hereinafter also referred to as "other layers"). Examples of other layers include contrast-enhancing layers.

[0395] Regarding the contrast-enhancing layer, it is described in paragraph 0134 of International Publication No. 2018 / 179640. Furthermore, regarding other layers, they are described in paragraphs 0194 to 0196 of Japanese Patent Application Publication No. 2014-85643. The contents of these publications are incorporated herein by reference.

[0396] [Manufacturing method of photosensitive transfer material]

[0397] The manufacturing method of the photosensitive transfer material involved in this invention is not particularly limited, and known manufacturing methods, such as known methods for forming each layer, can be used.

[0398] The following is for reference. Figure 1 The method for manufacturing the photosensitive transfer material according to the present invention will be described. However, the photosensitive transfer material according to the present invention is not limited to having... Figure 1 The material of the structure shown.

[0399] Figure 1 This is a schematic diagram illustrating an example of the structure of the photosensitive transfer material involved in the present invention. Figure 1 The photosensitive transfer material 100 shown has a structure 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 stacked in sequence.

[0400] As a method for manufacturing the aforementioned photosensitive transfer material 100, an example method may include the following steps: applying a thermoplastic resin composition to the surface of a temporary support 10 and drying the coating of the thermoplastic resin composition to form a thermoplastic resin layer 12; applying an intermediate layer composition to the surface of the thermoplastic resin layer 12 and drying the coating of the intermediate layer composition to form an intermediate layer 14; applying a photosensitive resin composition to the surface of the intermediate layer 14 and drying the coating of the photosensitive resin composition to form a photosensitive resin layer 16; and pressing a cover film 18 onto the photosensitive resin layer 16.

[0401] In the case where a photosensitive resin layer is directly applied to a temporary support, the photosensitive resin composition is coated onto the surface of the temporary support.

[0402] In the method for manufacturing the photosensitive transfer material according to the present invention, when a photosensitive resin composition (or a thermoplastic resin composition in the case of a laminated thermoplastic resin layer) is applied to the surface of a temporary support, and the temporary support is virtually divided into two regions along its center in the thickness direction, the composition is applied to the surface on the side of the region with fewer impurities. Thus, when the temporary support is designated as a first region from the center in the thickness direction to the side of the photosensitive resin layer, and a second region from the center in the thickness direction to the side opposite to the photosensitive resin layer, it is possible to manufacture a photosensitive transfer material in which the number of impurities in the first region is less than the number of impurities in the second region.

[0403] The inventors have gained the following insight: when a temporary support is virtually divided into two regions at its center along the thickness direction, the side with fewer impurities is the side that does not contact the casting roller during the manufacture of the temporary support. Therefore, in the manufacturing method of the present invention, it is preferable to apply a photosensitive resin composition (or a thermoplastic resin composition in the case of laminated thermoplastic resin layers) to the side that does not contact the casting roller during the manufacture of the temporary support.

[0404] In the above-described manufacturing method, it is preferable to use a thermoplastic resin composition containing at least one selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents, an intermediate layer composition containing at least one selected from water and water-miscible organic solvents, and a photosensitive resin composition containing polymer A, polymeric compound B, and at least one selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents. This suppresses the mixing of components contained in the thermoplastic resin layer 12 with components contained in the intermediate layer 14 during storage of the laminate having the intermediate layer composition coated on the surface of the thermoplastic resin layer 12 and / or the laminate having the intermediate layer composition. Furthermore, it suppresses the mixing of components contained in the intermediate layer 14 with components contained in the photosensitive resin layer 16 during storage of the laminate having the photosensitive resin composition coated on the surface of the intermediate layer 14 and / or the laminate having the photosensitive resin composition.

[0405] As a method for manufacturing the photosensitive transfer material involved in the present invention, it is preferable to manufacture a photosensitive transfer material 100 having a temporary support 10, a thermoplastic resin layer 12, an intermediate layer 14, a photosensitive resin layer 16 and a cover film 18 by including a step of setting a cover film 18 in contact with the second surface of the photosensitive resin layer 16.

[0406] After manufacturing the photosensitive transfer material 100, a roller-shaped photosensitive transfer material can also be manufactured and stored by winding the photosensitive transfer material 100. The roller-shaped photosensitive transfer material can be provided as is in the bonding process with the substrate in the roll-to-roll method described later.

[0407] [Methods for manufacturing resin patterns and circuit wiring]

[0408] There are no particular restrictions on the method of manufacturing resin patterns as long as it is a method of manufacturing resin patterns using the above-mentioned photosensitive transfer material.

[0409] The preferred method for manufacturing a resin pattern includes, in sequence, a process of bonding a side of the photosensitive transfer material that does not oppose the temporary support of the photosensitive resin layer (i.e., the second side) to a substrate (hereinafter also referred to as the "bonding process"), a process of exposing the photosensitive resin layer to a pattern (hereinafter also referred to as the "exposure process"), and a process of developing the photosensitive resin layer after the pattern exposure process to form the resin pattern (hereinafter also referred to as the "development process").

[0410] There are no particular restrictions on the manufacturing method of the circuit wiring as long as it uses the aforementioned photosensitive transfer material.

[0411] The preferred method for manufacturing circuit wiring includes the above-described bonding process, the above-described exposure process, the above-described development process, and a process of etching the substrate in areas where no resin pattern is configured (hereinafter also referred to as the "etching process").

[0412] The following describes the process involved in manufacturing the resin pattern and the circuit wiring. Unless otherwise stated, the description of the process involved in manufacturing the resin pattern also applies to the process involved in manufacturing the circuit wiring.

[0413] [Lamination process]

[0414] The preferred method for manufacturing resin patterns includes a lamination process.

[0415] In the bonding process, it is preferable to press the photosensitive transfer material and the substrate by contacting the substrate (or the conductive layer if a conductive layer is provided on the surface of the substrate) with the second side of the photosensitive resin layer. If the above method is used, in order to improve the adhesion between the second side of the photosensitive resin layer and the substrate, it is preferable to use an etch resist when etching the photosensitive resin layer formed by the pattern after exposure and development.

[0416] Alternatively, if the photosensitive transfer material has a cover film, it can be laminated after removing the cover film from the surface of the photosensitive resin layer.

[0417] Furthermore, the bonding process is carried out in the following manner: when the photosensitive transfer material has a layer other than the cover film (for example, at least one layer selected from high refractive index layer and low refractive index layer) on the second side of the photosensitive resin layer, the second side of the photosensitive resin layer is bonded to the substrate via the layer.

[0418] There are no particular limitations on the method of using the pressing substrate and the photosensitive transfer material, and known transfer methods and lamination methods can be used.

[0419] The photosensitive transfer material is preferably bonded to a substrate by stacking the substrate on the second side of the photosensitive resin layer and applying pressure and heat using a device such as rollers. Known laminators such as laminators, vacuum laminators, and automated cutting laminators that can further improve productivity can be used during bonding.

[0420] The manufacturing method of the resin pattern, including the bonding process, and the manufacturing method of the circuit wiring are preferably carried out by roll-to-roll method.

[0421] The following explains the roll-to-roll method.

[0422] A roll-to-roll method refers to the following: using a substrate capable of being wound and unwound as a substrate, including a process of unwinding a structure containing the substrate or a substrate before any step included in a resin pattern manufacturing method or a circuit wiring manufacturing method (also called an "unwinding process") and a process of winding a structure containing the substrate or a substrate after any step (also called a "winding process"), while carrying the structure containing the substrate or a substrate, performing at least one step (preferably all steps except all steps or heating steps).

[0423] There are no particular restrictions on the unwinding method in the unwinding process and the winding method in the winding process; any known method can be used in the manufacturing method applicable to the roll-to-roll method.

[0424] <Substrate>

[0425] As the substrate for forming the resin pattern using the photosensitive transfer material according to the present invention, a known substrate can be used. The substrate is preferably a substrate having a conductive layer, and more preferably a substrate having a conductive layer on the surface of a substrate.

[0426] The substrate can have any layer other than the conductive layer, as needed.

[0427] Examples of substrates that form a substrate include glass, silicon, and resin films.

[0428] The substrate is preferably transparent. In this specification, "transparent" means that the transmittance of light with a wavelength of 400nm to 700nm is 80% or more. Furthermore, the refractive index of the substrate is preferably 1.50 to 1.52.

[0429] Examples of transparent glass substrates include tempered glass such as Gorilla Glass from Corning Incorporated Co., Ltd. Furthermore, materials described in Japanese Patent Application Publication Nos. 2010-86684, 2010-152809, and 2010-257492 can be used as transparent glass substrates.

[0430] When a resin film is used as a substrate, the substrate is preferably a resin film with low optical distortion and / or high transparency. Examples of such resin films include polyethylene terephthalate (PET) films, polyethylene naphthalate (PET) films, polycarbonate films, triacetyl cellulose films, and cyclic olefin polymer films.

[0431] When manufactured in a roll-to-roll manner, the substrate is preferably a resin film. Furthermore, when manufacturing circuit wiring for a touch panel using a roll-to-roll manner, the substrate is preferably a resin sheet.

[0432] As a conductive layer in a substrate, examples include conductive layers used in typical circuit wiring or touch panel wiring.

[0433] From the viewpoint of conductivity and fine line formation, the conductive layer is preferably selected from at least one layer selected from metal layers, conductive metal oxide layers, graphene layers, carbon nanotube layers and conductive polymer layers, more preferably metal layers, and even more preferably copper layers or silver layers.

[0434] The substrate may have a single conductive layer or two or more conductive layers. When the substrate has two or more conductive layers, it is preferable that the substrate has two or more conductive layers of different materials.

[0435] Materials that can be used as conductive layers include metals and conductive metal oxides.

[0436] Examples of metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au.

[0437] Examples of conductive metal oxides include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO2. Furthermore, in this specification, "conductivity" refers to a volume resistivity of less than 1 × 10⁻⁶. 6 Ωcm. The volume resistivity of conductive metal oxides is preferably less than 1×10⁻⁶. 4 Ωcm.

[0438] When using a substrate with multiple conductive layers to manufacture resin patterns, it is preferable that at least one of the multiple conductive layers contains a conductive metal oxide.

[0439] The conductive layer is preferably an electrode pattern of a sensor for the visible portion of a capacitive touch panel or wiring for the peripheral portion of the sensor.

[0440] [Exposure process]

[0441] The preferred method for manufacturing the resin pattern includes a process of exposing the photosensitive resin layer to the pattern after the above-mentioned bonding process (exposure process).

[0442] There are no particular limitations on the configuration of the detailed content and specific dimensions of the pattern in the pattern exposure. At least a portion of the pattern (preferably the electrode pattern and / or the lead-out wiring portion of the touch panel) preferably includes fine lines with a width of 20 μm or less, more preferably fine lines with 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 a circuit wiring manufacturing method, and reduce the area occupied by the lead-out wiring.

[0443] There are no particular restrictions on the light source used for exposure, as long as it is a light source capable of illuminating the photosensitive resin layer at a wavelength (e.g., 365nm or 405nm), and it 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).

[0444] The optimal exposure level is 5 mJ / cm. 2 ~200mJ / cm 2 More preferably 10 mJ / cm 2 ~100mJ / cm 2 .

[0445] In the exposure process, pattern exposure can be performed after the temporary support is peeled off from the photosensitive resin layer, or pattern exposure can be performed through the temporary support and then the temporary support is peeled off. When exposure is performed after peeling off the temporary support, the mask can be in contact with the photosensitive resin layer for exposure, or the mask can be brought close to the photosensitive resin layer without contact. When exposure is performed without peeling off the temporary support, the mask can be in contact with the temporary support for exposure, or the mask can be brought close to the temporary support without contact. To prevent mask contamination caused by contact between the photosensitive resin layer and the mask, and to avoid the effects of impurities adhering to the mask on the exposure, it is preferable to perform pattern exposure without peeling off the temporary support. Furthermore, when the exposure method is contact exposure, appropriate methods can be selected for contact exposure, non-contact exposure, such as proximity exposure, projection exposure using a lens system or mirror system, or direct exposure using an exposure laser. In the case of projection exposure using a lens system or mirror system, an exposure machine with an appropriate number of lens apertures (NA) can be used according to the required resolution and depth of focus. In the direct exposure method, exposure can be performed directly on the photosensitive resin layer, or by projecting a reduced image onto the photosensitive resin layer through a lens. Furthermore, exposure can be performed not only under atmospheric conditions, but also under reduced pressure or a vacuum. Additionally, a liquid such as water can be inserted between the light source and the photosensitive resin layer for exposure.

[0446] [Developing process]

[0447] The preferred method for manufacturing resin patterns includes a process (development process) that develops the exposed photosensitive resin layer after the above-mentioned exposure process to form the resin pattern.

[0448] When the photosensitive transfer material has a thermoplastic resin and an intermediate layer, the thermoplastic resin layer and intermediate layer of the non-exposed area are removed together with the photosensitive resin layer of the non-exposed area during the developing process. Furthermore, the thermoplastic resin layer and intermediate layer of the exposed area can also be removed by dissolving or dispersing them in the developing solution during the developing process.

[0449] The exposed photosensitive resin layer can be developed using a developing solution.

[0450] There are no particular limitations on the developer as long as it can remove the non-image portion (non-exposed portion) of the photosensitive resin layer. For example, known developers such as the developer described in Japanese Patent Application Publication No. 5-72724 can be used.

[0451] The developer is preferably an alkaline aqueous solution containing a compound with a pKa of 7 to 13 at a concentration of 0.05 mol / L to 5 mol / L. The developer may contain at least one selected from water-soluble organic solvents and surfactants. The developer is also preferably the one described in paragraph 0194 of International Publication No. 2015 / 093271.

[0452] There are no particular restrictions on the development method; it can be any of the following: water pit development, spray development, spray and spin development, and immersion development. Spray development involves spraying developing solution onto the exposed photosensitive resin layer, thereby removing the unexposed areas.

[0453] After the developing process, it is preferable to remove developing residue by spraying a cleaning agent while wiping with a brush.

[0454] There are no particular restrictions on the temperature of the developer, but it is preferably 20℃ to 40℃.

[0455] [Etching process]

[0456] The method for manufacturing circuit wiring preferably includes an etching process (etching process) in which a substrate in a region without a resin pattern is etched in a laminate of resin patterns manufactured by a manufacturing method including the above-described bonding process, the above-described exposure process and the above-described development process are sequentially laminated.

[0457] In the etching process, the resin pattern formed by the photosensitive resin layer is used as an etching resist to etch the substrate.

[0458] As a method for etching, known methods can be applied, such as the methods described in paragraphs 0209 to 0210 of Japanese Patent Application Publication No. 2017-120435, the methods described in paragraphs 0048 to 0054 of Japanese Patent Application Publication No. 2010-152155, wet etching by immersion in etching solution, and dry etching methods such as plasma etching.

[0459] For wet etching, the etching solution can be either acidic or alkaline, depending on the object being etched.

[0460] Examples of acidic etching solutions include aqueous solutions of acidic components selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, as well as mixed aqueous solutions of acidic components with salts selected from ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component can also be a combination of multiple acidic components.

[0461] 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 (such as tetramethylammonium hydroxide), as well as aqueous solutions of alkaline components mixed with salts (e.g., potassium permanganate). The alkaline component can also be a combination of multiple alkaline components.

[0462] [Removal process]

[0463] In the manufacturing method of circuit wiring, it is preferable to perform a process to remove residual resin patterns (removal process).

[0464] There are no particular restrictions on the removal process, and it can be performed as needed, but it is preferred to perform it after the etching process.

[0465] There are no particular limitations on the method for removing residual resin patterns; methods such as removal by chemical treatment are examples. However, methods using a removal solution are preferred for removing residual resin patterns.

[0466] As a method for removing the photosensitive resin layer, one example is to immerse a substrate with residual resin patterns in a removal solution at a temperature preferably 30°C to 80°C, more preferably 50°C to 80°C, under stirring for 1 to 30 minutes.

[0467] Examples of removal solutions include those that dissolve inorganic or organic base components in water, dimethyl sulfoxide, N-methylpyrrolidone, or mixtures thereof. Examples of inorganic base components include sodium hydroxide and potassium hydroxide. Examples of organic base components include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

[0468] Furthermore, residual resin patterns can also be removed using a removal liquid and by known methods such as spraying, rinsing, and spin-dip methods.

[0469] (Other processes)

[0470] The manufacturing method of circuit wiring may include any steps other than those described above (other steps). For example, the following steps can be cited, but are not limited to these steps.

[0471] Furthermore, as exposure, development and other processes applicable to the manufacturing method of circuit wiring, examples include the processes described in paragraphs 0035 to 0051 of Japanese Patent Application Publication No. 2006-23696.

[0472] <Covering film peeling process>

[0473] When the photosensitive transfer material has a cover film, the method for manufacturing the resin pattern preferably includes a step of peeling off the cover film from the photosensitive transfer material. There are no particular limitations on the method for peeling off the cover film; known methods can be used.

[0474] <Process for reducing visible light reflectivity>

[0475] The manufacturing method of circuit wiring may include a process of performing a treatment to reduce the visible light reflectivity of a portion or all of the conductive layer on the substrate.

[0476] Oxidation is an example of a process to reduce visible light reflectivity. When the substrate has a conductive layer containing copper, copper is oxidized to obtain copper oxide, which blackens the conductive layer, thereby reducing the visible light reflectivity of the conductive layer.

[0477] Treatments for reducing visible light reflectivity are described in paragraphs 0017 to 0025 of Japanese Patent Application Publication No. 2014-150118 and paragraphs 0041, 0042, 0048 and 0058 of Japanese Patent Application Publication No. 2013-206315, the contents of which are incorporated herein by reference.

[0478] <The process of forming an insulating film, and the process of forming a new conductive layer on the surface of the insulating film>

[0479] The manufacturing method of the circuit wiring preferably includes a step of forming an insulating film on the surface of the circuit wiring and a step of forming a new conductive layer on the surface of the insulating film. Through the above steps, a second electrode pattern that is insulated from the first electrode pattern can be formed.

[0480] There are no particular limitations on the process of forming the insulating film, and known methods for forming permanent films can be cited. Furthermore, using a photosensitive material with insulating properties, an insulating film with a desired pattern can also be formed by photolithography.

[0481] There are no particular limitations on the process of forming a new conductive layer on an insulating film. For example, a new conductive layer with a desired pattern can be formed by using a conductive photosensitive material and by photolithography.

[0482] The manufacturing method of the circuit wiring preferably uses a substrate having multiple conductive layers on both surfaces of the substrate to sequentially or simultaneously form circuits on the conductive layers formed on both surfaces of the substrate. With this structure, it is possible to form circuit wiring for a touch panel with a first conductive pattern formed on one surface of the substrate and a second conductive pattern formed on the other surface. Furthermore, it is also preferable to form this type of circuit wiring for a touch panel from both sides of the substrate in a roll-to-roll manner.

[0483] [Applications of circuit wiring]

[0484] The circuit wiring manufactured using the circuit wiring manufacturing method can be applied to various devices. Examples of devices equipped with circuit wiring manufactured using the above method include input devices, preferably touch panels, and more preferably capacitive touch panels. Furthermore, the above-mentioned input devices can be applied to display devices such as organic EL display devices and liquid crystal display devices.

[0485] [Manufacturing method of touch panel]

[0486] There are no particular restrictions on the manufacturing method of the touch panel as long as it uses the aforementioned photosensitive transfer material.

[0487] The preferred method for manufacturing a touch panel includes the above-described bonding process, the above-described exposure process, the above-described development process, and an etching process (hereinafter also referred to as the "etching process") for etching the substrate in areas where no resin pattern is configured.

[0488] The specific methods and order of each step in the manufacturing method of the touch panel are as described in the section on "Manufacturing Method of Circuit Wiring" above, and the preferred methods are also the same.

[0489] In the manufacturing method of the touch panel, the wiring for the touch panel is formed by the method described above. Otherwise, any known manufacturing method of the touch panel can be referred to. Furthermore, the manufacturing method of the touch panel may include any process other than the process described above (other processes).

[0490] By using the above-described method for manufacturing a touch panel, a touch panel having at least wiring for a touch panel is manufactured. The touch panel preferably has a transparent substrate, electrodes, an insulating layer, or a protective layer.

[0491] Various known detection methods for touch panels include resistive film detection, capacitive detection, ultrasonic detection, electromagnetic induction detection, and optical detection. Among these, capacitive detection is preferred.

[0492] Example

[0493] The following examples provide a more detailed description of the embodiments of the present invention. The materials, amounts, proportions, processing contents, and processing steps shown in the following examples can be appropriately modified 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. Furthermore, unless otherwise specified, "parts" and "%" are based on mass.

[0494] <Preparation of Photosensitive Resin Composition>

[0495] The components used to prepare the photosensitive resin composition are as follows.

[0496] [Polymer A (alkali-soluble resin)]

[0497] 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.

[0498] St: Styrene (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0499] MAA: Methacrylic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0500] MMA: Methyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0501] V-601: 2,2'-Dimethyl azobis(isobutyrate) (manufactured by FUJIFILM Wako Pure Chemical Corporation, polymerization initiator)

[0502] PGMEA: Propylene Glycol Monomethyl Ether Acetate

[0503] 116.5 parts of PGMEA were added to a three-necked flask, and the mixture was heated to 90°C under a nitrogen atmosphere. While maintaining the liquid temperature in the three-necked 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-necked flask over 2 hours. After the addition was complete, the mixture was stirred for 2 hours while maintaining the liquid temperature at 90°C ± 2°C, thereby obtaining a composition containing 30.0% by mass of polymer A. Polymer A has an acid value of 189 mg KOH / g, a weight-average molecular weight of 60,000, and a glass transition temperature of 131°C.

[0504] <Polymers A-1, A-2, A-4, and A-5>

[0505] As shown in Table 1 below, the types and amounts of monomers used in the synthesis of polymers were changed. Otherwise, polymers A-1, A-2, A-4 and A-5 were synthesized by the same method as polymer A-3, and compositions containing 30.0% by mass of polymers were obtained.

[0506] Additionally, BnMA in Table 1 refers to benzyl methacrylate (manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC.).

[0507] Furthermore, Table 1 records the weight-average molecular weight (Mw), acid value, and glass transition temperature (Tg) of the obtained polymers.

[0508] [Table 1]

[0509]

[0510] [Polymerizing compound B]

[0511] • Polymerizable compound B-1: NK ESTER BPE-500 (2,2-bis(4-(methacryloyloxypentethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0512] • Polymerizable compound B-2: NK ESTER BPE-200 (2,2-bis(4-(methacryloyloxydiethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0513] • Polymerizable compound B-3: NK ESTER A-TMPT (trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0514] • Polymerizable compound B-4: ARONIX TO-2349 (a compound having the following structure, manufactured by TOAGOSEI CO., Ltd.)

[0515] [Chemical Formula 3]

[0516]

[0517] [Photopolymerization initiator]

[0518] • B-CIM (photoradical polymerization initiator, 2-(2-chlorophenyl)-4,5-diphenylimidazolium dimer, manufactured by Hampford Company)

[0519] [Sensitizer]

[0520] ·SB-PI 701 (4,4'-bis(diethylamino)benzophenone, manufactured by SANYO TRADING CO., LTD.)

[0521] [Pigment N]

[0522] • Pigment N-1: LCV (colorless crystal violet, manufactured by Tokyo Chemical Industry Co., Ltd., color development via free radicals)

[0523] • Pigment N-2: Brilliant Green (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0524] [Rust Inhibitor]

[0525] A mixture of 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole (mass ratio 1:1)

[0526] [Antioxidants]

[0527] Irganox 245 (ethylene bis(oxyethylene)bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate), manufactured by BASF)

[0528] [Polymerization inhibitor]

[0529] • N-Nitrophenylhydroxylamine aluminum salt (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0530] A photosensitive resin composition was prepared by mixing the following ingredients.

[0531] • Polymer A-1 (solids concentration 30.0%): 53.27 parts

[0532] • Polymerizable compound B-1: 22.50 parts

[0533] • Polymerizable compound B-2: 10.00 parts

[0534] • Polymerizable compound B-3: 10.00 parts

[0535] • Photopolymerization initiator: 3.00 parts

[0536] • Sensitizer: 0.30 parts

[0537] • Pigment N-1: 0.60 parts

[0538] Pigment N-2: 0.02 parts

[0539] Rust inhibitor: 0.10 parts

[0540] • Antioxidant: 0.20 parts

[0541] • Polymerization inhibitor: 0.01 parts

[0542] • Methyl ethyl ketone (manufactured by SANKYO CHEMICAL CO., LTD.): 100.00 parts

[0543] ·PGMEA (made by SHOWA DENKO KK): 50.00 copies

[0544] • Methanol (manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC.): 10.00 parts

[0545] <Preparation of Photosensitive Transfer Materials>

[0546] [Example 1]

[0547] A PET film with a thickness of 30 μm was prepared as a temporary support. A photosensitive resin composition was applied to the surface of the temporary support using a slit nozzle, resulting in a coating width of 1.0 μm and a layer thickness of 5 μm after drying. The coating of the photosensitive resin composition was dried at 80°C for 40 seconds to form a photosensitive resin layer, thereby obtaining a photosensitive transfer material.

[0548] [Examples 2-13, Comparative Example 1, Comparative Example 2]

[0549] The thickness of the photosensitive resin layer, the type and amount of polymer A and polymeric compound B contained in the photosensitive resin layer were changed to the values ​​recorded in Tables 2 and 3. Otherwise, the photosensitive transfer material was obtained by the same method as in Example 1.

[0550] In Tables 2 and 3, the "styrene content" for "polymer A" indicates the content of styrene-derived structural units 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. Regarding polymeric compound B, the content (mass %) of each polymeric compound relative to the total mass of the photosensitive resin layer is listed. Furthermore, the "M / B ratio" indicates the ratio of the content of polymeric compound B relative to the content of polymer A.

[0551] <Preparation of the Intermediate Layer Composition>

[0552] An intermediate layer composition was prepared by mixing the following ingredients.

[0553] • Ion-exchanged water: 38.12 parts

[0554] • Methanol (manufactured by MITSUBISHI GAS CHEMICAL C0MPANY, INC.): 57.17 parts

[0555] • KURARAY POVAL PVA-205 (polyvinyl alcohol, manufactured by KURARAY CO., LTD.): 3.22 parts

[0556] • Polyvinylpyrrolidone K-30 (manufactured by NIPPON SHOKUBAI CO., Ltd.): 1.49 parts

[0557] Megaface F-444 (fluorinated nonionic surfactant, manufactured by DIC CORPORATION): 0.0015 parts

[0558] <Preparation of Thermoplastic Resin Compositions>

[0559] A thermoplastic resin composition was prepared by mixing the following ingredients.

[0560] • Benzyl methacrylate, copolymer of methacrylic acid and acrylic acid (solids concentration 30.0%, Mw 30000, acid value 153 mgKOH / g): 42.85 parts

[0561] • NK ESTER A-DCP (Tricyclodecanedimethyl diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.): 4.63 parts

[0562] • 8UX-015A (Multifunctional polyurethane acrylate compound, manufactured by Taisei Fine Chemical Co., Ltd.): 2.31 parts

[0563] • ARONIX TO-2349 (manufactured by TOAGOSEI CO., Ltd.): 0.77 servings

[0564] • Compounds with the structure shown below (photoacid generators, compounds synthesized according to the method described in paragraph 0227 of Japanese Patent Application Publication No. 2013-47765): 0.32 parts

[0565] [Chemical Formula 4]

[0566]

[0567] • Compounds with the structure shown below (pigments that develop color via acid): 0.08 parts

[0568] [Chemical Formula 5]

[0569]

[0570] Megaface F552 (made by DIC CORPORATION): 0.03 copies

[0571] • Methyl ethyl ketone (manufactured by SANKYO CHEMICAL CO., LTD.): 39.50 parts

[0572] ·PGMEA (made by SHOWA DENKO KK): 9.51 servings

[0573] <Preparation of Photosensitive Transfer Materials>

[0574] [Example 14]

[0575] 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, resulting in a coating width of 1.0 μm and a dried layer thickness of 3.0 μm. The thermoplastic resin composition coating, dried at 80°C for 40 seconds, formed a thermoplastic resin layer. An intermediate layer composition was applied to the surface of the formed thermoplastic resin layer using a slit nozzle, resulting in a coating width of 1.0 μm and a dried layer thickness of 1.2 μm. The intermediate layer composition coating, dried at 80°C for 40 seconds, formed an intermediate layer. A photosensitive resin composition was applied to the surface of the formed intermediate layer using a slit nozzle, resulting in a coating width of 1.0 μm and a dried layer thickness of 2 μm. The photosensitive resin composition coating, dried at 80°C for 40 seconds, formed a photosensitive resin layer, thereby obtaining a photosensitive transfer material.

[0576] Using the photosensitive transfer materials obtained in the examples and comparative examples, turbidity was measured, and resolution, buffering capacity, and scum formation were evaluated. The measurement and evaluation methods are as follows. The evaluation results are shown in Tables 2 and 3.

[0577] <Turbidity>

[0578] 0.02 μm was obtained from the photosensitive transfer materials obtained in the examples and comparative examples. 2 The sample was tested. 0.02 mg of sodium carbonate was added to 200 mL of a 1% (w / w) sodium carbonate aqueous solution. 2The sample was stirred at 30°C for 4 hours while taking care to avoid introducing air bubbles. After stirring, the turbidity of the solution containing the sample was measured. A turbidimeter (product name "NDH4000", manufactured by NIPPON DENSHOKU INDUSTRIES Co., LTD.) was used, and a dedicated liquid measurement cell with a 20 mm optical path length was used to measure the turbidity.

[0579] <resolution>

[0580] First, a copper layer with a thickness of 200 nm was formed on a 100 μm thick polyethylene terephthalate (PET) film by sputtering, thereby creating a PET substrate with a copper layer.

[0581] After the photosensitive transfer material is unwound in the form of a roll, it is laminated with a PET substrate containing a copper layer, so that the photosensitive resin layer and the copper layer come into contact with each other, thus obtaining a laminate. The lamination process is 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.

[0582] The photosensitive resin layer was exposed by irradiating an ultra-high pressure mercury lamp (main exposure wavelength: 365nm) through a photomask on the temporary support side of the obtained laminate. The photomask used for exposure had a line and space pattern with a duty ratio of 1:1 between the width of the transparent area and the width of the shading area and a stepwise variation in 1μm intervals from 1μm to 20μm.

[0583] In addition, the exposure amount relative to the photosensitive resin layer is adjusted so that the line width of the resin pattern formed by exposure of the region with a line width of 20 μm and a spatial width of 20 μm in the photomask becomes 20 μm.

[0584] After the temporary support was peeled off from the exposed laminate, the laminate was spray-developed for 30 seconds using a 1.0% by mass sodium carbonate aqueous solution at 25°C. This development process removed the unexposed photosensitive resin layer from the laminate, creating a resin pattern with the aforementioned phased lines and spatial patterns on the surface of the copper layer.

[0585] In the example of a laminated intermediate layer and thermoplastic resin layer, the intermediate layer and thermoplastic resin layer can also be removed by this developing process.

[0586] For the formed resin patterns, a scanning electron microscope (product name "S-4800", manufactured by Hitachi High-Tech Co., Ltd.) was used to observe the presence of any residue of the photosensitive resin layer in the pattern shape and spatial areas at each linewidth. The resolution was determined by the smallest linewidth among the resin patterns where the cured photosensitive resin layer in the lines had not peeled off and there was no residue of the photosensitive resin layer. The evaluation criteria are as follows: 3 or higher is considered a level that is practically sound.

[0587] 5: Resolution below 4μm.

[0588] 4: The resolution is 5μm or 6μm.

[0589] 3: The resolution is 7μm or 8μm.

[0590] 2: The resolution is 9μm or 10μm.

[0591] 1: Resolution of 11μm or higher.

[0592] <Buffering>

[0593] First, a 200 nm thick copper layer was formed on a 100 μm thick polyethylene terephthalate (PET) film by sputtering, thus creating a PET substrate with a copper layer. The PET substrate with the copper layer was etched to create a substrate with a height difference, consisting of copper patterns of 200 nm height and 1000 μm width. After unwinding a photosensitive transfer material in the form of a roller, the photosensitive transfer material and the substrate were laminated to bring the photosensitive resin layer and the copper layer into contact, resulting in a laminate. The lamination process was performed under atmospheric pressure at a linear pressure of 1.0 MPa and a linear speed of 4 m / min, while changing the roller temperature every 5°C. For the height difference, the lowest temperature at which lamination can be achieved without air bubbles (hereinafter referred to as the "temperature at which lamination can be achieved without air bubbles") was used as an indicator of buffering performance. It can be said that the lower the temperature at which lamination can be achieved without air bubbles, the better the buffering performance. The evaluation criteria are as follows: 3 and above indicates a level that is practically problem-free.

[0594] 5: The temperature at which the layers can be stacked without bubbles is below 70℃.

[0595] 4: The temperature at which the layers can be stacked without bubbles is above 75℃ and below 85℃.

[0596] 3: The temperature at which the layers can be stacked without bubbles is above 90℃ and below 100℃.

[0597] 2: The temperature at which the layers can be stacked without bubbles is above 105℃ and below 115℃.

[0598] 1: The temperature at which the layers can be stacked without bubbles is above 120℃.

[0599] <Scum Formation>

[0600] 0.5 μm of photosensitive transfer material was obtained from the examples and comparative examples, respectively. 2 Evaluation sample. 0.5m 2 The evaluation sample was dissolved in 1 L of a 1% sodium carbonate aqueous solution. The solution containing the evaluation sample was sprayed at 0.15 MPa and circulated for 3 hours. After 3 hours, 200 mL of the solution was recovered and filtered using a polypropylene membrane filter (HDCII Pall) with a pore size of 0.45 μm. After filtration, the filter was vacuum-dried at 80°C to evaporate the moisture. The mass of the filter residue was calculated from the mass of the filter before and after filtration. The residue was then placed in a room at 25°C for 24 hours. After 24 hours, the formation of scum (flocculation) in the tank containing the residue was visually observed. The evaluation criteria are as follows: 3 or higher indicates a level that is practically sound.

[0601] 6: The mass of the filter residue was less than 1 mg and no scum (aggregate) was observed in the tank.

[0602] 5: The mass of the filter residue was more than 1 mg and less than 2 mg, and no scum (aggregate) was observed in the tank.

[0603] 4: The mass of the filter residue is more than 1mg and less than 2mg, but the formation of scum (aggregates) is observed in the tank.

[0604] 3: The mass of the filter residue is more than 2mg and less than 5mg.

[0605] 2: The mass of the filter residue is more than 5mg and less than 10mg.

[0606] 1: The mass of the filter residue is more than 10mg or a large amount of solid scum (aggregate) is observed in the tank.

[0607] [Table 2]

[0608]

[0609] [Table 3]

[0610]

[0611] As shown in Tables 2 and 3, it can be seen that in Examples 1 to 14, 0.1 mg of sodium carbonate was dissolved in 1 liter of a 1% sodium carbonate aqueous solution at 30°C. 2The turbidity of the solution obtained by using photosensitive transfer materials is below 60%, thus producing less scum (aggregates).

[0612] On the other hand, as shown in Table 3, it can be seen that in Comparative Example 1 and Comparative Example 2, the turbidity of the above solutions was 100% and 68.2%, respectively, and a large amount of scum (aggregates) was generated.

[0613] In Example 3, the acid value of the alkali-soluble resin contained in the photosensitive resin layer is above 120 mg KOH / g. Therefore, compared with Example 1, less scum (aggregate) is generated and the resolution is excellent.

[0614] In Example 3, the ratio of the content of polymeric compound to the content of alkali-soluble resin contained in the photosensitive resin layer was less than 0.85 by mass, so less scum (aggregate) was generated compared with Example 13.

[0615] In Example 8, the alkali-soluble resin contained in the photosensitive resin layer contains structural units derived from styrene, thus resulting in less scum (aggregate) formation compared to Example 7.

[0616] In Example 10, the thickness of the photosensitive resin layer was less than 10 μm, so less scum (aggregates) was generated compared with Example 9.

[0617] In Example 11, a polymeric compound with acid groups was contained, resulting in less scum (aggregate) formation compared to Example 8.

[0618] The photosensitive transfer material of this invention can be suitably used for various applications requiring precision microfabrication based on photolithography. After patterning the photosensitive resin layer, the photosensitive resin layer can be etched as a substrate or electroformed, primarily by electroplating. Furthermore, the cured film obtained through patterning can be used as a permanent film. The cured film can be used, for example, as an interlayer insulating film, a wiring protection film, or a wiring protection film with a refractive index matching layer. Moreover, the photosensitive transfer material of this invention is preferably used as a material for forming various wirings in semiconductor packages, printed circuit boards, sensor substrates, etc., and for forming touch panels, electromagnetic shielding materials, conductive films such as thin-film heaters, liquid crystal sealing materials, and structures in the fields of microcomputers and microelectronics.

[0619] Furthermore, the entire disclosure of Japanese Patent Application No. 2020-079534, filed on April 28, 2020, is incorporated herein by reference. Moreover, all documents, patent applications, and technical specifications described in this specification are incorporated herein by reference to the same extent that each document, patent application, and technical specification is specifically and separately described as being incorporated by reference.

Claims

1. A photosensitive transfer material comprising a temporary support and a photosensitive resin layer disposed on the temporary support, The photosensitive resin layer is a negative photosensitive resin layer and contains alkali-soluble resin and polymeric compounds. The alkali-soluble resin contains structural units derived from styrene. Dissolve 0.1 mg of sodium carbonate in 1 liter of a 1% (w / w) sodium carbonate aqueous solution at 30°C. 2 The turbidity of the solution obtained from the photosensitive transfer material is below 60%. The polymeric compounds include polymeric compounds having acid groups.

2. The photosensitive transfer material according to claim 1, wherein, The thickness of the photosensitive resin layer is less than 10 μm.

3. The photosensitive transfer material according to claim 1 or 2, wherein, The ratio of the content of the polymeric compound to the content of the alkali-soluble resin is 0.85 or less by mass.

4. The photosensitive transfer material according to claim 1 or 2, wherein, The acid value of the alkali-soluble resin is above 120 mg KOH / g.

5. The photosensitive transfer material according to claim 1 or 2, wherein, The content of styrene-derived structural units is 40% by mass or more relative to the total mass of the alkali-soluble resin.

6. The photosensitive transfer material according to claim 1 or 2, further comprising a thermoplastic resin layer between the temporary support and the photosensitive resin layer.

7. A method for manufacturing a resin pattern, comprising: A process of bonding the side of the photosensitive resin layer in the photosensitive transfer material according to any one of claims 1 to 6 that is not opposite to the temporary support to the substrate. A process of pattern exposure of the photosensitive resin layer in the photosensitive transfer material following the bonding process; and The process of developing the photosensitive resin layer after the exposure of the pattern to form a resin pattern.

8. A method for manufacturing circuit wiring, comprising: A process of bonding the side of the photosensitive resin layer in the photosensitive transfer material according to any one of claims 1 to 6 that is not opposite to the temporary support to the substrate. A process of pattern exposure of the photosensitive resin layer in the photosensitive transfer material after the bonding process; The process of developing the photosensitive resin layer after the exposure of the pattern to form the resin pattern; and The process of etching the substrate in the area where the resin pattern is not configured.

9. A method for manufacturing a touch panel, comprising: A process of bonding the side of the photosensitive resin layer in the photosensitive transfer material according to any one of claims 1 to 6 that is not opposite to the temporary support to the substrate. A process of pattern exposure of the photosensitive resin layer in the photosensitive transfer material after the bonding process; The process of developing the photosensitive resin layer after the exposure of the pattern to form the resin pattern; and The process of etching the substrate in the area where the resin pattern is not configured.

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