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

Abstract

Provided is a photosensitive material capable of forming a film having a low relative dielectric constant. Also provided are a pattern forming method, a circuit wiring manufacturing method, a touch panel manufacturing method, and a transfer film relating to the photosensitive material. This photosensitive material satisfies at least one of the following requirements (V01) and (W01). (V01) contains a polymer A having a carboxyl group and a compound [beta] having a structure b0 in which the amount of the carboxyl group contained in the polymer A is reduced by exposure to light. (W01) contains a polymer Ab0 which is the polymer A and which further has a structure b0 in which the amount of the carboxyl group contained in the polymer A is reduced by exposure to light.

Description

[0001] This application is a divisional application of the application with the application date of March 18, 2021, Chinese application number 202180022202.4, and invention name “Photosensitive material, transfer film, circuit wiring manufacturing method, touch panel manufacturing method, pattern formation method”. Technical Field

[0002] The present invention relates to a photosensitive material, a transfer film, a method for manufacturing circuit wiring, a method for manufacturing a touch panel, and a pattern forming method. Background Art

[0003] In a display device having a touch panel such as an electrostatic capacitive input device (specifically, an organic electroluminescent (EL) display device and a liquid crystal display device, etc.), a conductive pattern such as an electrode pattern of a sensor corresponding to a visual recognition part, a peripheral wiring part, and wiring of a lead-out wiring part is arranged inside the touch panel.

[0004] A resin pattern is usually placed on the conductive pattern as a protective film (permanent film) to prevent problems such as metal corrosion, increased resistance between the electrode and the driving circuit, and disconnection. A photosensitive material is generally used in the formation of the resin pattern.

[0005] For example, Patent Document 1 discloses “a photosensitive resin composition comprising a binder polymer having a carboxyl group having an acid value of 75 mgKOH / g or more on a substrate, a photopolymerizable compound, and a polymerization initiator.”

[0006] Previous technical literature

[0007] Patent Literature

[0008] Patent Document 1: International Publication No. 2013 / 084886 Summary of the Invention

[0009] Technical issues to be solved by the invention

[0010] The photosensitive resin composition (photosensitive material) described in Patent Document 1 is sometimes required to have a low relative dielectric constant when used in a film or the like for protecting electrodes such as a sensor thin film.

[0011] The present inventors have studied the above-mentioned photosensitive materials and have found that there is still room for improvement in the relative dielectric constant of the formed films.

[0012] Therefore, the present invention aims to provide a photosensitive material capable of forming a film with a low relative dielectric constant, a method for forming a pattern of the photosensitive material, a method for manufacturing a circuit wiring, a method for manufacturing a touch panel, and a transfer film.

[0013] Means for solving technical problems

[0014] The present inventors have conducted intensive studies on the above-mentioned problems and have found that the above-mentioned problems can be solved by the following configuration.

[0015] [1]

[0016] A photosensitive material that satisfies at least one of the following requirements (V01) and the following requirements (W01):

[0017] (V01) contains a polymer A having carboxyl groups and a compound β having a structure b0 in which the amount of the carboxyl groups in the polymer A is reduced by exposure.

[0018] (W01) includes a polymer Ab0, which is the polymer A and further has a structure b0 in which the amount of the carboxyl groups in the polymer A is reduced by exposure.

[0019] [2]

[0020] The photosensitive material according to [1], wherein

[0021] In the above requirement (V01), the compound β is compound B, and the compound B is a compound wherein the structure b0 is a structure b capable of accepting electrons from the carboxyl group in a photoexcited state.

[0022] In the above requirement (W01), the polymer Ab0 is a polymer Ab, and the polymer Ab is a polymer in which the structure b0 is a structure b capable of accepting electrons from the carboxyl group in a photoexcited state.

[0023] 〔3〕

[0024] The photosensitive material according to [1] or [2], which satisfies at least the above requirement (V01),

[0025] The compound β is an aromatic compound.

[0026] [4]

[0027] The photosensitive material according to any one of [1] to [3], which satisfies at least the above requirement (V01),

[0028] The compound β is an aromatic compound having a substituent.

[0029] 〔5〕

[0030] The photosensitive material according to any one of [1] to [4], which satisfies at least the above requirement (V01),

[0031] The compound β is a compound that satisfies one or more of the following requirements (1) to (4).

[0032] (1) Having polycyclic aromatic rings.

[0033] (2) It has a heteroaromatic ring.

[0034] (3) Having an aromatic carbonyl group.

[0035] (4) It has an aromatic imide group.

[0036] [6]

[0037] The photosensitive material according to any one of [1] to [5], which satisfies at least the above requirement (V01),

[0038] The molar absorption coefficient ε of the above compound β at 365 nm is 1×10 3 (cm·mol / L) -1 the following.

[0039] [7]

[0040] The photosensitive material according to any one of [1] to [6], which satisfies at least the above requirement (V01),

[0041] The ratio of the molar absorption coefficient ε of the compound β at 365 nm to the molar absorption coefficient ε′ of the compound β at 313 nm is 3 or less.

[0042] 〔8〕

[0043] The photosensitive material according to any one of [1] to [7], which satisfies at least the above requirement (V01),

[0044] The pKa of the compound β in the ground state is 2.0 or higher.

[0045] 〔9〕

[0046] The photosensitive material according to any one of [1] to [8], which satisfies at least the above requirement (V01),

[0047] The pKa of the compound β in the ground state is 9.0 or less.

[0048]

[10]

[0049] The photosensitive material according to any one of [1] to [9], which satisfies at least the above requirement (V01),

[0050] The compound β is one or more selected from the group consisting of pyridine and pyridine derivatives, quinoline and quinoline derivatives, and isoquinoline and isoquinoline derivatives.

[0051]

[11]

[0052] The photosensitive material according to any one of [1] to

[10] , wherein

[0053] The polymer A has repeating units based on (meth)acrylic acid.

[0054]

[12]

[0055] The photosensitive material according to any one of [1] to

[11] , wherein

[0056] The polymer A has a repeating unit having a polymerizable group.

[0057]

[13]

[0058] The photosensitive material according to any one of [1] to

[12] , which satisfies at least the above requirement (V01),

[0059] In the above requirement (V01), the compound β is compound B, and the compound B is a compound wherein the structure b0 is a structure b capable of accepting electrons from the carboxyl group in a photoexcited state.

[0060] In the photosensitive material, the total number of the structures b in the compound B relative to the total number of carboxyl groups in the polymer A is 5 mol% or more.

[0061]

[14]

[0062] The photosensitive material according to any one of [1] to

[13] , further comprising a polymerizable compound.

[0063]

[15]

[0064] The photosensitive material according to any one of [1] to

[14] , further comprising a photopolymerization initiator.

[0065]

[16]

[0066] The photosensitive material according to

[15] , wherein

[0067] The photopolymerization initiator is one or more selected from oxime ester compounds and aminoacetophenone compounds.

[0068]

[17]

[0069] A pattern forming method, comprising:

[0070] A step of forming a photosensitive layer on a substrate using the photosensitive material described in

[15] or

[16] ;

[0071] exposing the photosensitive layer to a pattern;

[0072] a step of developing the exposed photosensitive layer using an alkaline developer to form a patterned photosensitive layer; and

[0073] a step of exposing the patterned photosensitive layer to light.

[0074]

[18]

[0075] A method for manufacturing a circuit wiring, comprising:

[0076] A step of forming a photosensitive layer on a substrate having a conductive layer using the photosensitive material described in

[15] or

[16] ;

[0077] exposing the photosensitive layer to a pattern;

[0078] a step of developing the exposed photosensitive layer using an alkaline developer to form a patterned photosensitive layer;

[0079] exposing the patterned photosensitive layer to light to form an etching resist film; and

[0080] A step of etching the conductive layer in a region where the etching resist film is not provided.

[0081]

[19]

[0082] A method for manufacturing a touch panel, comprising:

[0083] A step of forming a photosensitive layer on a substrate having a conductive layer using the photosensitive material described in

[15] or

[16] ;

[0084] exposing the photosensitive layer to a pattern;

[0085] a step of developing the exposed photosensitive layer using an alkaline developer to form a patterned photosensitive layer; and

[0086] a step of exposing the patterned photosensitive layer to light to form a protective film or an insulating film for the conductive layer.

[0087] 〔20〕

[0088] A transfer film comprising a temporary support and a photosensitive layer formed using the photosensitive material described in any one of [1] to

[16] .

[0089] 〔twenty one〕

[0090] The transfer film according to

[20] , wherein the transmittance of the photosensitive layer at 365 nm is 65% or more.

[0091] 〔twenty two〕

[0092] The transfer film according to

[20] or

[21] , wherein

[0093] The ratio of the transmittance of the photosensitive layer at 365 nm to the transmittance of the photosensitive layer at 313 nm is 1.5 or more.

[0094] 〔twenty three〕

[0095] The transfer film according to any one of

[20] to

[22] , wherein

[0096] The content of the carboxyl group in the photosensitive layer is reduced at a reduction rate of 5 mol % or more by irradiation with actinic rays or radiation.

[0097] Effects of the Invention

[0098] The present invention provides a photosensitive material capable of forming a film having a low relative dielectric constant, a pattern forming method, a circuit wiring manufacturing method, a touch panel manufacturing method, and a transfer film using the photosensitive material. BRIEF DESCRIPTION OF THE DRAWINGS

[0099] Figure 1 It is a schematic diagram showing an example of the layer structure of the transfer film according to the embodiment. DETAILED DESCRIPTION

[0100] Hereinafter, the present invention will be described in detail.

[0101] In addition, in this specification, the numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0102] Furthermore, in the numerical ranges described at various stages in this specification, the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described at various stages. Furthermore, in the numerical ranges described in this specification, the upper limit or lower limit described in a certain numerical range may be replaced with the value shown in the Examples.

[0103] Furthermore, the term "process" in this specification encompasses not only independent processes but also processes that achieve the intended purpose of the process even when the process cannot be clearly distinguished from other processes.

[0104] In this specification, "transparent" means an average transmittance of visible light with a wavelength of 400 to 700 nm of 80% or more, preferably 90% or more. Therefore, for example, a "transparent resin layer" means a resin layer having an average transmittance of visible light with a wavelength of 400 to 700 nm of 80% or more.

[0105] The average transmittance of visible light is a value measured using a spectrophotometer, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

[0106] In this specification, "actinic rays" or "radiation" refers to, for example, the bright line spectrum of mercury lamps such as g-rays, h-rays, and i-rays, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams (EB). Furthermore, in the present invention, light refers to actinic rays or radiation.

[0107] Unless otherwise specified, the term "exposure" in this specification includes not only exposure using a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light, X-rays, and EUV light, but also drawing using a particle beam such as an electron beam and an ion beam.

[0108] In this specification, unless otherwise specified, the content ratio of each structural unit of a polymer is a molar ratio.

[0109] In addition, in this specification, unless otherwise specified, the refractive index is a value measured at a wavelength of 550 nm using an ellipsometer.

[0110] In this specification, unless otherwise specified, the molecular weight when there is a molecular weight distribution is the weight average molecular weight.

[0111] In this specification, the weight average molecular weight of a resin is a weight average molecular weight determined in terms of polystyrene by gel permeation chromatography (GPC).

[0112] In this specification, “(meth)acrylic acid” is a concept including both acrylic acid and methacrylic acid, and “(meth)acryloyl” is a concept including both acryloyl and methacryloyl.

[0113] In this specification, unless otherwise specified, the thickness of a layer (film thickness) is as follows: for thicknesses of 0.5 μm or more, it is the average thickness measured using a scanning electron microscope (SEM); for thicknesses of less than 0.5 μm, it is the average thickness measured using a transmission electron microscope (TEM). The above average thickness is the average thickness obtained by measuring the thickness of five arbitrary points on a slice of the object to be measured using an ultramicrotome and taking the arithmetic average of these measurements.

[0114] [Photosensitive materials]

[0115] The photosensitive material of the present invention satisfies at least one of the following requirements (V01) and the following requirements (W01).

[0116] (V01) contains a polymer A having carboxyl groups and a compound β having a structure b0 in which the amount of the carboxyl groups in the polymer A is reduced by exposure.

[0117] (W01) includes a polymer Ab0, which is the polymer A and further has a structure b0 in which the amount of the carboxyl groups in the polymer A is reduced by exposure.

[0118] Although the mechanism by which the problems of the present invention are solved by such a configuration is not yet clear, the present inventors believe the following.

[0119] Specifically, structure b0 is introduced by including at least one of compound β and polymer Ab0 in the photosensitive material of the present invention. Structure b0 reduces the amount of the carboxyl groups present in polymer A upon exposure. More specifically, for example, structure b0 causes the carboxyl groups, which have become acidic groups, to be released from polymer A as carbon dioxide. Furthermore, since polymer Ab0 is a form of polymer A, the released carboxyl groups can be carboxyl groups already present in polymer Ab0. Furthermore, the carboxyl groups on which structure b0 reacts can also become anions.

[0120] If structure b0 reduces the amount of the carboxyl group possessed by the polymer A, the polarity of the portion decreases. That is, the layer (photosensitive layer) formed using the photosensitive material of the present invention produces a change in polarity in the exposed portion caused by the detachment of the carboxyl group of polymer A. In the portion where the change in polarity occurs, the solubility in the developer changes, and in particular, the solubility in the developer (alkaline developer or organic solvent-based developer) changes in the exposed portion. For example, in the exposed portion, the solubility in the alkaline developer decreases, and the solubility in the organic solvent-based developer increases. By utilizing this change in solubility produced in the exposed portion, a positive or negative patterned film can be formed using the photosensitive material of the present invention. Hereinafter, the patterned film will also be referred to as a pattern.

[0121] And, think as follows: because the existence of carboxyl group helps the rising of the relative dielectric constant of film, therefore in the film (pattern) formed by negative development using the photosensitive material of the present invention, make at least a portion in the carboxyl group of exposure portion be broken away from as carbon dioxide, so the relative dielectric constant of the film obtained is also reduced.In addition, in the film (pattern) formed by positive development, after development, further expose to remaining film (pattern), thereby as mentioned above, at least a portion in the carboxyl group of polymer A in film becomes carbon dioxide and breaks away from.Therefore, think in the film (pattern) formed by positive development, the relative dielectric constant of the film obtained can also be reduced.

[0122] Furthermore, as described later, the photosensitive material of the present invention also preferably contains a polymerizable compound.

[0123] When the carboxyl groups are released as carbon dioxide, free radicals are generated at the sites on polymer A where the carboxyl groups are released as carbon dioxide. These free radicals initiate free radical polymerization of the polymerizable compound, thereby polymerizing the exposed portions of polymer A. It is believed that since the film formed in this manner also releases at least a portion of the carboxyl groups in the exposed portions as carbon dioxide, the relative dielectric constant is reduced.

[0124] As described later, the photosensitive material of the present invention preferably further contains a polymerizable compound and a photopolymerization initiator.

[0125] When the photosensitive material of the present invention contains a photopolymerization initiator, the aforementioned carboxyl group dissociation and polymerization initiation reactions can occur at different times. For example, a photosensitive layer formed using this photosensitive material can first be exposed to light at a wavelength or exposure level that minimizes carboxyl group dissociation, followed by polymerization with the photopolymerization initiator to cure the layer. Subsequently, the cured photosensitive layer can be exposed to light for a second time to cause carboxyl group dissociation. In this case, the carboxyl group dissociation can also be achieved, thereby producing a film with a reduced relative dielectric constant.

[0126] Alternatively, the first exposure may be patterned exposure, and a development step for removing unexposed portions or exposed portions may be performed before the second exposure, followed by further performing the second exposure to obtain a pattern (a patterned film).

[0127] As described above, the relative dielectric constant of a film formed from the photosensitive material of the present invention is reduced. Furthermore, the moisture permeability (water vapor permeability, WVTR) of the film is also reduced. Furthermore, the photosensitive material of the present invention not only exhibits excellent patterning properties but also suppresses film loss during patterning.

[0128] The present invention can be said to have the following effects: the ability to reduce the relative dielectric constant of a film formed by a photosensitive material, the ability to reduce the moisture permeability of a film formed by a photosensitive material, the excellent pattern forming properties of the photosensitive material, and the ability to inhibit the reduction of the film formed by the photosensitive material when forming a pattern. The one in which one or more of these characteristics is more excellent can also be said to have a more excellent effect of the present invention.

[0129] <Requirements (V01), Requirements (W01)>

[0130] The photosensitive material of the present invention satisfies at least one of the following requirements (V01) and the following requirements (W01).

[0131] (V01) contains a polymer A having carboxyl groups and a compound β having a structure b0 in which the amount of the carboxyl groups in the polymer A is reduced by exposure.

[0132] (W01) includes a polymer Ab0, which is the polymer A and further has a structure b0 in which the amount of the carboxyl groups in the polymer A is reduced by exposure.

[0133] The photosensitive material of the present invention may satisfy only requirement (V01) and not requirement (W01), may satisfy only requirement (W01) and not requirement (V01), or may satisfy both requirements (V01) and (W01). It is preferred that at least requirement (V01) be satisfied.

[0134] The structure b0 is a structure that, when exposed to light, exhibits an effect of reducing the amount of carboxyl groups contained in polymer A. As the structure b0, preferably, a structure that transitions from a ground state to an excited state by exposure and, in the excited state, exhibits an effect of reducing the amount of carboxyl groups in polymer A. As the structure b0, for example, a structure that is exposed to light to enter a photoexcited state and accepts electrons from the carboxyl groups contained in polymer A (structure b) is preferred.

[0135] When structure b is exposed to light, its electron-accepting properties increase, and it transfers electrons from the carboxyl groups in polymer A. Furthermore, during this electron transfer, the carboxyl groups can become anions. Furthermore, since polymer Ab0 is a form of polymer A, the carboxyl groups in polymer Ab0 can also transfer electrons to structure b.

[0136] When the carboxyl group transfers electrons to the structure b, the carboxyl group becomes unstable and is released as carbon dioxide. This allows the amount of the carboxyl group in the polymer A to be reduced by exposure.

[0137] Among them, in the above requirement (V01), the compound β is preferably compound B. Compound B is a preferred embodiment of compound β, in which structure b0 in compound β is structure b (a structure capable of accepting electrons from the carboxyl group in a photoexcited state).

[0138] Furthermore, in the above requirement (W01), the polymer Ab0 is also preferably polymer Ab. The polymer Ab is a preferred embodiment of polymer Ab0, wherein structure b0 in polymer Ab0 is a polymer having structure b (a structure capable of accepting electrons from the carboxyl group in a photoexcited state).

[0139] Below, polyacrylic acid as polymer A and quinoline as compound B are given as an example, and the inferred mechanism of the process (decarboxylation process) of desorption by becoming the above-mentioned carbon dioxide (the inferred mechanism that uses structure b as the starting point and can reduce the content of carboxyl groups from polymer A by exposure) is described in detail.

[0140] As shown in the figure below, the carboxyl groups of polyacrylic acid coexist with the nitrogen atoms of quinoline to form hydrogen bonds. When quinoline is exposed to light, its electron-accepting properties increase, and it transfers electrons from the carboxyl groups of polyacrylic acid (Step 1: Photoexcitation). When the carboxyl groups of polyacrylic acid transfer electrons to quinoline, they become unstable and escape as carbon dioxide (Step 2: Decarboxylation). After this decarboxylation reaction, free radicals are generated in the residues of polyacrylic acid, and a free radical reaction proceeds. Free radical reactions can occur between polyacrylic acid residues, between polyacrylic acid residues and optionally included polymerizable compounds (monomers (M)), and between hydrogen atoms in the atmosphere (Step 3: Polarity conversion, crosslinking, and polymerization). Furthermore, after the free radical reaction ends, compound B is regenerated and can once again contribute to the decarboxylation process of polymer A (Step 4: Regeneration of compound B (catalyst)).

[0141] [Chemical Formula 1]

[0142]

[0143] <Requirements (V), Requirements (W)>

[0144] As described above, structure b0 is preferably structure b.

[0145] That is, the requirement (V01) is preferably the following requirement (V), and the requirement (W01) is preferably the following requirement (W).

[0146] (V) A compound B comprising a polymer A having a carboxyl group and a structure b capable of accepting electrons from the carboxyl group of the polymer A in a photoexcited state.

[0147] (W) includes a polymer Ab, which is the polymer A and further has a structure b in which the amount of the carboxyl groups in the polymer A is reduced by exposure.

[0148] The photosensitive material of the present invention preferably satisfies at least one of the above-mentioned requirements (V) and (W).

[0149] The photosensitive material of the present invention may satisfy only requirement (V) and not requirement (W), may satisfy only requirement (W) and not requirement (V), or may satisfy both requirements (V) and (W). It is preferred that at least requirement (V) be satisfied.

[0150] The polymer A (including polymer Ab0 and polymer Ab) and the compound β (including compound B) will be described in detail later.

[0151] <Method>

[0152] The photosensitive material of the present invention is preferably in the following aspects, for example.

[0153] Mode 1: A mode in which the photosensitive material satisfies at least one of the requirements (V01) and (W01) (preferably the requirements (V) and (W)) and does not contain a polymerizable compound and a photopolymerization initiator.

[0154] Mode 2: A mode in which the photosensitive material satisfies at least one of the requirements (V01) and (W01) (preferably the requirements (V) and (W)), further contains a polymerizable compound, and does not contain a photopolymerization initiator.

[0155] Aspect 3: Aspect in which the photosensitive material satisfies at least one of the requirements (V01) and (W01) (preferably the requirements (V) and (W)) and further contains a polymerizable compound and a photopolymerization initiator.

[0156] In addition, in the above-mentioned embodiment 1, the photosensitive material does not contain a polymerizable compound, which means that the photosensitive material does not substantially contain a polymerizable compound, and the content of the polymerizable compound relative to the total solid content of the photosensitive material can be less than 3 mass %, preferably 0 to 1 mass %, and more preferably 0 to 0.1 mass %.

[0157] In the above-mentioned embodiments 1 and 2, the photosensitive material does not contain a photopolymerization initiator, which means that the photosensitive material does not substantially contain a photopolymerization initiator, and the content of the photopolymerization initiator relative to the total solid content of the photosensitive material can be less than 0.1% by mass, preferably 0 to 0.05% by mass, and more preferably 0 to 0.01% by mass.

[0158] In this specification, the solid content of the photosensitive material refers to the components in the photosensitive material excluding the solvent. Furthermore, even liquid components are considered solid components as long as they are not the solvent.

[0159] Hereinafter, the components contained in the photosensitive material of the present invention will be described in detail.

[0160] <Polymer A>

[0161] The photosensitive material includes polymer A.

[0162] Polymer A is a polymer having a carboxyl group.

[0163] In addition, part or all of the carboxyl groups (-COOH) of the polymer A may be anionized or not anionized in the photosensitive material, and the anionized carboxyl groups (-COOH - ) and non-anionized carboxyl groups are collectively referred to as carboxyl groups.

[0164] That is, the polymer A may be anionized or not anionized in the photosensitive material, and both the anionized polymer A and the non-anionized polymer A are collectively referred to as polymer A.

[0165] Typically, polymer A is an alkali-soluble resin.

[0166] In the present invention, "alkali-soluble" means that the dissolution rate determined by the following method is 0.01 μm / sec or more.

[0167] A 25% by mass solution of propylene glycol monomethyl ether acetate containing a target compound (e.g., resin) was applied to a glass substrate and then heated in an oven at 100°C for 3 minutes to form a coating film (2.0 μm thick) of the target compound. The coating film was then immersed in a 1% by mass aqueous solution of sodium carbonate (liquid temperature 30°C) to determine the dissolution rate (μm / second) of the coating film.

[0168] When the target compound is not soluble in propylene glycol monomethyl ether acetate, the target compound is dissolved in an organic solvent other than propylene glycol monomethyl ether acetate and having a boiling point of less than 200° C. (for example, tetrahydrofuran, toluene, or ethanol).

[0169] The polymer A may further have an acid group other than a carboxyl group as an acid group. Examples of the acid group other than a carboxyl group include a phenolic hydroxyl group, a phosphoric acid group, and a sulfonic acid group.

[0170] From the viewpoint of developability, the acid value of the polymer A is preferably 60 to 300 mgKOH / g, more preferably 60 to 275 mgKOH / g, and even more preferably 75 to 250 mgKOH / g.

[0171] In this specification, the acid value of a resin is a value measured by the titration method specified in JIS K0070 (1992).

[0172] Polymer A may have structure b0 (preferably structure b). As described above, when structure b0 is exposed to light, it exhibits an effect of reducing the amount of carboxyl groups contained in polymer A. Structure b0 is preferably a structure that transitions from a ground state to an excited state upon exposure and exhibits an effect of reducing the amount of carboxyl groups in polymer A in the excited state.

[0173] Examples of the structure b0 possessed by the polymer A include a structure capable of accepting electrons from a carboxyl group contained in the polymer A in a photoexcited state (structure b).

[0174] A polymer A having structure b0 is also particularly referred to as polymer Ab0. A polymer A having structure b is also particularly referred to as polymer Ab. Furthermore, a polymer A not having structure b0 (including structure b) is also particularly referred to as polymer Aa. Polymer A may be polymer Aa or polymer Ab0 (preferably polymer Ab). When the photosensitive material contains two or more polymers A, it may contain one of polymer Aa and polymer Ab0 (preferably polymer Ab), or it may contain both. When the photosensitive material of the present invention satisfies requirement (W01) (preferably requirement (W)), the photosensitive material contains at least polymer Ab0 (preferably polymer Ab).

[0175] The polymer Aa does not have the structure b0, which means that the polymer A does not substantially have the structure b0. For example, the content of the structure b0 in the polymer Aa may be less than 1% by mass relative to the total mass of the polymer Aa, preferably 0 to 0.5% by mass, and more preferably 0 to 0.05% by mass.

[0176] The content of the structure b0 in the polymer Ab0 is preferably 1% by mass or more, more preferably 1 to 50% by mass, and even more preferably 5 to 40% by mass, relative to the total mass of the polymer Ab0.

[0177] The content of structure b in polymer Ab is preferably 1% by mass or more, more preferably 1 to 50% by mass, and even more preferably 5 to 40% by mass, relative to the total mass of polymer Ab.

[0178] When the polymer A includes the polymer Ab0 (preferably the polymer Ab), the content of the polymer Ab0 (preferably the polymer Ab) relative to the total mass of the polymer A is preferably 5 to 100% by mass.

[0179] Structure b0 reduces the amount of carboxyl groups contained in polymer A by light irradiation. For example, structure b, which is a preferred embodiment of structure b0, is excited by light irradiation and, in the excited state, accepts electrons from carboxyl groups (preferably anionized carboxyl groups) in polymer A. As a result, the carboxyl groups in polymer A become carboxyl radicals and then decarboxylate.

[0180] It is considered that the effect of the structure b0 (preferably structure b) causes a change in the solubility of the polymer A in the developer (such as insolubilization in the alkaline developer) in the exposed portion, thereby enabling pattern formation.

[0181] Among them, examples of the structure b0 (preferably structure b) possessed by the polymer A include heteroaromatic rings.

[0182] The heteroaromatic ring may be monocyclic or polycyclic, preferably polycyclic. The polycyclic heteroaromatic ring is formed by condensing multiple (e.g., 2 to 5) aromatic ring structures, and at least one of the multiple aromatic ring structures has a heteroatom as a ring member.

[0183] The heteroaromatic ring has one or more heteroatoms (such as nitrogen atoms, oxygen atoms, and sulfur atoms) as ring members, preferably 1 to 4 heteroatoms. Furthermore, the heteroaromatic ring preferably has one or more (for example, 1 to 4) nitrogen atoms as ring members.

[0184] The heteroaromatic ring preferably has 5 to 15 ring members.

[0185] Examples of the heteroaromatic ring include monocyclic heteroaromatic rings such as a pyridine ring, a pyrazine ring, a pyrimidine ring, and a triazine ring; heteroaromatic rings obtained by condensing two rings such as a quinoline ring, an isoquinoline ring, a quinoxaline ring, and a quinazoline ring; and heteroaromatic rings obtained by condensing three rings such as an acridine ring, a phenanthridine ring, a phenanthroline ring, and a phenazine ring.

[0186] The heteroaromatic ring may have one or more (e.g., 1 to 5) substituents. Examples of such substituents include alkyl groups, aryl groups, halogen atoms, acyl groups, alkoxycarbonyl groups, arylcarbonyl groups, carbamoyl groups, hydroxyl groups, cyano groups, and nitro groups. Furthermore, when the aromatic ring has two or more substituents, the multiple substituents may be bonded to each other to form a non-aromatic ring.

[0187] Furthermore, it is also preferred that the heteroaromatic ring and the carbonyl group are directly bonded.

[0188] It is also preferred that the heteroaromatic ring is bonded to an imide group to form a heteroaromatic imide group in compound B. The imide group in the heteroaromatic imide group may or may not form an imide ring together with the heteroaromatic ring.

[0189] In addition, in polymer A, multiple aromatic rings (for example, 2 to 5 aromatic rings) form a series of aromatic ring structures bonded by structures selected from single bonds, carbonyl groups and multiple bonds (for example, vinylene groups that may have substituents, -C≡C-, -N=N-, etc.), and when one or more of the multiple aromatic rings constituting the above-mentioned series of aromatic ring structures are the above-mentioned heteroaromatic rings, the above-mentioned series of aromatic ring structures as a whole are regarded as one structure b0 (including structure b).

[0190] The weight average molecular weight of polymer A is preferably 5000 or more, more preferably 10000 or more. The upper limit of the weight average molecular weight of polymer A is not particularly limited, but can be 100,000, and is preferably 50,000 or less.

[0191] As a preferred embodiment of the weight average molecular weight of the polymer A, it is preferably 5,000 to 200,000, more preferably 10,000 to 100,000, and even more preferably 11,000 to 49,000.

[0192] (Repeating unit having a carboxyl group)

[0193] The polymer A preferably has a repeating unit having a carboxyl group.

[0194] Examples of the repeating unit having a carboxyl group include repeating units represented by the following general formula (A).

[0195] [Chemical Formula 2]

[0196]

[0197] In the general formula (A), R A1 represents a hydrogen atom, a halogen atom, or an alkyl group. The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 5, more preferably 1.

[0198] A 1 represents a single bond or a divalent linking group. Examples of the divalent linking group include -CO-, -O-, -S-, -SO-, -SO2-, and -NR N -(R N is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), a hydrocarbon group (for example, an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group such as a phenylene group, etc.), and a linking group formed by linking a plurality of these groups.

[0199] Examples of the monomer derived from a repeating unit having a carboxyl group include (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-(meth)acryloyloxyethylsuccinic acid, and styrenecarboxylic acid, and (meth)acrylic acid is preferred.

[0200] That is, the repeating unit having a carboxyl group is preferably a repeating unit based on (meth)acrylic acid.

[0201] The polymer A preferably has repeating units based on (meth)acrylic acid.

[0202] In addition, in this specification, when referring to a repeating unit based on a specific monomer or a repeating unit derived from a specific monomer, the repeating unit may be a repeating unit having a structure formed by polymerization of the specific monomer. For example, when a repeating unit formed using a monomer different from the specific monomer is modified or deprotected to obtain a repeating unit having the same structure as a repeating unit having a structure formed by polymerization of the specific monomer, the repeating unit obtained in this manner is also referred to as a repeating unit based on the specific monomer or a repeating unit derived from the specific monomer.

[0203] In the polymer A, the content of the repeating unit having a carboxyl group is preferably 5 to 100 mol % relative to all the repeating units of the polymer A, more preferably 10 to 65 mol %, and even more preferably 15 to 45 mol %.

[0204] Furthermore, in the polymer A, the content of the repeating unit having a carboxyl group is preferably 1 to 100% by mass, more preferably 5 to 70% by mass, and even more preferably 12 to 50% by mass, based on all the repeating units of the polymer A.

[0205] In addition, all the repeating units of the above-mentioned polymer A may be all the repeating units of polymer Aa only, all the repeating units of polymer Ab0 only (preferably polymer Ab), or all the repeating units of both polymer Aa and polymer Ab0 (preferably polymer Ab).

[0206] The repeating unit having a carboxyl group may be used alone or in combination of two or more.

[0207] (Repeating unit having a polymerizable group)

[0208] The polymer A preferably includes a repeating unit having a polymerizable group in addition to the above-mentioned repeating units.

[0209] Examples of the polymerizable group include ethylenically unsaturated groups (e.g., (meth)acryloyl, vinyl, and styryl groups) and cyclic ether groups (e.g., epoxy, oxetane groups), among which ethylenically unsaturated groups are preferred, and (meth)acryloyl groups are more preferred.

[0210] Examples of the repeating unit having a polymerizable group include repeating units represented by the following general formula (B).

[0211] [Chemical Formula 3]

[0212]

[0213] In the general formula (B), X B1 and X B2 Each independently represents -O- or -NR N -. R N represents a hydrogen atom or an alkyl group. The alkyl group may be linear or branched, and preferably has 1 to 5 carbon atoms.

[0214] L represents an alkylene group or an arylene group. The alkylene group may be linear or branched, and preferably has 1 to 5 carbon atoms. The arylene group may be monocyclic or polycyclic, and preferably has 6 to 15 carbon atoms. The alkylene group and arylene group may have a substituent, and examples of such substituents include a hydroxyl group.

[0215] R B1 and R B2 Each independently represents a hydrogen atom or an alkyl group. The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 5, more preferably 1.

[0216] When the polymer A has a repeating unit having a polymerizable group, the content thereof is preferably 3 to 60 mol % relative to all repeating units of the polymer A, more preferably 5 to 40 mol %, and even more preferably 10 to 30 mol %.

[0217] In the polymer A, the content of the repeating unit having a polymerizable group is preferably 1 to 70% by mass, more preferably 5 to 50% by mass, and even more preferably 12 to 45% by mass, based on all the repeating units of the polymer A.

[0218] In addition, all the repeating units of the above-mentioned polymer A may be all the repeating units of polymer Aa only, all the repeating units of polymer Ab0 only (preferably polymer Ab), or all the repeating units of both polymer Aa and polymer Ab0 (preferably polymer Ab).

[0219] The repeating unit having a polymerizable group may be used alone or in combination of two or more.

[0220] (Repeating unit with structure b0)

[0221] The polymer A preferably also includes a repeating unit having structure b0 (preferably structure b) in addition to the above-mentioned repeating units.

[0222] The structures b0 and b are as described above.

[0223] The structure b0 (preferably structure b) in the repeating unit having structure b0 (preferably structure b) may be present in the main chain or in a side chain, preferably in a side chain. When structure b0 (preferably structure b) is present in a side chain, structure b0 (preferably structure b) is bonded to the polymer main chain via a single bond or a linking group.

[0224] Repeating units having structure b0 (preferably structure b) are, for example, repeating units based on monomers having a heteroaromatic ring (specifically, vinyl heteroaromatic rings such as vinylpyridine and vinyl (iso)quinoline, and (meth)acrylate monomers having a heteroaromatic ring).

[0225] Specific examples of the repeating unit having structure b0 (preferably structure b) are shown below, but the present invention is not limited thereto.

[0226] [Chemical Formula 4]

[0227]

[0228] When polymer A has a repeating unit having structure b0 (preferably structure b), its content relative to all repeating units of polymer A is preferably 3 to 75 mol%, more preferably 5 to 60 mol%, and even more preferably 10 to 50 mol%.

[0229] When polymer A has repeating units having structure b0 (preferably structure b), the content thereof is preferably 1 to 75% by mass, more preferably 3 to 60% by mass, and even more preferably 5 to 30% by mass relative to all repeating units of polymer A.

[0230] In addition, when polymer A includes polymer Aa and polymer Ab0 (preferably polymer Ab), all repeating units of the above-mentioned polymer A may be all repeating units only for polymer Ab0 (preferably polymer Ab), or may include all repeating units of both polymer Aa and polymer Ab.

[0231] The repeating unit having structure b0 (preferably structure b) may be used alone or in combination of two or more.

[0232] (Repeating unit having an aromatic ring)

[0233] In addition to the above-mentioned repeating units, the polymer A also preferably has a repeating unit having an aromatic ring (preferably an aromatic hydrocarbon ring).

[0234] Examples of the repeating unit having an aromatic ring include repeating units based on (meth)acrylates, styrene, and polymerizable styrene derivatives having an aromatic ring.

[0235] Examples of the (meth)acrylate having an aromatic ring include benzyl (meth)acrylate, phenethyl (meth)acrylate, and phenoxyethyl (meth)acrylate.

[0236] Examples of styrene and polymerizable styrene derivatives include methylstyrene, vinyltoluene, tert-oxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer.

[0237] As the repeating unit having an aromatic ring, a repeating unit represented by the following general formula (C) is also preferred.

[0238] [Chemical Formula 5]

[0239]

[0240] In the general formula (C), R C1 represents a hydrogen atom, a halogen atom, or an alkyl group. The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 5, more preferably 1.

[0241] Ar C The phenyl group and the naphthyl group may have one or more substituents, and examples of the substituents include an alkyl group, an alkoxy group, an aryl group, a halogen atom, and a hydroxyl group.

[0242] Hereinafter, examples of repeating units having an aromatic ring are given.

[0243] [Chemical Formula 6]

[0244]

[0245] Among them, the following structures are preferred as the repeating unit having an aromatic ring.

[0246] [Chemical Formula 7]

[0247]

[0248] When the polymer A has a repeating unit having an aromatic ring, the content thereof is preferably 5 to 80 mol % relative to all repeating units of the polymer A, more preferably 15 to 75 mol %, and even more preferably 30 to 70 mol %.

[0249] When the polymer A has a repeating unit having an aromatic ring, the content thereof is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and even more preferably 30 to 70% by mass relative to all repeating units of the polymer A.

[0250] In addition, all the repeating units of the above-mentioned polymer A may be all the repeating units of polymer Aa only, all the repeating units of polymer Ab0 only (preferably polymer Ab), or all the repeating units of both polymer Aa and polymer Ab0 (preferably polymer Ab).

[0251] The repeating unit having an aromatic ring may be used alone or in combination of two or more.

[0252] (Repeating unit having an alicyclic structure)

[0253] In addition to the above-mentioned repeating units, the polymer A preferably also has a repeating unit having an alicyclic structure. The alicyclic structure may be monocyclic or polycyclic.

[0254] Examples of the alicyclic structure include a dicyclopentane ring structure, a dicyclopentene ring structure, an isocamphenyl ring structure, an adamantane ring structure, and a cyclohexyl ring structure.

[0255] Examples of the monomer derived from a repeating unit having an alicyclic structure include dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, and cyclohexyl (meth)acrylate.

[0256] When the polymer A contains a repeating unit having an alicyclic structure, the content thereof is preferably 3 to 70 mol % relative to all repeating units of the polymer A, more preferably 5 to 60 mol %, and even more preferably 10 to 55 mol %.

[0257] When the polymer A contains a repeating unit having an alicyclic structure, the content thereof is preferably 3 to 90% by mass, more preferably 5 to 70% by mass, and even more preferably 25 to 60% by mass relative to all repeating units of the polymer A.

[0258] In addition, all the repeating units of the above-mentioned polymer A may be all the repeating units of polymer Aa only, all the repeating units of polymer Ab0 only (preferably polymer Ab), or all the repeating units of both polymer Aa and polymer Ab0 (preferably polymer Ab).

[0259] The repeating unit having an alicyclic structure may be used alone or in combination of two or more.

[0260] (Other repeating units)

[0261] The polymer A may have other repeating units in addition to the above-mentioned repeating units.

[0262] As the above-mentioned other repeating units, alkyl (meth)acrylates can be mentioned, and as the alkyl group, an alkyl group having a chain structure can be mentioned. The chain structure can be a straight chain structure or a branched structure. The alkyl group can also have a substituent such as a hydroxyl group. As the number of carbon atoms of the alkyl group, 1 to 50 can be mentioned, and 1 to 10 are more preferred. As specific examples, repeating units based on methyl methacrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate can be mentioned.

[0263] When the polymer A contains other repeating units, the content thereof is preferably 1 to 70 mol %, more preferably 2 to 50 mol %, and even more preferably 3 to 20 mol % relative to all repeating units of the polymer A.

[0264] When the polymer A contains other repeating units, the content thereof is preferably 1 to 70% by mass, more preferably 2 to 50% by mass, and even more preferably 5 to 35% by mass, relative to all repeating units of the polymer A.

[0265] In addition, all the repeating units of the above-mentioned polymer A may be all the repeating units of polymer Aa only, all the repeating units of polymer Ab0 only (preferably polymer Ab), or all the repeating units of both polymer Aa and polymer Ab0 (preferably polymer Ab).

[0266] The other repeating units may be used alone or in combination of two or more.

[0267] In the photosensitive material of the present invention, the content of polymer A is preferably 25 to 100% by mass relative to the total solids content of the photosensitive material. However, when the photosensitive material of the present invention does not satisfy requirement (W01) and / or requirement (W), the content of polymer A is preferably 25 to 99% by mass relative to the total solids content of the photosensitive material.

[0268] In the photosensitive material of embodiment 1, the content of polymer A is preferably 40 to 98% by mass, more preferably 50 to 96% by mass, and even more preferably 60 to 93% by mass relative to the total solid content of the photosensitive material.

[0269] In the photosensitive material of embodiment 2, the content of the polymer A is preferably 30 to 85% by mass, more preferably 45 to 75% by mass, based on the total solid content of the photosensitive material.

[0270] In the photosensitive material of embodiment 3, the content of the polymer A is preferably 30 to 85% by mass, more preferably 45 to 75% by mass, based on the total solid content of the photosensitive material.

[0271] The content of the polymer A is the total content of the polymer Aa and the polymer Ab0 (preferably the polymer Ab) when the polymer A includes the polymer Aa and the polymer Ab0.

[0272] From the perspective of patterning properties and reliability, the content of residual monomers used to produce the repeating units in polymer A in the photosensitive material is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, and even more preferably 500 mass ppm or less, relative to the total mass of polymer A. The lower limit is not particularly limited, but is preferably 1 mass ppm or more, and more preferably 10 mass ppm or more.

[0273] From the perspective of patterning properties and reliability, the residual monomer content is preferably 3,000 ppm by mass or less, more preferably 600 ppm by mass or less, and even more preferably 100 ppm by mass or less, relative to the total solids content of the photosensitive material. The lower limit is not particularly limited, but is preferably 0.1 ppm by mass or more, and more preferably 1 ppm by mass or more.

[0274] The above-mentioned residual monomer amount is also preferably within the above-mentioned range when synthesizing polymer A by high molecular weight reaction. For example, when synthesizing polymer A by reacting glycidyl acrylate with a carboxyl side chain, the glycidyl acrylate content is preferably within the above-mentioned range.

[0275] <Compound β>

[0276] The photosensitive material preferably contains compound β.

[0277] Compound β is a compound having a structure (structure b0) in which exposure to light reduces the amount of carboxyl groups in polymer A. Structure b0 is as described above.

[0278] Among them, the structure b0 is preferably a structure (structure b) capable of accepting electrons from the carboxyl group of polymer A in a photoexcited state. That is, the compound β is preferably a compound B having a structure (structure b) capable of accepting electrons from the carboxyl group of polymer A in a photoexcited state.

[0279] Compound β reduces the amount of carboxyl groups contained in polymer A by being irradiated with light. For example, compound B, which is a preferred embodiment of compound β, is excited by light irradiation and, in the excited state, accepts electrons from carboxyl groups (preferably anionized carboxyl groups) in polymer A. As a result, the carboxyl groups in polymer A become carboxyl radicals and then decarboxylate.

[0280] It is considered that the action of the compound β (preferably the compound B) causes a change in the solubility of the polymer A in the developer (eg, insolubilization in the alkaline developer) in the exposed portion, thereby enabling pattern formation.

[0281] The structure b0 (preferably structure b) of compound β (preferably compound B) may be a structure constituting the entire compound β (preferably compound B) or a partial structure constituting a portion of compound β (preferably compound B).

[0282] The compound β (preferably the compound B) may be a high molecular weight compound or a low molecular weight compound, but is preferably a low molecular weight compound.

[0283] The molecular weight of the compound β (preferably compound B) as a low molecular weight compound is preferably less than 5,000, more preferably less than 1,000, further preferably 65 to 300, and particularly preferably 75 to 250.

[0284] From the viewpoint of achieving more excellent effects of the present invention, the compound β (preferably the compound B) is preferably an aromatic compound. The aromatic compound is also preferably an aromatic compound having a substituent.

[0285] Here, the aromatic compound refers to a compound having one or more aromatic rings.

[0286] The aromatic ring may be present in only one or more than one aromatic ring in compound β (preferably compound B). When there are more than one aromatic ring, the aromatic ring may be present in a side chain of a resin, for example.

[0287] In compound β (preferably compound B), an aromatic ring can serve as structure b capable of accepting electrons from the carboxyl group of polymer A in the photoexcited state. The aromatic ring may be an integral structure constituting the entire compound β (preferably compound B) or a partial structure constituting a portion of compound β (preferably compound B).

[0288] The aromatic ring may be monocyclic or polycyclic, preferably polycyclic. A polycyclic aromatic ring is, for example, an aromatic ring formed by condensing multiple (e.g., 2 to 5) aromatic ring structures, at least one of which preferably has a heteroatom as a ring member.

[0289] The aromatic ring may be a heteroaromatic ring, preferably having one or more (e.g., 1 to 4) heteroatoms (e.g., nitrogen atoms, oxygen atoms, sulfur atoms) as ring members, more preferably one or more (e.g., 1 to 4) nitrogen atoms as ring members.

[0290] The aromatic ring preferably has 5 to 15 ring members.

[0291] The compound β (preferably the compound B) is preferably a compound having a 6-membered aromatic ring having a nitrogen atom as a ring member.

[0292] Examples of the aromatic ring include monocyclic aromatic rings such as a pyridine ring, a pyrazine ring, a pyrimidine ring, and a triazine ring; aromatic rings formed by condensing two rings such as a quinoline ring, an isoquinoline ring, a quinoxaline ring, and a quinazoline ring; and aromatic rings formed by condensing three rings such as an acridine ring, a phenanthidine ring, a phenanthroline ring, and a phenanthrazine ring.

[0293] The aromatic ring may have one or more (e.g., 1 to 5) substituents. Examples of such substituents include alkyl groups, aryl groups, halogen atoms, acyl groups, alkoxycarbonyl groups, arylcarbonyl groups, carbamoyl groups, hydroxyl groups, cyano groups, amino groups, and nitro groups. Furthermore, when the aromatic ring has two or more substituents, the multiple substituents may be bonded to each other to form a non-aromatic ring.

[0294] Furthermore, it is also preferred that the aromatic ring is directly bonded to the carbonyl group to form an aromatic carbonyl group in compound β (preferably compound B). It is also preferred that a plurality of aromatic rings are bonded via a carbonyl group.

[0295] It is also preferred that the aromatic ring is bonded to an imide group to form an aromatic imide group in compound β (preferably compound B). The imide group in the aromatic imide group may or may not form an imide ring together with the aromatic ring.

[0296] In addition, when multiple aromatic rings (for example, 2 to 5 aromatic rings) form a series of aromatic ring structures bonded by structures selected from single bonds, carbonyl groups and multiple bonds (for example, vinylene groups that may have substituents, -C≡C-, -N=N-, etc.), the above series of aromatic ring structures as a whole are regarded as one structure b.

[0297] Furthermore, it is preferred that at least one of the plurality of aromatic rings constituting the series of aromatic ring structures be the heteroaromatic ring.

[0298] From the viewpoint of achieving a more excellent effect of the present invention, compound β (preferably compound B) is preferably a compound that satisfies one or more (e.g., one to four) of the following requirements (1) to (4). Among these, it is preferred that at least requirement (2) is satisfied, and the heteroatom possessed by the heteroaromatic ring preferably contains at least a nitrogen atom.

[0299] (1) having a polycyclic aromatic ring,

[0300] (2) having a heteroaromatic ring,

[0301] (3) having an aromatic carbonyl group,

[0302] (4) It has an aromatic imide group.

[0303] Specific examples of compound β (preferably compound B) include monocyclic aromatic compounds such as pyridine and pyridine derivatives, pyrazine and pyrazine derivatives, pyrimidine and pyrimidine derivatives, and triazine and triazine derivatives; compounds in which two rings are condensed to form an aromatic ring such as quinoline and quinoline derivatives, isoquinoline and isoquinoline derivatives, quinoxaline and quinoxaline derivatives, and quinazoline and quinazoline derivatives; and compounds in which three or more rings are condensed to form an aromatic ring such as acridine and acridine derivatives, phenanthidine and phenanthidine derivatives, phenanthroline and phenanthroline derivatives, and phenanthrazine and phenanthrazine derivatives.

[0304] Among them, compound β (preferably compound B) is preferably one or more selected from pyridine and pyridine derivatives, quinoline and quinoline derivatives, and isoquinoline and isoquinoline derivatives, more preferably one or more selected from quinoline and quinoline derivatives, and isoquinoline and isoquinoline derivatives, and further preferably one or more selected from isoquinoline and isoquinoline derivatives.

[0305] These compounds and their derivatives may further have a substituent. As the above-mentioned substituent, an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxyl group, a cyano group, an amino group or a nitro group is preferred, an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxyl group, a cyano group or a nitro group is more preferred, an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxyl group, a cyano group or a nitro group is further preferred, and an alkyl group (for example, a linear or branched alkyl group having 1 to 10 carbon atoms) is particularly preferred.

[0306] Furthermore, from the viewpoint of achieving a better pattern forming ability and / or lowering the moisture permeability of the formed pattern, compound β (preferably compound B) is preferably an aromatic compound having a substituent (a compound having a substituent at a structural atom of the aromatic ring contained in compound β (preferably compound B)), and more preferably a compound satisfying one or more (for example, 1 to 4) of the above-mentioned requirements (1) to (4) and further having a substituent.

[0307] Regarding the position of the substituent, for example, in the case of compound β (preferably compound B) quinoline and quinoline derivatives, it is preferred that a substituent be present at at least the 2nd and 4th positions on the quinoline ring from the perspective of further improving pattern forming ability and / or reducing the moisture permeability of the formed pattern. Furthermore, for example, in the case of compound β (preferably compound B) isoquinoline and isoquinoline derivatives, it is preferred that a substituent be present at at least the 1st position on the isoquinoline ring from the perspective of further improving pattern forming ability and / or reducing the moisture permeability of the formed pattern. Furthermore, the substituent is preferably an alkyl group (e.g., a linear or branched alkyl group having 1 to 10 carbon atoms).

[0308] When compound β (preferably compound B) is a polymer, structure b0 (preferably structure b) may be a polymer bonded to the polymer main chain via a single bond or a linking group.

[0309] The polymerized compound β (preferably compound B) is obtained, for example, by polymerizing a monomer having a heteroaromatic ring (specifically, a (meth)acrylate monomer having a vinyl heteroaromatic ring and / or structure b0 (preferably structure b, more preferably a heteroaromatic ring)). It may be copolymerized with other monomers as needed.

[0310] From the viewpoint of further improving the pattern forming ability and / or lowering the moisture permeability of the formed pattern, the molar absorption coefficient (molar absorption coefficient ε) of compound β (preferably compound B) for light of a wavelength of 365 nm is, for example, 1×10 3 (cm·mol / L) -1 Below, preferably 1×10 3 (cm·mol / L) -1 less than 5×10 2 (cm·mol / L) -1 , more preferably 1×10 2 (cm·mol / L) -1 The lower limit of the molar absorption coefficient ε is not particularly limited, for example, it is greater than 0 (cm·mol / L) -1 .

[0311] When a photosensitive layer formed using a photosensitive material is exposed through a temporary support (preferably a PET film), the advantage of compound β (preferably compound B) having a molar absorption coefficient ε within the above range is particularly advantageous. Specifically, because the molar absorption coefficient ε is moderately low, even when exposure is performed through a temporary support, the generation of bubbles due to decarboxylation can be suppressed, thereby preventing degradation of the pattern shape.

[0312] Furthermore, when the photosensitive material of the present invention is used for the production of a permanent film, coloring of the film can be suppressed by setting the molar absorption coefficient ε of compound β (preferably compound B) within the above range.

[0313] As the compound having such a molar absorption coefficient ε, the above-mentioned monocyclic aromatic compound or the aromatic compound having two rings condensed to form an aromatic ring is preferred, and pyridine or a pyridine derivative, quinoline or a quinoline derivative, or isoquinoline or an isoquinoline derivative is preferred.

[0314] Furthermore, from the perspective of achieving superior pattern forming ability and / or lowering the moisture permeability of the formed pattern, the ratio of the molar absorptivity of compound β (preferably compound B) at 365 nm (molar absorptivity ε) to the molar absorptivity of compound β (preferably compound B) at 313 nm (molar absorptivity ε') (i.e., the ratio represented by molar absorptivity ε / molar absorptivity ε') is preferably 3 or less, more preferably 2 or less, and even more preferably less than 1. The lower limit is not particularly limited, but is, for example, 0.01 or more.

[0315] The molar absorptivity of compound β (preferably compound B) for light at a wavelength of 365 nm (molar absorptivity ε) and the molar absorptivity of compound β (preferably compound B) for light at a wavelength of 313 nm (molar absorptivity ε') are molar absorptivity coefficients measured by dissolving compound β (preferably compound B) in acetonitrile. If compound β (preferably compound B) is not soluble in acetonitrile, the solvent in which compound β (preferably compound B) is dissolved can be appropriately changed.

[0316] Specific examples of compound β (preferably compound B) include 5,6,7,8-tetrahydroquinoline, 4-acetylpyridine, 4-benzoylpyridine, 1-phenylisoquinoline, 1-n-butylisoquinoline, 1-n-butyl-4-methylisoquinoline, 1-methylisoquinoline, 2,4,5,7-tetramethylquinoline, 2-methyl-4-methoxyquinoline, 2,4-dimethylquinoline, phenanthidine, 9-methylacridine, 9-phenylacridine, pyridine, isoquinoline, quinoline, acridine, 4-aminopyridine, and 2-chloropyridine.

[0317] As the lower limit of the pKa of compound β (preferably compound B) in the ground state, it is preferably 0.5 or more, and from the viewpoint that the pattern forming ability is more excellent and / or the moisture permeability of the formed pattern becomes lower, it is more preferably 2.0 or more. Furthermore, as the upper limit of the pKa of compound β (preferably compound B) in the ground state, it is preferably 10.0 or less, and from the viewpoint that the pattern forming ability is more excellent and / or the moisture permeability of the formed pattern becomes lower, it is more preferably 9.0 or less. From the viewpoint that the pattern forming ability is more excellent and / or the moisture permeability of the formed pattern becomes lower, the upper limit of the pKa of compound β (preferably compound B) in the ground state is smaller, the more preferably, further preferably 8.0 or less, and particularly preferably 7.0 or less. In addition, the pKa of compound β (preferably compound B) in the ground state represents the pKa of compound β (preferably compound B) in an unexcited state, which can be obtained by acid titration. When compound β (preferably compound B) is a nitrogen-containing aromatic compound, the pKa of compound β (preferably compound B) in the ground state represents the pKa of the conjugated acid of compound β (preferably compound B) in the ground state.

[0318] Furthermore, when forming a photosensitive layer by coating the photosensitive material of the present invention, the molecular weight of compound β (preferably compound B) is preferably 120 or greater, more preferably 130 or greater, and even more preferably 180 or greater, from the viewpoint of being less likely to volatilize during the coating process and achieving a better residual rate in the photosensitive layer (furthermore, from the viewpoint of better pattern forming ability and / or lower moisture permeability of the formed pattern). The upper limit of the molecular weight of compound β (preferably compound B) is not particularly limited, but is, for example, 50,000 or less.

[0319] Furthermore, when compound β (preferably compound B) is a compound exhibiting a cationic state (e.g., a nitrogen-containing aromatic compound), the energy level of the HOMO (highest occupied molecular orbital) of compound β (preferably compound B) in the cationic state is preferably -8.5 eV or less. From the perspective of achieving superior pattern forming ability and / or lowering the moisture permeability of the formed pattern, it is more preferably -7.8 eV or less. The lower limit is not particularly limited, but is more preferably -13.6 eV or greater.

[0320] In the present specification, the energy level of the HOMO of compound β (preferably compound B) in the cationic state (HOMO in the first electronic excited state) is calculated by the quantum chemical calculation program Gaussian09 (Gaussian n09, Revision A.02, MJ Frisch, GW Trucks, HB Schlegel, GE Cuseri a, MA Robb, JR Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G.A Petersson, H. Nakatsuji, M. Caricato, X. Li, HP Hratchian, AF Izmaylov, J. Bloino, G. Zheng, JL Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fuk uda,J.Hasegawa,M.Ishida,T.Nakajima,Y.Honda,O.Kitao,H.Nakai,T.Vreven,JAMontgomery,Jr.,JEPeralta,F.Ogliaro,M.Bearpark,J JHeyd,E.Brothers,KNKudin,VNStaroverov,R.Kobayashi,J.Normand,K.Raghavachari,A.Rendell,JCBurant,SSIyengar,J.Tomasi,M.Cos si,N.Rega,JMMillam,M.Klene,JEKnox,JBCross,V.Bakken,C.Ad amo,J.Jaramillo,R.Gomperts,REStratmann,O.Yazyev,AJAustin,R.Cammi,C.Pomelli,JWOchterski,RLMartin,K.Morokuma,VGZakrzew ski, GAVoth, P. Salvador, JJ Dannenberg, S. Dapprich, AD Daniels, O. Farkas, JB Foresman, JVOrtiz, J. Cioslowski, and D.J. Fox, Gaussia n, Inc., Wallingford CT, 2009.) to calculate.

[0321] The calculation method employed a time-dependent density functional method using B3LYP for the functional and 6-31+G(d,p) for the basis function. Furthermore, to enhance solvent effects, the PCM method was used using parameters set for chloroform in Gaussian09. This method was used to perform structural optimization calculations of the first electronic excited state to determine the structure with the lowest energy, and the energy of the HOMO in this structure was calculated.

[0322] The following shows a representative example of compound β (preferably compound B) with respect to its cation state HOMO energy level (eV) and molecular weight.

[0323] [Table 1]

[0324] Table 1

[0325]

[0326] From the viewpoint of achieving more excellent effects of the present invention, the content of compound β (preferably compound B) in the photosensitive material of the present invention is preferably 0.1 to 50% by mass based on the total solid content of the photosensitive material.

[0327] In the photosensitive material of embodiment 1, the content of compound β (preferably compound B) is, for example, 0.2 to 45 mass %, preferably 2.0 to 40 mass %, more preferably 4 to 35 mass %, and further preferably 8 to 30 mass % relative to the total solid content of the photosensitive material.

[0328] In the photosensitive material of embodiment 2, the content of compound β (preferably compound B) is preferably 0.5 to 20% by mass, more preferably 1.0 to 10% by mass, based on the total solid content of the photosensitive material.

[0329] In the photosensitive material of embodiment 3, the content of compound β (preferably compound B) is preferably 0.3 to 20% by mass, more preferably 0.5 to 8% by mass, based on the total solid content of the photosensitive material.

[0330] The compound β (preferably compound B) may be used alone or in combination of two or more.

[0331] Furthermore, the preferred range of the total content of compound β (preferably compound B) and repeating units having structure b0 (preferably structure b) in polymer A is also the same as the preferred range of the content of compound β (preferably compound B) described above.

[0332] From the viewpoint of achieving a more excellent effect of the present invention, in the photosensitive material, the total number of structures b0 (preferably structure b) possessed by compound β (preferably compound B) is preferably 1 mol% or more, more preferably 3 mol% or more, further preferably 5 mol% or more, particularly preferably 10 mol% or more, and most preferably 20 mol% or more, relative to the total number of carboxyl groups possessed by polymer A.

[0333] There is no particular upper limit on the total number of structures b0 (preferably structure b) possessed by compound β (preferably compound B), but from the perspective of the film quality of the obtained film, the total number of carboxyl groups possessed by polymer A is preferably 200 mol% or less, more preferably 100 mol% or less, and further preferably 80 mol% or less.

[0334] When the photosensitive material contains a compound having a carboxyl group in addition to the polymer A, the total number of structures b0 (preferably structure b) possessed by compound β (preferably compound B) is preferably within the above range relative to the total number of all carboxyl groups in the photosensitive material.

[0335] Furthermore, the preferred range of the total number obtained by adding the total number of structures b0 (preferably structure b) possessed by compound β (preferably compound B) and the total number of structures b0 (preferably structure b) that polymer A can possess is also the same as the above-mentioned range as the preferred range of the total number of structures b0 (structure b possessed by compound B) possessed by compound β.

[0336] <Polymerizable compounds>

[0337] The photosensitive material of the present invention also preferably contains a polymerizable compound.

[0338] However, the photosensitive materials of Embodiments 2 and 3 contain a polymerizable compound as an essential component.

[0339] The polymerizable compound is preferably a component different from the polymer A. For example, it is preferably a compound having a molecular weight (weight average molecular weight when there is a molecular weight distribution) of less than 5000, and is also preferably a polymerizable monomer.

[0340] The polymerizable compound is a polymerizable compound having one or more (for example, 1 to 15) ethylenically unsaturated groups in one molecule.

[0341] The polymerizable compound preferably contains a polymerizable compound having two or more functional groups.

[0342] Here, the term "bifunctional or higher functional polymerizable compound" refers to a polymerizable compound having two or more (eg, 2 to 15) ethylenically unsaturated groups in one molecule.

[0343] Examples of the ethylenically unsaturated group include a (meth)acryloyl group, a vinyl group, and a styryl group, and a (meth)acryloyl group is preferred.

[0344] As the polymerizable compound, (meth)acrylate is preferred.

[0345] The photosensitive material preferably contains a bifunctional polymerizable compound (preferably a bifunctional (meth)acrylate) and a trifunctional or higher functional polymerizable compound (preferably a trifunctional or higher functional (meth)acrylate).

[0346] The bifunctional polymerizable compound is not particularly limited and can be appropriately selected from known compounds.

[0347] Examples of the bifunctional polymerizable compound include tricyclodecane dimethanol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate.

[0348] More specifically, as bifunctional polymerizable compounds, for example, tricyclodecane dimethanol diacrylate (manufactured by A-DCP Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (manufactured by DCP Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (manufactured by A-NOD-NShin-Nakamura Chemical Co., Ltd.), and 1,6-hexanediol diacrylate (manufactured by A-HD-NShin-Nakamura Chemical Co., Ltd.) can be cited.

[0349] The trifunctional or higher-functional polymerizable compound is not particularly limited and can be appropriately selected from known compounds.

[0350] Examples of trifunctional or higher-functional polymerizable compounds include dipentaerythritol (tri / tetra / penta / hexa) (meth)acrylate, pentaerythritol (tri / tetra) (meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerol tri(meth)acrylate skeleton.

[0351] Here, “(tri / tetra / penta / hexa) (meth)acrylate” is a concept including tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate and hexa(meth)acrylate, and “(tri / tetra) (meth)acrylate” is a concept including tri(meth)acrylate and tetra(meth)acrylate.

[0352] In addition, examples of polymerizable compounds include caprolactone-modified compounds of (meth)acrylate compounds (such as KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd. and A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd.), alkylene oxide-modified compounds of (meth)acrylate compounds (such as KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd. and ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd. and EBECRYL (registered trademark) 135 manufactured by DAICEL-ALLNEX LTD.), and ethoxylated triacrylates (such as A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0353] Examples of polymerizable compounds include urethane (meth)acrylates (preferably trifunctional or higher urethane (meth)acrylates). The lower limit of the number of functional groups is more preferably 6 or higher, and even more preferably 8 or higher. The upper limit of the number of functional groups can be, for example, 20 or lower.

[0354] Examples of trifunctional or higher-functional urethane (meth)acrylates include 8UX-015A (manufactured by TAISEIFINE CHEMICAL CO., LTD.); UA-32P, U-15HA, UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.); AH-600 (manufactured by KYOEISHA CHEMICAL Co., LTD.); UA-306H, UA-306T, UA-306I, UA-510H, UX-5000 (manufactured by Nippon Kayaku Co., Ltd.);

[0355] Furthermore, from the viewpoint of improving developability and improving perspiration resistance of the cured film, the polymerizable compound preferably contains a polymerizable monomer having an acid group.

[0356] Examples of the acid group include a phosphoric acid group, a sulfonic acid group, and a carboxyl group, and a carboxyl group is preferred.

[0357] Examples of the polymerizable compound having an acid group include tri- to tetra-functional polymerizable compounds having an acid group (compounds obtained by introducing a carboxyl group into the skeleton of pentaerythritol triacrylate and pentaerythritol tetraacrylate [PETA] (acid value = 80 to 120 mgKOH / g)) and penta- to hexa-functional polymerizable compounds having an acid group (compounds obtained by introducing a carboxyl group into the skeleton of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate [DPHA] (acid value = 25 to 70 mgKOH / g)).

[0358] These trifunctional or higher-functional polymerizable compounds having an acid group may be used in combination with a bifunctional polymerizable compound having an acid group, as needed.

[0359] The polymerizable compound having an acid group is preferably at least one selected from a polymerizable compound having two or more functional groups and a carboxyl group and a carboxylic anhydride thereof.

[0360] The bifunctional or higher-functional polymerizable compound having a carboxyl group is not particularly limited and can be appropriately selected from known compounds.

[0361] Examples of the bifunctional or higher-functional polymerizable compound having a carboxyl group include ARONIX (registered trademark) TO-2349 (manufactured by TOAGOSEI CO., LTD.), ARONIX M-520 (manufactured by TOAGOSEI CO., LTD.), and ARONIX M-510 (manufactured by TOAGOSEI CO., LTD.).

[0362] Examples of the polymerizable compound having an acid group include those described in paragraphs 0025 to 0030 of JP-A-2004-239942, the contents of which are incorporated herein by reference.

[0363] The weight average molecular weight (Mw) of the polymerizable compound that may be contained in the photosensitive material is preferably 200 to 3000, more preferably 250 to 2600, and even more preferably 280 to 2200.

[0364] When the photosensitive material contains a polymerizable compound, the molecular weight of the polymerizable compound with the smallest molecular weight among all the polymerizable compounds contained in the photosensitive material is preferably 250 or more, more preferably 280 or more.

[0365] When the photosensitive material of the present invention contains a polymerizable compound, the content thereof is preferably 3 to 70% by mass, more preferably 10 to 70% by mass, and particularly preferably 20 to 55% by mass relative to the total solid content of the photosensitive material.

[0366] When the photosensitive material of the present invention contains a polymerizable compound, the mass ratio of the polymerizable compound to the polymer A (mass of the polymerizable compound / mass of the polymer A) is preferably 0.2 to 2.0, and more preferably 0.4 to 0.9.

[0367] The polymerizable compound may be used alone or in combination of two or more.

[0368] Furthermore, when the photosensitive material of the present invention contains a bifunctional polymerizable compound and a trifunctional or higher polymerizable compound, the content of the bifunctional polymerizable compound is preferably 10 to 90% by mass, more preferably 20 to 85% by mass, and even more preferably 30 to 80% by mass relative to all the polymerizable compounds contained in the photosensitive material.

[0369] In this case, the content of the trifunctional or higher-functional polymerizable compound is preferably 10 to 90% by mass, more preferably 15 to 80% by mass, and even more preferably 20 to 70% by mass based on all polymerizable compounds contained in the photosensitive material.

[0370] Furthermore, when the photosensitive material of the present invention contains a difunctional or higher-functional polymerizable compound, the photosensitive material may further contain a monofunctional polymerizable compound.

[0371] When the photosensitive material of the present invention contains a difunctional or higher-functional polymerizable compound, it is preferred that the difunctional or higher-functional polymerizable compound be a main component among the polymerizable compounds contained in the photosensitive material.

[0372] Specifically, when the photosensitive material of the present invention contains a difunctional or higher-functional polymerizable compound, the content of the difunctional or higher-functional polymerizable compound is preferably 60 to 100 mass %, more preferably 80 to 100 mass %, and even more preferably 90 to 100 mass % relative to the total content of the polymerizable compounds contained in the photosensitive material.

[0373] Furthermore, when the photosensitive material of the present invention contains a polymerizable compound having an acid group (preferably a polymerizable compound having two or more functions and having a carboxyl group or its carboxylic anhydride), the content of the polymerizable compound having an acid group is preferably 1 to 50% by mass, more preferably 1 to 20% by mass, and further preferably 1 to 10% by mass relative to the total solid content of the photosensitive material.

[0374] <Photopolymerization initiator>

[0375] The photosensitive material of the present invention also preferably contains a photopolymerization initiator.

[0376] However, the photosensitive material of embodiment 3 contains a photopolymerization initiator as an essential component.

[0377] The photopolymerization initiator may be a photoradical polymerization initiator, a photocationic polymerization initiator, or a photoanionic polymerization initiator, but is preferably a photoradical polymerization initiator.

[0378] There are no particular limitations on the photopolymerization initiator, and a known photopolymerization initiator can be used.

[0379] The photopolymerization initiator is preferably one or more selected from an oxime ester compound (a photopolymerization initiator having an oxime ester structure) and an aminoacetophenone compound (a photopolymerization initiator having an aminoacetophenone structure), and more preferably a compound comprising both. When both compounds are included, the content of the oxime ester compound is preferably 5 to 90% by mass, more preferably 15 to 50% by mass, relative to the total content of the compounds. Other photopolymerization initiators may be used in combination, for example, hydroxyacetophenone compounds, acylphosphine oxide compounds, bistriphenylimidazole compounds, etc.

[0380] Furthermore, as the photopolymerization initiator, for example, polymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-095716 and paragraphs 0064 to 0081 of JP-A-2015-014783 can be used.

[0381] Specific examples of the photopolymerization initiator include the following photopolymerization initiators.

[0382] Examples of the oxime ester compound include 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (trade name: IRGACURE OXE-01, IRGACURE series are manufactured by BASF), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF), [8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazole][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone-(O-acetyloxime) (trade name: IRGACURE OXE-03, manufactured by BASF), 1-[4-[4-(2-benzofuranylcarbonyl)phenyl]thio]phenyl]-4-methylpentanone-1-(O-acetoxime) (trade name: IRGACURE OXE-04, manufactured by BASF), trade name: Lunar6, DKSH Japan KK), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyl oxime) (trade name: TR-PBG-305, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyl oxime) (trade name: TR-PBG-326, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyl oxime) (trade name: TR-PBG-391, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.).

[0383] Examples of the aminoacetophenone compound include 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, Omnirad series products are manufactured by IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907), and APi-307 (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, manufactured by Shenzhen UV-ChemTech Ltd.).

[0384] Examples of other photopolymerization initiators include 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propane-1-one (trade name: Omnirad 127), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (trade name: Omnirad 369), 2-hydroxy-2-methyl-1-phenyl-propane-1-one (trade name: Omnirad 1173), 1-hydroxy-cyclohexyl-phenyl ketone (trade name: Omnirad 184), 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: Omnirad 651), and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO). H) and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad819).

[0385] When the photosensitive material of the present invention contains a photopolymerization initiator, the content thereof is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, and particularly preferably 1 to 5% by mass relative to the total solid content of the photosensitive material.

[0386] The photopolymerization initiator may be used alone or in combination of two or more.

[0387] Surfactants

[0388] The photosensitive material of the present invention may contain a surfactant.

[0389] Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants, and nonionic surfactants are preferred.

[0390] Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based surfactants, and fluorine-based surfactants.

[0391] As the surfactant, for example, the surfactants described in paragraphs 0120 to 0125 of International Publication No. 2018 / 179640 can also be used.

[0392] Furthermore, as the surfactant, surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Patent Application Laid-Open No. 2009-237362 can also be used.

[0393] Examples of commercially available fluorochemical surfactants include 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-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-562, F-563, F-564, F-565, F-566, F-567, F-568, F-569, F-570, F-571, F-572, F-573, F-574, F-575, F-576, F-577, F-578, F-579, F-580, F-581, F-582, F-583, F-584, F-585, F-586, F-587, F-588, F-589, F-590, F-591, F-592, F-593, F-594, F-595, F-596, F-597, F-598, F-599, F-591, F-597, F-598, F-599, F-591, F-599, F-591, F-591, F-592, F-593, F-594, F-595, F-596, F-597, F-598, F-599, F-599, F-591, F-599, F-591, -565, 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 (all DIC Corporation), Fluorad FC 430, FC431, FC171 (all manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC Inc.), Poly Fox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA Solutions Inc.), FTERGENT710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (all manufactured by ENEOS Corporation), etc.

[0394] Furthermore, acrylic compounds can also be preferably used as fluorochemical surfactants. These acrylic compounds have a molecular structure with a functional group containing a fluorine atom, and when heat is applied, the functional group containing a fluorine atom is partially cleaved, causing the fluorine atom to volatilize. Examples of such fluorochemical surfactants include the MEGAFACE DS series manufactured by DIC Corporation (Chemical Industry Daily (February 22, 2016), Nikkei Industry News (February 23, 2016)), such as MEGAFACE DS-21.

[0395] Furthermore, as the fluorine-based surfactant, a polymer of a fluorine-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound is also preferably used.

[0396] Furthermore, block polymers can also be used as fluorine-based surfactants.

[0397] Furthermore, as the fluorine-based surfactant, a fluorine-containing polymer compound comprising a structural unit derived from a (meth)acrylate compound having a fluorine atom and a structural unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy and propyleneoxy) can also be preferably used.

[0398] Furthermore, as fluorine-based surfactants, fluorine-containing polymers having a group containing an ethylenically unsaturated bond in a side chain can also be used, such as MEGAFACE RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0399] From the viewpoint of improving environmental compatibility, the fluorine-based surfactant is preferably a surfactant derived from an alternative material to compounds having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS).

[0400] Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, Pluronic L10, L31, L61, L62, 10R5, 17R2, and 25R2 (all manufactured by BASF), Tetronic 304, 701, 704, 901, 904, and 150R1 (all manufactured by BASF), Solsperse 20000 (all manufactured by Japan Lubrizol Corporation), NCW-101, NCW-1001, and NCW-1002 (all manufactured by FUJIFILM Wako), and Tetronic 304, 701, 704, 901, 904, and 150R1. Pure Chemical Corporation), PIONIND-6112, D-6112-W, D-6315 (all manufactured by Takemoto Oil & Fat Co., Ltd.), OLFINE 1010, Surfynol 104, 400, 440 (all manufactured by Nissin Chemical Co., Ltd.), and the like.

[0401] Examples of the silicone surfactant include linear polymers composed of siloxane bonds and modified silicone polymers in which an organic group is introduced into a side chain or a terminal.

[0402] Specific examples of surfactants include DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.) and X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (all manufactured by Shin-Etsu Chemical Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials Inc.), BYK307, BYK323, BYK330 (all manufactured by BYK Chemie GmbH), etc.

[0403] The content of the surfactant is preferably 0.0001 to 10% by mass, more preferably 0.001 to 5% by mass, and even more preferably 0.005 to 3% by mass, relative to the total solid content of the photosensitive material.

[0404] The surfactant may be used alone or in combination of two or more.

[0405] Solvents

[0406] From the viewpoint of forming a photosensitive layer by coating, the photosensitive material of the present invention may contain a solvent.

[0407] As the solvent, any commonly used solvent can be used without particular limitation.

[0408] As the solvent, an organic solvent is preferred.

[0409] Examples of the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam, n-propanol, 2-propanol, and mixed solvents thereof.

[0410] The solvent is preferably a mixed solvent of methyl ethyl ketone and propylene glycol monomethyl ether acetate, a mixed solvent of diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate, or a mixed solvent of methyl ethyl ketone, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate.

[0411] When the photosensitive material of the present invention contains a solvent, the solid content of the photosensitive material is preferably 5 to 80% by mass, more preferably 8 to 40% by mass, and even more preferably 10 to 30% by mass. In other words, when the photosensitive material of the present invention contains a solvent, the content of the solvent is preferably 20 to 95% by mass, more preferably 60 to 95% by mass, and even more preferably 70 to 95% by mass relative to the total mass of the photosensitive material.

[0412] When the photosensitive material of the present invention contains a solvent, the viscosity (25° C.) of the photosensitive material is preferably 1 to 50 mPa·s, more preferably 2 to 40 mPa·s, and even more preferably 3 to 30 mPa·s from the viewpoint of coating properties.

[0413] The viscosity is measured using, for example, VISCOMETER TV-22 (manufactured by TOKI SANGYO CO. LTD.).

[0414] When the photosensitive material of the present invention contains a solvent, the surface tension (25° C.) of the photosensitive material is preferably 5 to 100 mN / m, more preferably 10 to 80 mN / m, and even more preferably 15 to 40 mN / m from the viewpoint of coating properties.

[0415] The surface tension is measured using, for example, Automatic Surface Tensiometer CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.).

[0416] As the solvent, Solvent described in paragraphs 0054 and 0055 of US Patent Application Publication No. 2005 / 282073 can also be used, and the contents of this specification are incorporated herein.

[0417] Furthermore, as the solvent, an organic solvent (high boiling point solvent) having a boiling point of 180 to 250° C. can be used as needed.

[0418] Furthermore, when the photosensitive material of the present invention is used to form a photosensitive layer (a photosensitive layer formed using a photosensitive material) in a transfer film or the like described later, it is also preferred that the photosensitive layer contain substantially no solvent. "Substantially no solvent" means that the content of the solvent is less than 1% by mass relative to the total mass of the photosensitive material (photosensitive layer), preferably 0 to 0.5% by mass, and more preferably 0 to 0.001% by mass.

[0419] <Other ingredients>

[0420] The photosensitive material of the present invention may contain other components in addition to the above-mentioned components.

[0421] As other components, for example, known additives such as the metal oxidation inhibitors described later, metal oxide particles, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, colorants, thermal free radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic precipitation inhibitors may be further included.

[0422] Preferred embodiments of these components are described in paragraphs 0165 to 0184 of Japanese Patent Application Laid-Open No. 2014-085643, the contents of which are incorporated herein by reference.

[0423] The photosensitive material may contain impurities.

[0424] Examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Among these, halide ions, sodium ions, and potassium ions are particularly preferably contained in the following amounts because they are easily incorporated as impurities.

[0425] The content of impurities in the photosensitive material is preferably 80 mass ppm or less, more preferably 10 mass ppm or less, and even more preferably 2 mass ppm or less relative to the total mass of the photosensitive material. The content of impurities in the photosensitive material can be set to 1 mass ppb or more, or can be set to 0.1 mass ppm or more relative to the total mass of the photosensitive material.

[0426] Examples of methods for keeping the impurity content within the above range include selecting a raw material with a low impurity content as the raw material for the photosensitive material, preventing the incorporation of impurities during the formation of the photosensitive material, and cleaning and removing impurities. These methods can keep the impurity content within the above range.

[0427] For example, impurities can be quantified using known methods such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, and ion chromatography.

[0428] The photosensitive material preferably contains a low content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane. The content of each of these compounds in the photosensitive material is preferably 100 ppm by mass or less, more preferably 20 ppm by mass or less, and even more preferably 4 ppm by mass or less, relative to the total mass of the photosensitive material.

[0429] The lower limit of the above content can be set to 10 ppb by mass or greater, or 100 ppb by mass or greater, relative to the total mass of the photosensitive material. The content of these compounds can be suppressed using the same methods as for the above-mentioned metal impurities. Furthermore, they can be quantified using known measurement methods.

[0430] From the viewpoint of improving patterning properties, the content of water in the photosensitive material is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass, relative to the total mass of the photosensitive material.

[0431] [Transfer film]

[0432] The transfer film of the present invention includes a temporary support and a photosensitive layer (hereinafter also simply referred to as "photosensitive layer") formed using the photosensitive material of the present invention.

[0433] The transfer film of the present invention can be preferably used to form a film (pattern) on a substrate. When forming a film on a substrate using the transfer film of the present invention, for example, the photosensitive layer of the transfer film of the present invention is transferred to the substrate on which the film (pattern) is to be formed, and the photosensitive layer transferred to the substrate is subjected to exposure and development, thereby forming the film (pattern) on the substrate.

[0434] The transfer film of the present invention can achieve the same effects as those achieved by the photosensitive material of the present invention, that is, a film having a reduced relative dielectric constant can be formed on a substrate.

[0435] Therefore, the transfer film of the present invention is particularly suitable for use as a film in forming a protective film for a touch panel.

[0436] Hereinafter, the transfer film of the present invention will be described in detail.

[0437] Figure 1 It is a schematic cross-sectional view showing an example of an embodiment of the transfer film of the present invention.

[0438] Figure 1 The transfer film 100 shown in FIG. 1 has a structure in which a temporary support 12 , a photosensitive layer (a layer having photosensitivity formed using the photosensitive material of the present invention) 14 , and a cover film 16 are stacked in this order.

[0439] The cover film 16 may be omitted.

[0440] Temporary support

[0441] The temporary support is a support that supports the photosensitive layer and can be peeled from the photosensitive layer.

[0442] From the viewpoint of being able to expose the photosensitive layer via the temporary support when pattern-exposing the photosensitive layer, the temporary support preferably has light transparency.

[0443] Here, "having light transparency" means that the transmittance at the dominant wavelength of the light used for exposure (which may be pattern exposure or full-surface exposure) is 50% or higher. To achieve even better exposure sensitivity, the transmittance at the dominant wavelength of the light used for exposure is preferably 60% or higher, and more preferably 70% or higher. Transmittance can be measured using the MCPD Series manufactured by Otsuka Electronics Co., Ltd.

[0444] Specific examples of the temporary support include glass substrates, resin films, and paper. Resin films are preferred due to their superior strength and flexibility. Examples of the resin film include polyethylene terephthalate (PET) films, cellulose triacetate films, polystyrene films, and polycarbonate films. Among these, biaxially stretched polyethylene terephthalate films are particularly preferred.

[0445] From the perspective of pattern formation during pattern exposure through a temporary support and the transparency of the temporary support, it is preferred that the number of particles, foreign matter, and defects contained in the temporary support is small. The number of microparticles, foreign matter, and defects with a diameter of 2 μm or more is preferably 50 / 10 mm. 2 Less than 10 pieces / 10mm, more preferably 10 pieces / 10mm 2 Below, more preferably 3 / 10mm 2 There is no particular lower limit, but it can be set to 1 / 10mm. 2 above.

[0446] From the viewpoint of further improving the workability, it is preferred that particles having a diameter of 0.5 to 5 μm be present at a density of 1 particle / mm on the surface of the temporary support opposite to the side on which the photosensitive layer is formed. 2 More preferably, there are 1 to 50 layers / mm 2 .

[0447] The thickness of the temporary support is not particularly limited from the viewpoint of easy handling and excellent versatility, but is preferably 5 to 200 μm, more preferably 10 to 150 μm.

[0448] The thickness of the temporary support can be appropriately selected depending on the material from the viewpoints of strength as a support, flexibility required for lamination with a circuit wiring forming substrate, and light transmittance required in the initial exposure step.

[0449] Preferred forms of temporary supports are described, for example, in paragraphs 0017 to 0018 of Japanese Patent Application Publication No. 2014-085643, paragraphs 0019 to 0026 of Japanese Patent Application Publication No. 2016-027363, paragraphs 0041 to 0057 of WO2012 / 081680A1, and paragraphs 0029 to 0040 of WO2018 / 179370A1, and the contents of these publications are incorporated into this specification.

[0450] As the temporary support, for example, Cosmo Shine (registered trademark) A4100 manufactured by TOYOBO CO., LTD., Lumirror (registered trademark) 16FB40 manufactured by Toray Industries, Inc., or Lumirror (registered trademark) 16QS62 (16KS40) manufactured by Toray Industries, Inc. can be used.

[0451] Particularly preferred embodiments of the temporary support include a biaxially stretched polyethylene terephthalate film having a thickness of 16 μm, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, and a biaxially stretched polyethylene terephthalate film having a thickness of 9 μm.

[0452] <Photosensitive layer>

[0453] The photosensitive layer in the transfer film is formed using the photosensitive material of the present invention. For example, the photosensitive layer is preferably a layer consisting essentially only of the solid components of the photosensitive material. In other words, the photosensitive material constituting the photosensitive layer preferably contains the solid components (excluding the solvent) that can be contained in the photosensitive material at the above-mentioned content.

[0454] However, when the photosensitive layer is formed by applying and drying a photosensitive material containing a solvent, the photosensitive layer may contain a solvent because the solvent remains in the photosensitive layer even after drying.

[0455] The photosensitive layer contains polymer A and has a mechanism whereby the content of carboxyl groups derived from polymer A is reduced by exposure.

[0456] The content of carboxyl groups in the photosensitive layer is preferably reduced by a rate of 5 mol% or more, more preferably by a rate of 10 mol% or more, further preferably by a rate of 20 mol% or more, even more preferably by a rate of 31 mol% or more, particularly preferably by a rate of 40 mol% or more, even more preferably by a rate of 51 mol% or more, and most preferably by a rate of 71 mol% or more, due to irradiation of the photosensitive layer with actinic rays or radiation relative to the content of carboxyl groups in the photosensitive layer before irradiation. In addition, the upper limit is not particularly limited, and is, for example, 100 mol% or less.

[0457] Furthermore, the rate of reduction in the content of carboxyl groups derived from polymer A in the photosensitive layer can be calculated by measuring the amount of carboxyl groups in the photosensitive layer before and after exposure. When measuring the amount of carboxyl groups in the photosensitive layer before exposure, for example, analysis and quantification can be performed by potentiometric titration. Furthermore, when measuring the amount of carboxyl groups in the photosensitive layer after exposure, the hydrogen atoms of the carboxyl groups can be replaced with metal ions such as lithium, and the amount of the metal ions can be calculated by analysis and quantification using ICP-OES (Inductively coupled plasma optical emission spectrometer).

[0458] Furthermore, the reduction rate of the carboxyl group content of the polymer A in the photosensitive layer can be obtained by measuring the IR (infrared) spectrum of the photosensitive layer before and after exposure and calculating the reduction rate of the peak derived from the carboxyl group. The reduction rate of the carboxyl group content can also be obtained by calculating the peak of the C=O stretching of the carboxyl group (1710 cm -1 The peak value is obtained by the reduction rate of the peak value.

[0459] (Average thickness of photosensitive layer)

[0460] The average thickness of the photosensitive layer is preferably 0.5 to 20 μm. When the average thickness of the photosensitive layer is 20 μm or less, the pattern resolution is further improved. When the average thickness of the photosensitive layer is 0.5 μm or greater, it is preferred from the perspective of pattern linearity. The average thickness of the photosensitive layer is more preferably 0.8 to 15 μm, and even more preferably 1.0 to 10 μm. Specific examples of the average thickness of the photosensitive layer include 3.0 μm, 5.0 μm, and 8.0 μm.

[0461] (Method for Forming Photosensitive Layer)

[0462] For example, a photosensitive material containing the above-mentioned solid components (excluding the solvent) and a solvent can be prepared, and the photosensitive layer can be formed by coating and drying. Alternatively, the components can be dissolved in a solvent to prepare a solution, and the resulting solutions can be mixed in a predetermined ratio to prepare the photosensitive material. The photosensitive material containing a solvent prepared in the above manner is preferably filtered using a filter having a pore size of 0.2 to 30 μm, for example.

[0463] The photosensitive layer can be formed by applying a photosensitive material containing a solvent onto a temporary support or a cover film and drying the coated material.

[0464] The coating method is not particularly limited, and examples thereof include known methods such as slit coating, spin coating, curtain coating, and inkjet coating.

[0465] Furthermore, when a high refractive index layer and / or other layers described later are formed on a temporary support or a cover film, a photosensitive layer may be formed on the high refractive index layer and / or other layers.

[0466] From the perspective of achieving superior pattern forming capability and / or lower moisture permeability of the formed pattern, the transmittance of the photosensitive layer at 365 nm (transmittance of light with a wavelength of 365 nm) is preferably 20% or greater, more preferably 65% ​​or greater, and even more preferably 90% or greater. The upper limit, while not particularly limited, is 100% or less.

[0467] Furthermore, from the perspective of achieving a more excellent pattern forming ability and / or lowering the moisture permeability of the formed pattern, the ratio of the transmittance of the photosensitive layer at 365 nm (transmittance of light with a wavelength of 365 nm) to the transmittance of the photosensitive layer at 313 nm (transmittance of light with a wavelength of 313 nm) (ratio represented by transmittance of the photosensitive layer at 365 nm / transmittance of the photosensitive layer at 313 nm) is preferably 1 or more, more preferably 1.5 or more. The upper limit is not particularly limited, but is, for example, 1000 or less.

[0468] As such a photosensitive layer, a photosensitive layer formed using a photosensitive material that satisfies at least one of the above-mentioned requirements (V) and (W) is more preferable.

[0469] Furthermore, among these, the photosensitive layer is more preferably formed using a photosensitive material that satisfies any one of the above-mentioned aspects 1 to 3.

[0470] The visible light transmittance of the photosensitive layer per 1.0 μm of film thickness is preferably 80% or more, more preferably 90% or more, and most preferably 95% or more.

[0471] As for the visible light transmittance, it is preferable that the average transmittance at a wavelength of 400 to 800 nm, the minimum value of the transmittance at a wavelength of 400 to 800 nm, and the transmittance at a wavelength of 400 nm all satisfy the above conditions.

[0472] Preferred values ​​of the visible light transmittance per 1.0 μm of the film thickness of the photosensitive layer include 87%, 92%, and 98%.

[0473] From the perspective of suppressing residue during development, the dissolution rate of the photosensitive layer in a 1.0 mass% aqueous solution of sodium carbonate is preferably 0.01 μm / second or higher, more preferably 0.10 μm / second or higher, and even more preferably 0.20 μm / second or higher. Furthermore, from the perspective of the edge shape of the pattern, it is preferably 5.0 μm / second or lower. Specific preferred values ​​include, for example, 1.8 μm / second, 1.0 μm / second, and 0.7 μm / second.

[0474] The dissolution rate per unit time of the photosensitive layer in a 1.0 mass % sodium carbonate aqueous solution was measured as follows.

[0475] The photosensitive layer (with a thickness of 1.0 to 10 μm) formed on the glass substrate from which the solvent was sufficiently removed was shower-developed at 25° C. using a 1.0 mass % sodium carbonate aqueous solution until the photosensitive layer was completely dissolved (for a maximum of 2 minutes).

[0476] The dissolution rate was calculated by dividing the thickness of the photosensitive layer by the time required for the photosensitive layer to completely dissolve. If the film was not completely dissolved within 2 minutes, the dissolution rate was calculated in the same manner based on the change in film thickness up to that time.

[0477] During development, a 1 / 4 MINJJX030PP shower nozzle manufactured by H. IKEUCHI & CO., LTD. was used, and the spray pressure was set to 0.08 MPa. Under the above conditions, the shower flow rate per unit time was set to 1,800 mL / min.

[0478] From the viewpoint of pattern formation, the number of foreign particles having a diameter of 1.0 μm or more in the photosensitive layer is preferably 10 pieces / mm. 2 Below, more preferably 5 / mm 2 the following.

[0479] The amount of foreign matter was measured in the following manner.

[0480] Five random areas (1 mm x 1 mm) on the surface of the photosensitive layer were visually observed using an optical microscope from the normal direction of the surface of the photosensitive layer. The number of foreign matter with a diameter of 1.0 μm or greater in each area was measured and the arithmetic average was calculated.

[0481] As a specific preferred numerical value, for example, 0 pieces / mm can be cited. 2 , 1 piece / mm 2 , 4 pieces / mm 2 , 8 pieces / mm 2 wait.

[0482] From the viewpoint of suppressing the generation of aggregates during development, 1.0 cm2 of sodium carbonate was dissolved in 1.0 liter of a 30°C aqueous solution of 1.0 mass % sodium carbonate. 3 The haze of the solution obtained by coating the photosensitive layer is preferably 60% or less, more preferably 30% or less, further preferably 10% or less, and most preferably 1% or less.

[0483] The haze is measured in the following manner.

[0484] First, a 1.0 mass % sodium carbonate aqueous solution was prepared and the liquid temperature was adjusted to 30° C. 1.0 cm 3 The photosensitive layer was stirred at 30°C for 4 hours while avoiding the incorporation of bubbles. After stirring, the haze of the solution containing the photosensitive resin layer was measured. The haze was measured using a haze meter (product name "NDH4000", manufactured by NIPPON DENSHOKU INDUSTRIES Co., LTD) using a liquid measurement cell and a dedicated liquid measurement cell with an optical path length of 20 mm.

[0485] Specific preferred numerical values ​​include, for example, 0.4%, 1.0%, 9%, and 24%.

[0486] <High refractive index layer>

[0487] The transfer film preferably further includes a high refractive index layer.

[0488] The high refractive index layer is preferably disposed adjacent to the photosensitive layer, and is also preferably disposed on the side opposite to the temporary support when viewed from the photosensitive layer.

[0489] The high refractive index layer is not particularly limited except for a layer having a refractive index of 1.50 or higher at a wavelength of 550 nm.

[0490] The refractive index of the high refractive index layer is preferably 1.55 or higher, more preferably 1.60 or higher.

[0491] The upper limit of the refractive index of the high refractive index layer is not particularly limited, but is preferably 2.10 or less, more preferably 1.85 or less, further preferably 1.78 or less, and particularly preferably 1.74 or less.

[0492] Furthermore, the refractive index of the high refractive index layer is preferably higher than the refractive index of the photosensitive layer.

[0493] The high refractive index layer may be photocurable (ie, photosensitivity), thermosetting, or both.

[0494] The method in which the high refractive index layer is photosensitivity has the advantage that after transfer, the photosensitive layer and the high refractive index layer transferred onto the substrate can be patterned together by a single photolithography process.

[0495] The high refractive index layer preferably has alkali solubility (for example, solubility in a weakly alkaline aqueous solution).

[0496] Furthermore, the high refractive index layer is preferably a transparent layer.

[0497] The thickness of the high refractive index layer is preferably 500 nm or less, more preferably 110 nm or less, and even more preferably 100 nm or less.

[0498] Furthermore, the thickness of the high refractive index layer is preferably 20 nm or more, more preferably 55 nm or more, further preferably 60 nm or more, and particularly preferably 70 nm or more.

[0499] The high refractive index layer is sometimes sandwiched between a transparent electrode pattern (preferably an ITO pattern) and a photosensitive layer after transfer, thereby forming a laminate together with the transparent electrode pattern and the photosensitive layer. In this case, by reducing the refractive index difference between the transparent electrode pattern and the high refractive index layer, and the refractive index difference between the high refractive index layer and the photosensitive layer, light reflection is further reduced. As a result, the concealment of the transparent electrode pattern is further improved.

[0500] For example, when a transparent electrode pattern, a high refractive index layer, and a photosensitive layer are stacked in this order, the transparent electrode pattern is difficult to recognize when viewed from the transparent electrode pattern side.

[0501] The refractive index of the high refractive index layer is preferably adjusted according to the refractive index of the transparent electrode pattern.

[0502] For example, when the transparent electrode pattern has a refractive index in the range of 1.8 to 2.0, as in the case of using an oxide of In and Sn (ITO), the refractive index of the high refractive index layer is preferably 1.60 or higher. In this case, the upper limit of the refractive index of the high refractive index layer is not particularly limited, but is preferably 2.1 or lower, more preferably 1.85 or lower, further preferably 1.78 or lower, and particularly preferably 1.74 or lower.

[0503] For example, when the transparent electrode pattern has a refractive index exceeding 2.0 as in the case of forming the transparent electrode pattern using an oxide of In and Zn (IZO; Indium Zinc Oxide), the refractive index of the high refractive index layer is preferably 1.70 to 1.85.

[0504] The method for controlling the refractive index of the high refractive index layer is not particularly limited. Examples thereof include a method of using a resin having a predetermined refractive index alone, a method of using a resin and metal oxide particles or metal particles, and a method of using a composite of a metal salt and a resin.

[0505] There are no particular limitations on the types of metal oxide particles or metal particles, and known metal oxide particles or metal particles can be used. The metals in the metal oxide particles or metal particles also include semimetals such as B, Si, Ge, As, Sb, and Te.

[0506] For example, from the viewpoint of transparency, the average primary particle size of the particles (metal oxide particles or metal particles) is preferably 1 to 200 nm, more preferably 3 to 80 nm.

[0507] The average primary particle size of the particles was calculated by measuring the particle sizes of 200 random particles using an electron microscope and averaging the measurement results. If the particle shape was not spherical, the longest side was used as the particle size.

[0508] Specifically, the metal oxide particles are preferably at least one selected from zirconium oxide particles (ZrO 2 particles), Nb 2 O 5 particles, titanium oxide particles (TiO 2 particles), silicon dioxide particles (SiO 2 particles), and composite particles thereof.

[0509] Among these, the metal oxide particles are more preferably at least one selected from zirconium oxide particles and titanium oxide particles, for example, from the viewpoint of easily adjusting the refractive index of the high refractive index layer to 1.6 or more.

[0510] When the high refractive index layer contains metal oxide particles, the high refractive index layer may contain only one type of metal oxide particles, or may contain two or more types.

[0511] From the perspective of being able to improve the concealment of concealed objects such as electrode patterns and effectively improve the visibility of the concealed objects, the content of particles (metal oxide particles or metal particles) relative to the total mass of the high refractive index layer is preferably 1 to 95 mass %, more preferably 20 to 90 mass %, and further preferably 40 to 85 mass %.

[0512] When titanium oxide is used as the metal oxide particles, the content of the titanium oxide particles is preferably 1 to 95 mass %, more preferably 20 to 90 mass %, and even more preferably 40 to 85 mass % relative to the total mass of the high refractive index layer.

[0513] Examples of commercially available metal oxide particles include calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F04), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F74), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F75), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F76), zirconia particles (Nanouse OZ-S30M, manufactured by NISSAN Chemical Industries, Ltd.), and zirconia particles (Nanouse OZ-S30K, manufactured by NISSAN Chemical Industries, Ltd.).

[0514] The high refractive index layer preferably contains one or more selected from inorganic particles (metal oxide particles or metal particles, etc.) having a refractive index of 1.50 or more (more preferably 1.55 or more, further preferably 1.60 or more), a resin having a refractive index of 1.50 or more (more preferably 1.55 or more, further preferably 1.60 or more), and a polymerizable compound having a refractive index of 1.50 or more (more preferably 1.55 or more, further preferably 1.60 or more).

[0515] According to this embodiment, the refractive index of the high refractive index layer can be easily adjusted to 1.50 or higher (more preferably 1.55 or higher, particularly preferably 1.60 or higher).

[0516] Furthermore, the high refractive index layer preferably contains a binder polymer, a polymerizable monomer, and particles.

[0517] Regarding the components of the high refractive index layer, reference can be made to the components of the curable transparent resin layer described in paragraphs 0019 to 0040 and 0144 to 0150 of JP-A-2014-108541, the components of the transparent layer described in paragraphs 0024 to 0035 and 0110 to 0112 of JP-A-2014-010814, and the components of the composition containing an ammonium salt described in paragraphs 0034 to 0056 of WO 2016 / 009980.

[0518] Furthermore, the high refractive index layer also preferably contains a metal oxidation inhibitor.

[0519] The metal oxidation inhibitor is a compound (excluding compound β) that can perform surface treatment on a member in direct contact with the layer it contains (for example, a conductive member formed on a substrate).

[0520] When the high refractive index layer contains a metal oxidation inhibitor, when the high refractive index layer is transferred to a substrate (i.e., a transfer object), a member in direct contact with the high refractive index layer (e.g., a conductive member formed on the substrate) can be surface treated. This surface treatment imparts a metal oxidation inhibitory function (protective properties) to the member in direct contact with the high refractive index layer.

[0521] The metal oxidation inhibitor is preferably a compound having an aromatic ring containing a nitrogen atom. The compound having an aromatic ring containing a nitrogen atom may have a substituent.

[0522] The metal oxidation inhibitor is preferably a compound having a five-membered aromatic ring having a nitrogen atom as a ring member.

[0523] The aromatic ring containing a nitrogen atom is preferably an imidazole ring, a triazole ring, a tetrazole ring, a thiazole ring, a thiadiazole ring, or a condensed ring of any one of them with another aromatic ring, and more preferably an imidazole ring, a triazole ring, a tetrazole ring, or a condensed ring of any one of them with another aromatic ring.

[0524] The "other aromatic ring" forming the condensed ring may be a monocyclic ring or a heterocyclic ring, but is preferably a monocyclic ring, more preferably a benzene ring or a naphthalene ring, and even more preferably a benzene ring.

[0525] As the metal oxidation inhibitor, imidazole, benzimidazole, tetrazole, 5-amino-1H-tetrazole, hydroxythiadiazole or benzotriazole is preferred, and imidazole, benzimidazole, 5-amino-1H-tetrazole or benzotriazole is more preferred.

[0526] As the metal oxidation inhibitor, a commercially available product can be used. As the commercially available product, for example, BT120 manufactured by JOHOKU CHEMICAL CO., LTD. containing benzotriazole can be preferably used.

[0527] When the high refractive index layer contains a metal oxidation inhibitor, the content of the metal oxidation inhibitor is preferably 0.1 to 20 mass %, more preferably 0.5 to 10 mass %, and even more preferably 1 to 5 mass % relative to the total solid content of the high refractive index layer.

[0528] The high refractive index layer may contain other components in addition to the above-mentioned components.

[0529] Examples of other components that may be contained in the high refractive index layer include the same components as those that may be contained in the photosensitive material of the present invention.

[0530] The high refractive index layer also preferably contains a surfactant.

[0531] The method for forming the high refractive index layer is not particularly limited.

[0532] Examples of a method for forming the high refractive index layer include a method of applying a high refractive index layer-forming composition containing an aqueous solvent onto the photosensitive layer formed on a temporary support and drying the composition as needed.

[0533] The composition for forming a high refractive index layer can contain the above-mentioned components of the high refractive index layer.

[0534] The high refractive index layer-forming composition contains, for example, a binder polymer, a polymerizable monomer, particles, and an aqueous solvent.

[0535] Furthermore, as the composition for forming a high refractive index layer, a composition containing an ammonium salt as described in paragraphs 0034 to 0056 of International Publication No. 2016 / 009980 is also preferred.

[0536] The photosensitive layer and the high refractive index layer are preferably colorless. Specifically, in the CIE1976 (L*, a*, b*) color space of total reflection (incident angle 8°, light source: D-65 (2° viewing field)), L * The value is preferably 10 to 90, a * The value is preferably -1.0 to 1.0, b * The value is preferably -1.0 to 1.0.

[0537] <Cover film>

[0538] The transfer film of the present invention may further have a cover film on the side opposite to the temporary support when viewed from the photosensitive layer.

[0539] When the transfer film of the present invention includes a high refractive index layer, the cover film is preferably disposed on the side opposite to the temporary support (i.e., the side opposite to the photosensitive layer) when viewed from the high refractive index layer. In this case, the transfer film is, for example, a laminated body stacked in the order of "temporary support / photosensitive layer / high refractive index layer / cover film."

[0540] The number of fisheyes with a diameter of 80 μm or more contained in the cover film is preferably 5 / m 2 In addition, "fish eyes" refer to foreign matter, undissolved matter, and / or oxidative degradation products of the material that are incorporated into the film when the film is produced by methods such as hot melting, kneading, extrusion, and / or biaxial stretching and casting.

[0541] The number of particles with a diameter of 3 μm or more contained in the coating is preferably 30 particles / mm 2 Below, more preferably 10 / mm 2 Below, more preferably 5 / mm 2Thereby, it is possible to suppress defects caused by the transfer of the unevenness due to the particles contained in the cover film to the photosensitive resin layer.

[0542] The arithmetic mean roughness Ra of the cover film surface is preferably 0.01 μm or more, more preferably 0.02 μm or more, and further preferably 0.03 μm or more. When Ra is within these ranges, for example, when the transfer film is long, the winding property of the transfer film can be improved.

[0543] Furthermore, from the viewpoint of suppressing defects during transfer, Ra is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0544] Examples of the cover film include polyethylene terephthalate films, polypropylene films, polystyrene films, and polycarbonate films.

[0545] As the cover film, for example, films described in paragraphs 0083 to 0087 and 0093 of Japanese Patent Application Laid-Open No. 2006-259138 can be used.

[0546] As the cover film, for example, Alfan (registered trademark) FG-201 manufactured by Oji F-Tex Co., Ltd., Alfan (registered trademark) E-201F manufactured by Oji F-Tex Co., Ltd., Cerapeel (registered trademark) 25WZ manufactured by TORAY ADVANCED FILM CO., LTD., or Lumirror (registered trademark) 16QS62 (16KS40) manufactured by TORAY INDUSTRIES, INC. can be used.

[0547] <Other floors>

[0548] The transfer film may include other layers (hereinafter also referred to as “other layers”) in addition to the above-mentioned layers. Examples of the other layers include an intermediate layer and a thermoplastic resin layer, and known layers can be appropriately adopted.

[0549] Preferred embodiments of the thermoplastic resin layer are described in paragraphs 0189 to 0193 of JP-A-2014-085643, and preferred embodiments of other layers are described in paragraphs 0194 to 0196 of JP-A-2014-085643, the contents of which are incorporated herein.

[0550] <Method for manufacturing transfer film>

[0551] The method for producing the transfer film is not particularly limited, and a known production method can be applied.

[0552] The method for producing the transfer film preferably includes a step of forming a photosensitive layer by coating a photosensitive material containing a solvent on a temporary support and drying the coating. More preferably, the method includes further disposing a cover film on the photosensitive layer after forming the photosensitive layer.

[0553] Furthermore, after the step of forming the photosensitive layer, a step of forming a high refractive index layer by applying a high refractive index layer-forming composition and drying the composition may be further included. In this case, it is more preferable to further include a step of disposing a cover film on the high refractive index layer after the step of forming the high refractive index layer.

[0554] [Pattern Formation Method]

[0555] The pattern forming method according to the present invention (also referred to as "the pattern forming method of the present invention") is not particularly limited as long as it is a pattern forming method using the photosensitive material of the present invention. Preferably, the method comprises, in order, the steps of forming a photosensitive layer on a substrate using the photosensitive material of the present invention, exposing the photosensitive layer in a pattern, and developing the exposed photosensitive layer (alkaline development or organic solvent development). Furthermore, when the development is organic solvent development, the method preferably includes further exposing the obtained pattern.

[0556] When forming a photosensitive layer on a substrate using the photosensitive material of the present invention, a method may be employed in which the transfer film is prepared using the photosensitive material and the photosensitive layer is formed on the substrate using the transfer film. Specifically, this method includes bringing the surface of the photosensitive layer of the transfer film opposite to the temporary support into contact with the substrate, laminating the transfer film and the substrate, and forming the photosensitive layer of the transfer film as the photosensitive layer on the substrate.

[0557] As specific embodiments of the pattern forming method of the present invention, the pattern forming methods of Embodiment 1 and Embodiment 2 can be cited.

[0558] Hereinafter, each step of the pattern forming method according to Embodiment 1 and Embodiment 2 will be described in detail.

[0559] <Pattern Formation Method of Embodiment 1>

[0560] The pattern forming method of embodiment 1 comprises steps X1 to X3. Step X2, described below, corresponds to a step of reducing the content of carboxyl groups derived from polymer A in the photosensitive layer by exposure. If the developer in step X3 is an organic solvent-based developer, step X4 is further included after step X3.

[0561] Step X1: Step of forming a photosensitive layer on a substrate using the photosensitive material of the present invention

[0562] Step X2: Step of pattern-exposing the photosensitive layer

[0563] Step X3: Step of developing the pattern-exposed photosensitive layer using a developer

[0564] Step X4: After the development step of step X3, a step of further exposing the pattern formed by the development

[0565] When an alkaline developer is used as the developer in step X3, the photosensitive material layer is preferably a photosensitive material of embodiment 1 or embodiment 2. When an organic solvent developer is used as the developer in step X3, the photosensitive material layer is preferably a photosensitive material of embodiment 1.

[0566] Furthermore, the pattern forming method of the first embodiment is preferably applied to a transfer film including a photosensitive layer X formed using the photosensitive material of the first embodiment or the second embodiment.

[0567] (Process X1)

[0568] The pattern forming method of the first embodiment includes the step of forming a photosensitive layer on a substrate using the photosensitive material of the present invention.

[0569] Base material

[0570] The substrate is not particularly limited, and examples thereof include glass substrates, silicon substrates, resin substrates, and substrates having a conductive layer. Examples of substrates included in the substrate having a conductive layer include glass substrates, silicon substrates, and resin substrates.

[0571] The above-mentioned substrate is preferably transparent.

[0572] The refractive index of the substrate is preferably 1.50 to 1.52.

[0573] The substrate may be formed of a light-transmitting substrate such as a glass substrate. For example, tempered glass such as Gorilla Glass manufactured by Corning Incorporated Co., Ltd. may be used. Furthermore, materials included in the substrate are preferably those disclosed in Japanese Patent Application Laid-Open Nos. 2010-086684, 2010-152809, and 2010-257492.

[0574] When the substrate comprises a resin substrate, it is more preferable to use a resin film having small optical distortion and / or high transparency as the resin substrate. Specific raw materials include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.

[0575] As the substrate included in the substrate having a conductive layer, from the viewpoint of production by a roll-to-roll method, a resin substrate is preferred, and a resin film is more preferred.

[0576] As the conductive layer, any conductive layer used for general circuit wiring or touch panel wiring can be mentioned.

[0577] From the viewpoint of conductivity and thin line formability, the conductive layer is preferably one or more layers selected from a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, more preferably a metal layer, and still more preferably a copper layer or a silver layer.

[0578] Furthermore, the conductive layer in the substrate having the conductive layer may be a single layer or may be two or more layers.

[0579] When the substrate having a conductive layer includes two or more conductive layers, it is preferable that the respective conductive layers be made of materials different from each other.

[0580] Examples of the material for the conductive layer include simple metals and conductive metal oxides.

[0581] Examples of the metal element include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au.

[0582] Examples of conductive metal oxides include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO2. In addition, "conductive" means that the volume resistivity is less than 1×10 6 Ωcm, preferably the volume resistivity is less than 1×10 4 Ωcm.

[0583] When the substrate having a conductive layer has two or more conductive layers, it is preferred that at least one of the conductive layers contains a conductive metal oxide.

[0584] The conductive layer is preferably an electrode pattern of a sensor corresponding to a visual recognition portion used in a capacitive touch panel or wiring of a peripheral lead portion.

[0585] Furthermore, the conductive layer is preferably a transparent layer.

[0586] · Sequence of process X1

[0587] Step X1 is not particularly limited as long as a photosensitive layer can be formed on a substrate using the photosensitive material of the present invention.

[0588] For example, a photosensitive material containing a solvent can be applied to a substrate to form a coating film, and the coating film can be dried to form a photosensitive layer on the substrate. As a method for forming the photosensitive layer on such a substrate, for example, the same method as the method for forming the photosensitive layer described above in the description of the transfer film can be cited.

[0589] Furthermore, in step X1, the photosensitive material used to form the photosensitive layer on the substrate is preferably the photosensitive material contained in the transfer film (the photosensitive layer of the transfer film). In other words, the photosensitive layer formed in step X1 is preferably a layer formed using the transfer film.

[0590] When forming a photosensitive layer on a substrate using a transfer film, step X1 is preferably a step of bringing the surface of the photosensitive layer of the transfer film opposite to the temporary support into contact with the substrate and laminating the transfer film and the substrate. This step is also specifically referred to as step X1b.

[0591] The step X1b is preferably a laminating step of applying pressure and heating with a roller, etc. For laminating, a known laminator such as a laminator, a vacuum laminator, and an automatic cutting laminator can be used.

[0592] Since step X1b is preferably performed by a roll-to-roll method, the substrate to which the transfer film is bonded is preferably a resin film or a resin film having a conductive layer.

[0593] The roll-to-roll method is described below.

[0594] The roll-to-roll method refers to a method in which a substrate that can be wound up and unwound is used as a substrate, and before any process included in the pattern forming method of the present invention, a process of unwinding the substrate (also referred to as a "winding-up process") and after any process, a process of winding the substrate (also referred to as a "winding-up process") are included, and at least any process (preferably all processes or all processes except the heating process) are carried out while the substrate is transported.

[0595] The unwinding method in the unwinding step and the winding method in the winding step are not particularly limited, and any known method may be used in a production method employing a roll-to-roll system.

[0596] (Process X2)

[0597] The pattern forming method of Embodiment 1 includes a step (Step X2) of pattern-exposing the photosensitive layer after Step X1. Step X2 corresponds to a step of reducing the content of carboxyl groups derived from polymer A in the photosensitive layer by exposure. More specifically, the photosensitive layer is preferably pattern-exposed using light of a wavelength that excites structure b0 (preferably structure b) in the photosensitive layer.

[0598] In addition, the structure b0 (preferably structure b) in the above-mentioned photosensitive layer can be the structure possessed by the compound β (preferably compound B) contained in the photosensitive layer, or the structure possessed by the polymer A (polymer Ab0, preferably polymer Ab) contained in the photosensitive layer, or both.

[0599] In the exposure process, the detailed arrangement and specific size of the pattern are not particularly limited.

[0600] For example, when the pattern forming method of embodiment 1 is applied to the manufacture of circuit wiring, from the perspective of improving the display quality of a display device (for example, a touch panel) having an input device with circuit wiring manufactured by the pattern forming method of embodiment 1, and from the perspective of minimizing the area occupied by the lead-out wiring, at least a portion of the pattern (especially the portion corresponding to the electrode pattern and the lead-out wiring of the touch panel) is preferably a thin line of less than 100 μm, and more preferably a thin line of less than 70 μm.

[0601] The light source used for exposure can be appropriately selected as long as it irradiates light in a wavelength range that can reduce the content of carboxyl groups in the polymer A in the photosensitive layer (light of a wavelength that excites structure b0 (preferably structure b) in the photosensitive layer. For example, light in wavelength ranges such as 254 nm, 313 nm, 365 nm, and 405 nm can be mentioned). Specifically, ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes) can be mentioned.

[0602] The exposure dose is preferably 10 to 10,000 mJ / cm 2 , more preferably 50 to 3000 mJ / cm 2 .

[0603] If step X1 is step X1b, in step X2, pattern exposure may be performed after peeling the temporary support from the photosensitive layer, or pattern exposure may be performed through the temporary support before peeling the temporary support, and then peeling the temporary support. To prevent mask contamination caused by contact between the photosensitive layer and the mask and to avoid the influence of foreign matter attached to the mask on the exposure, pattern exposure is preferably performed without peeling the temporary support. Pattern exposure may be exposure through the mask or direct exposure using a laser or the like.

[0604] (Process X3)

[0605] The pattern forming method of embodiment 1 includes a step (step X3) of developing the pattern-exposed photosensitive layer using a developer (alkaline developer or organic solvent developer) after the above-mentioned step X2. + .

[0606] The photosensitive layer that has passed through process X2 reduces the content of carboxyl groups in the photosensitive layer through the exposed portion, thereby generating a difference in solubility in the developer (solution contrast) between the exposed portion and the unexposed portion. By forming a solubility contrast in the photosensitive layer, a pattern can be formed in process X3. In addition, when the developer of the above-mentioned process X3 is an alkaline developer, the unexposed portion is removed by implementing the above-mentioned process X3 to form a negative pattern. On the other hand, when the developer of the above-mentioned process X3 is an organic solvent-based developer, the exposed portion is removed by implementing the above-mentioned process X3 to form a positive pattern. The obtained positive pattern needs to be subjected to a treatment to reduce the content of carboxyl groups from polymer A through process X4 described later.

[0607] Alkaline developer

[0608] The alkaline developer is not particularly limited as long as it can remove the unexposed portion of the photosensitive resin layer. For example, a known developer such as one described in Japanese Patent Application Laid-Open No. 5-072724 can be used.

[0609] As the alkaline developer, for example, an alkaline aqueous solution-based developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 to 5 mol / L (liter) is preferable.

[0610] Furthermore, the alkali developer may further contain a water-soluble organic solvent, a surfactant, etc. As the alkali developer, for example, the developer described in paragraph 0194 of International Publication No. 2015 / 093271 is preferable.

[0611] Organic solvent-based developer

[0612] The organic solvent-based developer is not particularly limited as long as it can remove the exposed portion of the photosensitive resin layer. For example, developers containing organic solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents can be used.

[0613] In an organic solvent-based developer, the organic solvent may be mixed with a plurality of organic solvents or may be mixed with organic solvents other than the above or water for use. In order to fully exert the effects of the present invention, the organic solvent-based developer preferably has a water content of less than 10% by mass, and more preferably contains substantially no water. The concentration of the organic solvent in the organic solvent-based developer (total in the case of a plurality of mixed organic solvents) is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more. Furthermore, the upper limit may be, for example, 100% by mass or less.

[0614] The development method is not particularly limited and may be any of spin immersion development, spray development, rotary development, and dip development. In the case of spray development, the developer can be sprayed onto the exposed photosensitive resin layer to remove unnecessary portions. After development, it is also preferable to spray a cleaning agent, etc., while wiping with a brush, etc. to remove development residue. The developer temperature is preferably 20 to 40°C.

[0615] The pattern forming method of Embodiment 1 may further include a step of baking the pattern including the photosensitive layer obtained by development after heat treatment.

[0616] Post-baking is preferably performed in an environment of 8.1 to 121.6 kPa, more preferably in an environment of 50.66 kPa or higher, more preferably in an environment of 111.46 kPa or lower, and even more preferably in an environment of 101.3 kPa or lower.

[0617] The temperature of the post-baking is preferably 80 to 250°C, more preferably 110 to 170°C, and even more preferably 130 to 150°C.

[0618] The post-baking time is preferably 1 to 60 minutes, more preferably 2 to 50 minutes, and even more preferably 5 to 40 minutes.

[0619] Post-baking can be performed in an air environment or in a nitrogen-substituted environment.

[0620] (Process X4)

[0621] When the developer in step X3 is an organic solvent-based developer, step X4 is performed on the obtained positive pattern. Step X4 is equivalent to exposing the positive pattern obtained in step X3 to light, thereby reducing the content of carboxyl groups derived from polymer A. More specifically, the photosensitive layer is preferably pattern-exposed using light of a wavelength that excites structure b0 (preferably structure b) in the photosensitive layer.

[0622] The light source and exposure amount used for exposure are the same as those described in step X1, and preferred aspects are also the same.

[0623] <Pattern Formation Method of Embodiment 2>

[0624] The pattern forming method of the second embodiment sequentially includes step Y1, step Y2P, and step Y3, and further includes step Y2Q (a step of further exposing the photosensitive layer exposed in step Y2P) between step Y2P and step Y3 or after step Y3.

[0625] Step Y1: Step of forming a photosensitive layer on a substrate using the photosensitive material of the present invention

[0626] Step Y2P: step of exposing the photosensitive layer

[0627] Step Y2Q: Step of further exposing the exposed photosensitive layer

[0628] Step Y3: Step of developing the photosensitive layer using a developer

[0629] The pattern forming method of the second embodiment is preferably applied to a case where the photosensitive layer further contains a photopolymerization initiator and a polymerizable compound.

[0630] Hereinafter, the pattern forming method according to the second embodiment will be described. Since step Y1 and step Y3 are the same as step X1 and step X3, their description will be omitted.

[0631] In addition, step Y3 only needs to be performed after step Y2P at least, and step Y3 can be performed between step Y2P and step Y2Q.

[0632] In addition, the pattern forming method of Embodiment 2 may further include a post-baking step after Step Y3 for heat-treating the pattern including the photosensitive layer obtained by development. The post-baking step can be implemented using the same method as the post-baking step that may be included in the pattern forming method of Embodiment 1 described above. If Step Y3 is implemented between Step Y2P and Step Y2Q, the post-baking step may be implemented before or after Step Y2Q, as long as it is implemented after Step Y3.

[0633] (Process Y2P, Process Y2Q)

[0634] The pattern forming method of the second embodiment includes a step of exposing the photosensitive layer subjected to step Y1 (step Y2P) and a step of further exposing the exposed photosensitive layer (step Y2Q).

[0635] Either of the exposure processes (steps Y2P and Y2Q) is primarily for reducing the carboxyl group content of polymer A through exposure. Either of the exposure processes (steps Y2P and Y2Q) corresponds to exposure primarily for inducing a polymerization reaction of the polymerizable compound using a photopolymerization initiator. Furthermore, while the exposure processes (steps Y2P and Y2Q) can each be either full-surface exposure or pattern exposure, either exposure process is pattern exposure.

[0636] For example, when step Y2P is pattern exposure for reducing the carboxyl group content of polymer A by exposure, the developer used in step Y3 may be an alkaline developer or an organic solvent-based developer. When developing with an organic solvent-based developer, step Y2Q is typically performed after step Y3. In the developed photosensitive layer (pattern), a polymerization reaction of the polymerizable compound by the photopolymerization initiator is initiated, and the carboxyl group content of polymer A is reduced.

[0637] Furthermore, for example, if step Y2P is pattern exposure for inducing a polymerization reaction of a polymerizable compound using a photopolymerization initiator, the developer used in step Y3 is typically an alkaline developer. In this case, step Y2Q can be performed before or after step Y3; if performed before step Y3, step Y2Q is typically pattern exposure.

[0638] In process Y2P and process Y2Q, as the light source used for exposure, any light source that irradiates a wavelength range that can reduce the content of carboxyl groups in the polymer A in the photosensitive layer (light of a wavelength that excites structure b0 (preferably structure b) in the photosensitive layer. For example, light of a wavelength range such as 254 nm, 313 nm, 365 nm, and 405 nm can be cited), or light of a wavelength range that can cause a reaction of a polymerizable compound based on a photopolymerization initiator in the photosensitive layer (light of a wavelength that makes the photopolymerization initiator photosensitized. For example, light of 254 nm, 313 nm, 365 nm, and 405 nm can be appropriately selected. Specifically, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode) can be cited.

[0639] In the exposure for reducing the content of the carboxyl group of the polymer A in the photosensitive layer, the exposure dose is preferably 10 to 10,000 mJ / cm 2 , more preferably 50 to 3000 mJ / cm 2 .

[0640] In the exposure for initiating the reaction of the polymerizable compound by the photopolymerization initiator in the photosensitive layer, the exposure dose is preferably 5 to 200 mJ / cm 2 , more preferably 10 to 150 mJ / cm 2 .

[0641] When step Y1 is carried out in the same manner as step X1b, in step Y2P and / or step Y2Q, pattern exposure may be performed after peeling the temporary support from the photosensitive layer, or pattern exposure may be performed through the temporary support before peeling the temporary support, and then peeling the temporary support. In order to prevent contamination of the mask caused by contact between the photosensitive layer and the mask and to avoid the influence of foreign matter attached to the mask on the exposure, pattern exposure is preferably performed without peeling the temporary support. In addition, pattern exposure may be exposure through the mask or direct exposure using a laser or the like.

[0642] In the exposure process, the detailed arrangement and specific size of the pattern are not particularly limited.

[0643] For example, when the pattern forming method of embodiment 2 is applied to the manufacture of circuit wiring, from the perspective of improving the display quality of a display device (for example, a touch panel) having an input device with circuit wiring manufactured by the pattern forming method of embodiment 2, and from the perspective of minimizing the area occupied by the lead-out wiring, at least a portion of the pattern (especially the portion corresponding to the electrode pattern and the lead-out wiring of the touch panel) is preferably a thin line of less than 100 μm, and more preferably a thin line of less than 70 μm.

[0644] (Preferred method)

[0645] In the pattern forming method of Embodiment 2, step Y2P corresponds to step Y2A, step Y2Q corresponds to step Y2B, and the method preferably includes step Y1, step Y2A, step Y3, and step Y2B in this order. Furthermore, one of step Y2A and step Y2B corresponds to an exposure step for reducing the carboxyl group content of polymer A by exposure, and the other corresponds to an exposure step for inducing a reaction between a photopolymerization initiator and a polymerizable compound.

[0646] Step Y1: A step of forming a photosensitive layer on a substrate using the photosensitive material of the present invention (preferably, a step of bringing the surface of the photosensitive layer of the transfer film opposite to the temporary support into contact with the substrate and laminating the transfer film to the substrate)

[0647] Step Y2A: Step of exposing the photosensitive layer to a pattern

[0648] Step Y3: a step of developing the photosensitive layer using an alkaline developer to form a patterned photosensitive layer

[0649] Step Y2B: step of exposing the patterned photosensitive layer

[0650] The step Y2A is preferably an exposure step for inducing a reaction between a photopolymerization initiator and a polymerizable compound, and the step Y2B is preferably an exposure step for reducing the content of carboxyl groups derived from the polymer A by exposure.

[0651] <Optional Steps Possible in the Pattern Formation Methods of Embodiments 1 and 2>

[0652] The pattern forming methods of Embodiments 1 and 2 may include any steps (other steps) other than those described above. For example, the following steps may be mentioned, but the present invention is not limited to these steps.

[0653] (Cover film peeling process)

[0654] When a transfer film is used to form a photosensitive layer on a substrate, and the transfer film has a cover film, the pattern forming method preferably includes a step of peeling off the cover film of the transfer film (hereinafter also referred to as a "cover film peeling step"). The method of peeling off the cover film is not particularly limited, and a known method can be applied.

[0655] (Process of reducing visible light reflectivity)

[0656] When the substrate has a conductive layer, the pattern forming method may further include performing a treatment to reduce the visible light reflectivity of the conductive layer. Furthermore, when the substrate has multiple conductive layers, the treatment to reduce the visible light reflectivity may be performed on some or all of the conductive layers.

[0657] As a treatment for reducing the visible light reflectance, an oxidation treatment can be mentioned. For example, by oxidizing copper to form copper oxide and turning it black, the visible light reflectance of the conductive layer can be reduced.

[0658] Preferred aspects of the treatment for reducing the visible light reflectance are described in paragraphs 0017 to 0025 of Japanese Patent Application Laid-Open No. 2014-150118 and paragraphs 0041, 0042, 0048, and 0058 of Japanese Patent Application Laid-Open No. 2013-206315, the contents of which are incorporated herein.

[0659] (Etching process)

[0660] When the substrate is a substrate having a conductive layer, the above-mentioned pattern forming method preferably includes a process (etching process) of using the pattern formed by process X3 (or process X4) and process Y3 as an etching resist film, and etching the conductive layer in the area where the etching resist film is not configured.

[0661] As the etching method, a wet etching method described in paragraphs 0048 to 0054 of Japanese Patent Application Laid-Open No. 2010-152155 and a dry etching method such as known plasma etching can be applied.

[0662] For example, as an etching method, wet etching is generally performed by immersing the etching solution in an etching solution. The etching solution used in the wet etching can be appropriately selected from an acidic type or an alkaline type according to the etching target.

[0663] Examples of acidic etching solutions include aqueous solutions of acidic components such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid alone, and mixed aqueous solutions of acidic components with salts such as ferric chloride, ammonium fluoride, and potassium permanganate. A combination of multiple acidic components may be used as the acidic component.

[0664] Examples of alkaline etching solutions include aqueous solutions of a single alkaline component such as sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines such as tetramethylammonium hydroxide, and aqueous solutions mixed with a salt such as potassium permanganate. Alkaline components may be a combination of multiple alkaline components.

[0665] The temperature of the etching solution is not particularly limited, but is preferably 45°C or lower. In the circuit wiring manufacturing method of the present invention, the pattern formed in step X3 (or step X4) and step Y3, which serves as the etching resist film, preferably exhibits particularly excellent resistance to acidic and alkaline etching solutions in a temperature range of 45°C or lower. This structure prevents peeling of the etching resist film during the etching step, and allows selective etching of portions where no etching resist film is present.

[0666] After the etching process, in order to prevent contamination of the process line, a cleaning process for cleaning the etched substrate and a drying process for drying the cleaned substrate may be performed as needed.

[0667] The film used as the etching resist film may be removed, or may be left as a protective film (permanent film) for the conductive layer of the circuit wiring.

[0668] (Other embodiments)

[0669] In the above-mentioned pattern forming method, it is also preferable to use a substrate having a plurality of conductive layers on both surfaces, and pattern the conductive layers formed on both surfaces sequentially or simultaneously.

[0670] This structure enables the formation of a first conductive pattern on one surface of the substrate and a second conductive pattern on the other surface. Roll-to-roll formation from both sides of the substrate is also preferred.

[0671] <Pattern>

[0672] The patterns formed by the pattern forming methods of the first and second embodiments have a reduced content of carboxyl groups, and thus have reduced polarity and a reduced relative dielectric constant.

[0673] The carboxyl group content in the pattern is preferably reduced by 5 mol% or more, more preferably by 10 mol% or more, even more preferably by 20 mol% or more, even more preferably by 31 mol% or more, particularly preferably by 40 mol% or more, particularly preferably by 51 mol% or more, and most preferably by 71 mol% or more, relative to the carboxyl group content in the photosensitive layer formed in step X1 or step Y1. The upper limit is not particularly limited, but is, for example, 100 mol% or less.

[0674] The moisture permeability of the pattern is preferably reduced by 5% or more, more preferably by 10% or more, and further preferably by 20% or more relative to the moisture permeability of the photosensitive layer formed in step X1 or step Y1. The upper limit is not particularly limited, but is, for example, 100% or less.

[0675] The relative dielectric constant of the pattern is preferably reduced by 5% or more, more preferably by 10% or more, and even more preferably by 15% or more relative to the relative dielectric constant of the photosensitive layer formed in step X1 or step Y1. The upper limit is not particularly limited, but is, for example, 100% or less.

[0676] The average thickness of the pattern formed by the above-mentioned pattern forming method is preferably 0.5 to 20 μm, more preferably 0.8 to 15 μm, and even more preferably 1.0 to 10 μm.

[0677] The pattern formed by the above pattern forming method is preferably colorless. Specifically, total reflection (incident angle 8°, light source: D-65 (2° field of view)) is CIE1976 (L * 、a * 、b * ) color space, the pattern’s L * The value is preferably 10 to 90, and the pattern a * The value is preferably -1.0 to 1.0, and the b * The value is preferably -1.0 to 1.0.

[0678] The use of the pattern formed by the above-mentioned pattern forming method is not particularly limited, and the pattern can be used as various protective films or insulating films.

[0679] Specifically, the pattern can be used as a protective film (permanent film) to protect conductive patterns, as an interlayer insulating film between conductive patterns, and as an etching resist film during circuit wiring production. Because the above-mentioned pattern reduces the relative dielectric constant, it is particularly preferred to use it as a protective film (permanent film) to protect conductive patterns or as an interlayer insulating film between conductive patterns. Furthermore, after using the pattern as an etching resist film, it can be used directly as a protective film (permanent film).

[0680] In addition, the above-mentioned pattern can be used, for example, as a protective film (permanent film) for protecting conductive patterns such as electrode patterns of sensors corresponding to the visual recognition part arranged inside the touch panel, peripheral wiring parts and wiring of lead-out wiring parts, or as an interlayer insulating film between conductive patterns.

[0681] [Method for manufacturing circuit wiring]

[0682] The present invention also relates to a method for manufacturing the circuit wiring.

[0683] The method for manufacturing circuit wiring involved in the present invention (also referred to as "the method for manufacturing circuit wiring of the present invention") is not particularly limited as long as it is a method for manufacturing circuit wiring using the above-mentioned photosensitive material. It preferably includes, in sequence, a process of forming a photosensitive layer on a conductive layer in a substrate having a conductive layer using a photosensitive material (preferably a photosensitive material of method 3) (photosensitive layer forming process), a process of exposing the photosensitive layer to a pattern (first exposure process), a process of developing the exposed photosensitive layer using an alkaline developer to form a patterned photosensitive layer (alkaline development process), a process of forming an etching resist film by exposing the patterned photosensitive layer (second exposure process), and a process of etching the conductive layer in an area where the etching resist film is not provided (etching process).

[0684] The photosensitive layer forming step is preferably a step of laminating the transfer film and the substrate having a conductive layer by bringing the surface of the photosensitive layer of the transfer film opposite to the temporary support into contact with the conductive layer of the substrate having a conductive layer (laminating step).

[0685] In the method for manufacturing a circuit wiring of the present invention, the photosensitive layer forming step, the first exposure step, the alkali development step, and the second exposure step can all be performed in the same order as step Y1, step Y2A, step Y3, and step Y2B of the pattern forming method of the second embodiment described above. Furthermore, the substrate having a conductive layer used in the method for manufacturing a circuit wiring of the present invention is the same as the substrate having a conductive layer used in the above-mentioned step X1. Furthermore, the method for manufacturing a circuit wiring of the present invention may include other steps in addition to the above-mentioned steps. Examples of other steps include steps that are the same as any steps that may be included in the pattern forming methods of the first and second embodiments.

[0686] The method for producing a circuit wiring of the present invention is also preferably a method in which the four steps of the lamination step, the first exposure step, the development step, the second exposure step, and the etching step are repeated a plurality of times as a set.

[0687] The film used as the etching resist film can also serve as a protective film (permanent film) for the formed circuit wiring.

[0688] [Method for Manufacturing Touch Panel]

[0689] The invention also relates to a method for manufacturing a touch panel.

[0690] The method for manufacturing a touch panel involved in the present invention (also referred to as "the method for manufacturing a touch panel of the present invention") is not particularly limited as long as it is a method for manufacturing a touch panel using the above-mentioned photosensitive material. It preferably includes, in sequence, a step of forming a photosensitive layer on a conductive layer in a substrate having a conductive layer (preferably a patterned conductive layer, specifically, a conductive pattern such as a touch panel electrode pattern or a wiring pattern) using a photosensitive material (preferably a photosensitive material of mode 3) (photosensitive layer forming step), a step of exposing the photosensitive layer to a pattern (first exposure step), a step of developing the exposed photosensitive layer using an alkaline developer to form a patterned photosensitive layer (alkaline development step), and a step of forming a protective film or insulating film of the conductive layer by exposing the patterned photosensitive layer (second exposure step).

[0691] The protective film formed by the second exposure step functions as a film that protects the surface of the conductive layer. Furthermore, the insulating film functions as an interlayer insulating film between the conductive layers. Furthermore, when the second exposure step is a step of forming an insulating film for the conductive layer, the touch panel manufacturing method of the present invention preferably further includes a step of forming a conductive layer (preferably a patterned conductive layer, specifically, a conductive pattern such as a touch panel electrode pattern or wiring) on ​​the insulating film formed by the second exposure step.

[0692] The photosensitive layer forming step is preferably a step of laminating the transfer film and the substrate having a conductive layer by bringing the surface of the photosensitive layer of the transfer film opposite to the temporary support into contact with the conductive layer of the substrate having a conductive layer (laminating step).

[0693] In the touch panel manufacturing method of the present invention, the photosensitive layer forming step, the first exposure step, the alkali development step, and the second exposure step can all be performed in the same order as step Y1, step Y2A, step Y3, and step Y2B in the pattern forming method of the second embodiment described above. Furthermore, the substrate having a conductive layer used in the touch panel manufacturing method of the present invention is the same as the substrate having a conductive layer used in the above-described step X1. Other steps can be the same as any steps that may be included in the pattern forming methods of the first and second embodiments.

[0694] As a method for manufacturing a touch panel of the present invention, a known method for manufacturing a touch panel can be referred to for configurations other than the above-described embodiment.

[0695] The touch panel manufactured by the touch panel manufacturing method of the present invention preferably includes a transparent substrate, electrodes, and a protective layer (protective film).

[0696] The detection method in the touch panel may be any of known methods such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method. Among them, the capacitance method is preferred.

[0697] Examples of touch panel types include so-called in-cell types (e.g., those described in FIG. 5 , FIG. 6 , FIG. 7 , and FIG. 8 of Japanese Unexamined Patent Publication No. 2012-517051 ), so-called over-cell types (e.g., those described in FIG. 19 of Japanese Unexamined Patent Publication No. 2013-168125 , and those described in FIG. 2012-089102 ). Figure 1 and Figure 5), OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (for example, described in Figure 2 of Japanese Patent Publication No. 2013-054727), other structures (for example, described in Figure 6 of Japanese Patent Publication No. 2013-164871) and various embedded types (so-called GG, G1 / G2, GFF, GF2, GF1, G1F, etc.), etc.

[0698] Example

[0699] Hereinafter, the present invention will be further described in detail by way of examples. The materials, usage amounts, ratios, processing contents and processing sequences shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, unless otherwise specified, "parts" and "%" are weight references.

[0700] In the following examples, a high-pressure mercury lamp, H03-L31 manufactured by EYE GRAPHICS CO., LTD., was used unless otherwise specified. This high-pressure mercury lamp has a main wavelength of 365 nm and strong line spectra at 254 nm, 313 nm, 405 nm, and 436 nm.

[0701] As the ultrahigh-pressure mercury lamp, USH-2004MB manufactured by USHIO INC. was used unless otherwise specified. The ultrahigh-pressure mercury lamp has strong line spectra at 313 nm, 365 nm, 405 nm, and 436 nm.

[0702] [Example 1 Series]

[0703] Preparation of photosensitive materials

[0704] A styrene / acrylic acid copolymer (acid value: 200, Mw: 8500, manufactured by TOAGOSEICO, LTD., ARUFON UC3910 (trade name)) and compound β shown in Table 2 were mixed and dissolved in a 50 / 50 (mass ratio) mixed solvent of propylene glycol monomethyl ether acetate and methyl ethyl ketone to satisfy the blending amounts described in Table 2 (later described) and to achieve a final photosensitive material solids concentration of 25% by mass, thereby forming a mixed solution. MEGAFACE F551 (a fluorinated nonionic surfactant manufactured by DIC Corporation) was added as a surfactant to the mixed solution to a concentration of 100 ppm by mass relative to the total solids content of the photosensitive material, thereby preparing the photosensitive materials of each Example or Comparative Example.

[0705] In addition, the compounding amount (mass parts) shown in the table is the solid content of each component.

[0706] <Physical Property Evaluation of Compound β>

[0707] (Determination of pKa of Compound β in Ground State)

[0708] The pKa of compound β in the ground state was measured by the following method using an automatic titrator manufactured by HIRANUMACo., Ltd. When compound β is a nitrogen-containing aromatic compound, the pKa of compound β in the ground state represents the pKa of the conjugated acid of compound β.

[0709] 0.1 g of compound β was dissolved in 20 ml of methanol, and 20 ml of ultrapure water was added. The solution was titrated with 0.1 N aqueous HCl, and the pH at half the titration required to reach the equivalence point was defined as pKa (pKa of compound β in the ground state).

[0710] (Measurement and Evaluation of ε365 and ε365 / ε313)

[0711] Calculate the molar absorptivity of compound β at 365 nm (cm·mol / L) -1 , "ε365") and the molar absorption coefficient at 313 nm ((cm·mol / L) -1 , “ε313”), and calculated the value of ε365 divided by ε313 (ε365 / ε313).

[0712] ε365 and ε313 of compound β are molar absorption coefficients measured by dissolving compound β in acetonitrile. If compound β is not soluble in acetonitrile, the solvent in which compound β is dissolved can be appropriately changed. Preferably, 1 or less is used.

[0713] <Evaluation of photosensitive materials>

[0714] (Production of Photosensitive Layer)

[0715] The photosensitive material of each example or comparative example was spin-coated on a silicon wafer, and the obtained coating film was dried at 80° C. using a hot plate to obtain a photosensitive layer with a film thickness of 5 μm.

[0716] The obtained photosensitive layer was evaluated as follows.

[0717] (Evaluation of Carboxyl Group Consumption Rate (IR Measurement))

[0718] The obtained photosensitive layer was exposed to light over the entire surface using a high-pressure mercury lamp. The cumulative exposure dose measured by an illuminometer at 365 nm was 1000 mJ / cm 2 In addition, the light emitted from the high-pressure mercury lamp has a wavelength of 365 nm as a main wavelength and has strong line spectra at 254 nm, 313 nm, 405 nm and 436 nm.

[0719] The IR (infrared) spectrum of the photosensitive layer was measured before and after exposure, and the peak of the C=O stretch of the carboxyl group (1710 cm -1 The carboxyl group consumption rate (mol %) was calculated based on the decrease rate of the peak value of the reaction mixture.

[0720] The higher the carboxyl group consumption rate, the more the decarboxylation reaction proceeds.

[0721] The results are shown in Table 2 (see the column "Carboxyl group consumption rate (mol %) [IR measurement]").

[0722] (Evaluation of carboxyl group consumption rate (ashing measurement))

[0723] The carboxyl group consumption rate was determined by the following procedure.

[0724] ·Measurement of the amount of carboxyl groups in the photosensitive layer after exposure (Measurement of the amount of carboxyl groups after exposure)

[0725] The photosensitive layer obtained in the upper portion was exposed by the following exposure conditions.

[0726] Exposure Conditions

[0727] The obtained photosensitive layer was exposed to light over the entire surface using a high-pressure mercury lamp. The cumulative exposure dose measured by an illuminometer at 365 nm was 1000 mJ / cm 2 The light emitted from the high-pressure mercury lamp has a main wavelength of 365 nm and has strong line spectra at 254 nm, 313 nm, 405 nm, and 436 nm.

[0728] Next, about 20 mg of the exposed photosensitive layer was scraped off and frozen and crushed, and then 150 μL of NMP (N-methyl-2-pyrrolidone) was added. The mixture was then stirred for 6 days in a lithium carbonate (Li2CO3) aqueous solution (1.2 g / 100 mL. Lithium carbonate was dissolved in ultrapure water and then filtered.).

[0729] After stirring, the particles were precipitated by ultracentrifugation (140,000 rpm x 30 min). The supernatant was replaced with ultrapure water (repeated five times), and the resulting precipitate was dried and solidified to serve as an analytical sample (n = 2 samples). This analytical sample was analyzed using ICP-OES (Optima 7300DV, manufactured by Perkin Elmer Co., Ltd.).

[0730] In addition, the above-mentioned ICP-OES measurement was carried out by the following procedure.

[0731] About 1.5 mg to 2 mg (n=3) of the above-mentioned analytical sample was weighed, and 5 mL of a 60% HNO 3 aqueous solution was added, followed by MW Teflon ashing (microwave sample decomposition apparatus Ultra WAVE max: 260° C.).

[0732] After ashing, ultrapure water was added to 50 mL, and the amount of Li was quantified using an ICP-OES (Optima 7300DV manufactured by Perkin Elmer Co., Ltd.) according to the absolute calibration curve method.

[0733] ·Measurement of the amount of carboxyl groups in a photosensitive material before exposure (Measurement of the amount of carboxyl groups before exposure)

[0734] The carboxyl group content of the photosensitive material of each Example and Comparative Example used to form the above-mentioned photosensitive layer was measured according to the following procedure.

[0735] 1 g of the photosensitive material was dissolved in 63 ml of tetrahydrofuran, and 12 ml of ultrapure water was added. The resulting solution was then titrated with a 0.1N aqueous NaOH solution using an automatic titrator manufactured by HIRANUMACo., Ltd. The amount of carboxyl groups obtained by titration was converted to the solid content concentration to calculate the amount of carboxyl groups in the photosensitive material.

[0736] Calculation of decarboxylation rate

[0737] Based on the measurement results of the carboxyl group amounts before and after the exposure, the decarboxylation rate was calculated using the following formula.

[0738] Decarboxylation rate (%): {(amount of carboxyl groups before exposure - amount of carboxyl groups after exposure) / amount of carboxyl groups before exposure} × 100 (%)

[0739] Based on the obtained numerical values, evaluation was performed according to the following evaluation criteria.

[0740] However, the above method has a detection limit. When the carboxyl group content is 1.05 mmol / g or less, 90% or more of the Li can be substituted. In other regions, a calibration curve was prepared using a cross-linked polymer with a known acid value and calculations were performed.

[0741] Evaluation benchmark

[0742] A decarboxylation rate is 71 mol% or more

[0743] The B decarboxylation rate is 50 mol% or more and less than 71 mol%

[0744] The C decarboxylation rate is 31 mol% or more and less than 50 mol%

[0745] The D decarboxylation rate is 5 mol% or more and less than 31 mol%

[0746] E decarboxylation rate is less than 5 mol%

[0747] The results are shown in Table 2 (see the "Carboxyl group consumption rate [ashing measurement]" column).

[0748] (Pattern Formability Evaluation 1)

[0749] The obtained photosensitive layer was exposed to light using a high pressure mercury lamp through any of the following masks (1) to (3). The cumulative exposure dose measured by an illuminometer at 365 nm was 1000 mJ / cm 2 .

[0750] (1) Mask with line size = 25 μm and line:space = 1:1

[0751] (2) Mask with line size = 50 μm and line:space = 1:1

[0752] (3) Mask with line size = 250 μm and line:space = 1:1

[0753] The exposed photosensitive layer was dip-developed with a 1% by mass sodium carbonate aqueous solution for 30 seconds, then rinsed with pure water for 20 seconds and dried to obtain a pattern (line and space pattern).

[0754] The line and space patterns having a line and space width of 25 μm, 50 μm, or 250 μm produced in this manner were observed and evaluated in the following manner.

[0755] A: The line and space pattern was resolved (the photosensitive layer in the space portion was removed), and the film of the pattern was not reduced.

[0756] B: The line and space pattern is resolved, but the film of the pattern is slightly reduced.

[0757] C: Line and space pattern resolved, but a significant reduction in the film of the pattern was observed

[0758] D: Line and space pattern is not resolved (the photosensitive layer in the space portion remains or the pattern is completely dissolved and disappears)

[0759] (Relative dielectric constant evaluation 1)

[0760] A photosensitive material was spin-coated on an aluminum substrate having a thickness of 0.1 mm, and the obtained coating was dried on a hot plate at 80° C. to prepare a photosensitive layer having a thickness of 8 μm.

[0761] The obtained photosensitive layer was exposed to light over the entire surface using a high-pressure mercury lamp. The cumulative exposure dose measured by an illuminometer at 365 nm was 1000 mJ / cm 2 .

[0762] The relative dielectric constant of the photosensitive layer after exposure was measured at 1 kHz using LCRmeter 4284A and Dielectric Test Fixture 16451B manufactured by Agilent Technologies, Inc. under an environment of 23° C. and 50% RH.

[0763] The relative dielectric constant of the photosensitive layer formed using the photosensitive material of Comparative Example 1A after exposure was set as 100%. Compared with this, the reduction rate of the relative dielectric constant of the photosensitive layer formed using the photosensitive material of each example after exposure was calculated and evaluated according to the following criteria.

[0764] As the value of the reduction rate increases, the relative dielectric constant decreases compared to Comparative Example 1A, indicating that the film is effective as an insulating film.

[0765] A: Reduction rate is more than 15%

[0766] B: Reduction rate is 10% or more and less than 15%

[0767] C: Reduction rate is 5% or more and less than 10%

[0768] D: Reduction rate less than 5%

[0769] (Evaluation of relative dielectric constant before and after exposure 1)

[0770] A photosensitive layer after exposure was prepared in the same manner as in the above (Evaluation of Relative Permittivity 1). The relative permittivity of each photosensitive layer was measured before and after exposure in the same manner as in the above (Evaluation of Relative Permittivity 1).

[0771] The relative dielectric constant of each photosensitive layer before exposure was set to 100%, and the degree of reduction in the dielectric constant of each photosensitive layer due to exposure was calculated and evaluated according to the following criteria.

[0772] It can be determined that the larger the reduction rate, the more the decrease in dielectric constant due to the decarboxylation reaction caused by light exposure progresses.

[0773] A: Reduction rate is more than 15%

[0774] B: Reduction rate is 10% or more and less than 15%

[0775] C: Reduction rate is 5% or more and less than 10%

[0776] D: Reduction rate less than 5%

[0777] <Evaluation of transfer film (photosensitive transfer material)>

[0778] (Production of transfer film)

[0779] On a polyethylene terephthalate film (manufactured by Toray Industries, Inc., 16KS40 (16QS62)) (temporary support) having a thickness of 16 μm, the photosensitive material of each embodiment or comparative example was adjusted and coated using a slit nozzle to have a thickness of 5 μm after drying, and then dried at 100°C for 2 minutes to form a photosensitive layer.

[0780] A 16 μm-thick polyethylene terephthalate film (16KS40 (16QS62) manufactured by Toray Industries, Inc.) (cover film) was pressure-bonded onto the obtained photosensitive layer to produce a transfer film of Example 1.

[0781] (Evaluation of Carboxyl Group Consumption Rate (IR Measurement))

[0782] The cover film was peeled off from the transfer film prepared above and then laminated onto a silicon wafer, transferring the photosensitive layer of the transfer film onto the surface of the silicon wafer. Lamination conditions were: a touch panel substrate temperature of 40°C, a rubber roller temperature (i.e., lamination temperature) of 110°C, a linear pressure of 3 N / cm, and a conveyor speed of 2 m / min.

[0783] The transferred photosensitive layer was exposed under the following exposure conditions.

[0784] Exposure Conditions

[0785] After the temporary support was peeled off, the entire surface of the photosensitive layer was exposed using a high-pressure mercury lamp. The cumulative exposure dose measured by an illuminometer at 365 nm was 1000 mJ / cm 2The light emitted from the high-pressure mercury lamp has a main wavelength of 365 nm and has strong line spectra at 254 nm, 313 nm, 405 nm, and 436 nm.

[0786] The IR spectrum of the photosensitive layer was measured before and after exposure, and the peak of the C=O stretch of the carboxyl group (1710 cm -1 The carboxyl group consumption rate (mol %) was calculated based on the decrease rate of the peak value of the reaction mixture.

[0787] The higher the carboxyl group consumption rate, the more the decarboxylation reaction proceeds.

[0788] The results are shown in Table 1 (see the column "Carboxyl group consumption rate (mol %) [IR measurement]").

[0789] (Evaluation of carboxyl group consumption rate (ashing measurement))

[0790] The cover film was peeled off from the transfer film prepared above and laminated onto a glass (Eagle XG manufactured by Corning Incorporated Co., Ltd.) 10×10 cm 2 The photosensitive layer of the transfer film was transferred onto the glass surface. Lamination conditions were: a touch panel substrate temperature of 40°C, a rubber roller temperature (i.e., lamination temperature) of 110°C, a linear pressure of 3 N / cm, and a conveying speed of 2 m / min.

[0791] ·Measurement of the amount of carboxyl groups in the photosensitive layer after exposure (Measurement of the amount of carboxyl groups after exposure)

[0792] The transferred photosensitive layer was exposed under the following exposure conditions.

[0793] Exposure Conditions

[0794] After the temporary support was peeled off, the entire surface of the photosensitive layer was exposed using a high-pressure mercury lamp. The cumulative exposure dose measured by an illuminometer at 365 nm was 1000 mJ / cm 2 The light emitted from the high-pressure mercury lamp has a main wavelength of 365 nm and has strong line spectra at 254 nm, 313 nm, 405 nm, and 436 nm.

[0795] Next, about 20 mg of the exposed photosensitive layer was scraped off and frozen and crushed, and then 150 μL of NMP (N-methyl-2-pyrrolidone) was added. The mixture was then stirred for 6 days in a lithium carbonate (Li2CO3) aqueous solution (1.2 g / 100 mL. Lithium carbonate was dissolved in ultrapure water and then filtered.).

[0796] After stirring, the particles were precipitated by ultracentrifugation (140,000 rpm x 30 min). The supernatant was replaced with ultrapure water (repeated five times), and the resulting precipitate was dried and solidified to serve as an analytical sample (n = 2 samples). This analytical sample was analyzed using ICP-OES (Optima 7300DV, manufactured by Perkin Elmer Co., Ltd.).

[0797] In addition, the above-mentioned ICP-OES measurement was carried out by the following procedure.

[0798] About 1.5 mg to 2 mg (n=3) of the above-mentioned analytical sample was weighed, and 5 mL of a 60% HNO 3 aqueous solution was added, followed by MW Teflon ashing (microwave sample decomposition apparatus Ultra WAVE max: 260° C.).

[0799] After ashing, ultrapure water was added to 50 mL, and the amount of Li was quantified using an ICP-OES (Optima 7300DV manufactured by Perkin Elmer Co., Ltd.) according to the absolute calibration curve method.

[0800] ·Measurement of the amount of carboxyl groups in the photosensitive layer before exposure (Measurement of the amount of carboxyl groups before exposure)

[0801] The amount of carboxyl groups in the photosensitive layer of each Example and Comparative Example was measured according to the following procedure.

[0802] 1 g of the photosensitive layer before exposure was scraped off and dissolved in 63 ml of tetrahydrofuran, to which 12 ml of ultrapure water was added. The resulting solution was then titrated with a 0.1N aqueous NaOH solution using an automatic titrator manufactured by HIRANUMACo., Ltd. The amount of carboxyl groups obtained by titration was converted to solid content concentration to calculate the amount of carboxyl groups in the photosensitive layer.

[0803] Calculation of decarboxylation rate

[0804] Based on the measurement results of the carboxyl group amounts before and after the exposure, the decarboxylation rate was calculated using the following formula.

[0805] Decarboxylation rate (%): {(amount of carboxyl groups before exposure - amount of carboxyl groups after exposure) / amount of carboxyl groups before exposure} × 100 (%)

[0806] Based on the obtained numerical values, evaluation was performed according to the following evaluation criteria.

[0807] However, the above method has a detection limit. When the carboxyl group content is 1.05 mmol / g or less, 90% or more of the Li can be substituted. In other regions, a calibration curve was prepared using a cross-linked polymer with a known acid value and calculations were performed.

[0808] Evaluation benchmark

[0809] A decarboxylation rate is 71 mol% or more

[0810] The B decarboxylation rate is 50 mol% or more and less than 71 mol%

[0811] The C decarboxylation rate is 31 mol% or more and less than 50 mol%

[0812] The D decarboxylation rate is 5 mol% or more and less than 31 mol%

[0813] E decarboxylation rate is less than 5 mol%

[0814] The results are shown in Table 1 (see the "Carboxyl group consumption rate [Ashing measurement]" column).

[0815] (365nm transmittance)

[0816] The transmittance of the photosensitive layer at 365 nm was measured using an ultraviolet-visible spectrophotometer UV1800 manufactured by Shimadzu Corporation, and evaluated based on the following evaluation criteria.

[0817] A transmittance is more than 90%

[0818] B transmittance is 65% or more and less than 90%

[0819] C transmittance is 20% or more and less than 65%

[0820] D transmittance is less than 20%

[0821] (365nm transmittance / 313nm transmittance)

[0822] The transmittance of the photosensitive layer at 365 nm and 313 nm was measured using an ultraviolet-visible spectrophotometer UV1800 manufactured by Shimadzu Corporation, and the value calculated by dividing the 365 nm transmittance by the 313 nm transmittance was evaluated as follows.

[0823] A 1.5 or more

[0824] B 1 or more and less than 1.5

[0825] C is less than 1

[0826] (Lamination suitability evaluation)

[0827] The cover film was peeled off from the transfer film produced above and laminated onto a copper-foil-laminated PET film (touch panel substrate) from GEOMATEC Co., Ltd. The photosensitive layer of the transfer film was transferred onto the surface of the copper foil, resulting in a laminate with a structure of "temporary support / photosensitive layer / copper foil / substrate (PET film)." Lamination conditions were: a touch panel substrate temperature of 40°C, a rubber roller temperature (i.e., lamination temperature) of 110°C, a linear pressure of 3 N / cm, and a conveying speed of 2 m / min. The copper foil served as a film for the touch panel wiring.

[0828] The area of ​​the photosensitive layer adhered to the copper foil without bubbles or floating was visually evaluated, and the ratio (%) of the adhered area was calculated based on the following formula and evaluated according to the following criteria. It is considered that the larger the adhered area (%), the better the lamination suitability.

[0829] Ratio of adhered area (%) = Area of ​​adhered photosensitive layer ÷ Area of ​​laminated transfer film × 100

[0830] A: The ratio of the adhered area (%) is 95% or more

[0831] B: The ratio of the adhered area (%) is less than 95%

[0832] (Pattern Formability Evaluation 2)

[0833] Next, the temporary support was peeled off from the laminate, and the exposed photosensitive layer was exposed using a high-pressure mercury lamp. During the exposure, the exposure was performed through any mask of the following (1) to (3). The cumulative exposure dose measured by a 365nm illuminometer was 1000mJ / cm 2 .

[0834] (1) Mask with line size = 25 μm and line:space = 1:1

[0835] (2) Mask with line size = 50 μm and line:space = 1:1

[0836] (3) Mask with line size = 250 μm and line:space = 1:1

[0837] The exposed photosensitive layer was then developed for 40 seconds using a 1% by mass sodium carbonate aqueous solution (liquid temperature: 32° C.) as a developer. After development, it was rinsed with pure water for 20 seconds and further air-blown to remove moisture, thereby obtaining a pattern (line and space pattern).

[0838] The line and space patterns having a line and space width of 25 μm, 50 μm, or 250 μm produced in this manner were evaluated in the same manner as described above (Pattern Formability Evaluation 1).

[0839] (Relative dielectric constant evaluation 2)

[0840] The cover film was peeled off from the transfer film prepared above and laminated onto an aluminum substrate with a thickness of 0.1 mm under the same conditions as described above (Lamination Suitability Evaluation). A laminate having a laminate structure of "temporary support / photosensitive layer / aluminum substrate" was obtained. Next, the temporary support was peeled off from the laminate. The exposed photosensitive layer was fully exposed using a high-pressure mercury lamp. The cumulative exposure measured with a 365 nm illuminometer was 1000 mJ / cm 2 .

[0841] The relative dielectric constant of the photosensitive layer after exposure was measured at 1 kHz using LCRmeter 4284A and Dielectric Test Fixture 16451B manufactured by Agilent Technologies, Inc. under an environment of 23° C. and 50% RH.

[0842] The relative dielectric constant of the photosensitive layer formed using the photosensitive material of Comparative Example 1A after exposure was set as 100%. Compared with this, the reduction rate of the relative dielectric constant of the photosensitive layer formed using the photosensitive material of each example after exposure was calculated and evaluated according to the following criteria.

[0843] As the value of the reduction rate increases, the relative dielectric constant decreases compared to Comparative Example 1A, indicating that the film is effective as an insulating film.

[0844] A: Reduction rate is more than 15%

[0845] B: Reduction rate is 10% or more and less than 15%

[0846] C: Reduction rate is 5% or more and less than 10%

[0847] D: Reduction rate less than 5%

[0848] (Evaluation of relative dielectric constant before and after exposure 2)

[0849] A photosensitive layer after exposure was prepared in the same manner as in the above (Evaluation of Relative Permittivity 2). The relative permittivity of each photosensitive layer was measured before and after exposure in the same manner as in the above (Evaluation of Relative Permittivity 2).

[0850] The relative dielectric constant of each photosensitive layer before exposure was set to 100%, and the degree of reduction in the dielectric constant of each photosensitive layer due to exposure was calculated and evaluated according to the following criteria.

[0851] It can be determined that the larger the reduction rate, the more the decrease in dielectric constant due to the decarboxylation reaction caused by light exposure progresses.

[0852] A: Reduction rate is more than 15%

[0853] B: Reduction rate is 10% or more and less than 15%

[0854] C: Reduction rate is 5% or more and less than 10%

[0855] D: Reduction rate less than 5%

[0856] (Evaluation of Water Vapor Permeability (WVTR))

[0857] Preparation of samples for moisture permeability measurement

[0858] The photosensitive material of each example or comparative example was applied onto a 75 μm thick polyethylene terephthalate (PET) film (temporary support) using a slit nozzle and then dried to form an 8 μm thick photosensitive layer to obtain a transfer film for sample preparation.

[0859] Next, the sample preparation transfer film was laminated onto PTFE (tetrafluoroethylene resin) membrane filter FP-100-100 manufactured by Sumitomo Electric Industries, Ltd., forming a laminate A having a layered structure of "temporary support / 8 μm thick photosensitive layer / membrane filter." Lamination conditions were: membrane filter temperature 40°C, lamination roller temperature 110°C, linear pressure 3 N / cm, and conveyor speed 2 m / min.

[0860] Next, the temporary support was peeled from the laminate A.

[0861] A transfer film for sample preparation was further laminated on the exposed photosensitive layer of the laminate A in the same manner, and the temporary support was peeled off from the obtained laminate four times to form a laminate B having a laminate structure of "photosensitive layer / membrane filter with a total film thickness of 40 μm".

[0862] The entire surface of the photosensitive layer of the obtained laminate B was exposed using a high-pressure mercury lamp. The cumulative exposure dose measured with an illuminometer at 365 nm was 1000 mJ / cm 2 .

[0863] In the above manner, a sample for measuring moisture permeability having a laminated structure of "photosensitive layer after exposure with a total film thickness of 40 μm / membrane filter" was obtained.

[0864] Determination of water vapor permeability (WVTR)

[0865] The moisture permeability measurement was performed using a sample for moisture permeability measurement according to the cup method in accordance with JIS-Z-0208 (1976).

[0866] First, a circular sample with a diameter of 70 mm was cut out from the sample for measuring moisture permeability. Next, 20 g of dried calcium chloride was placed in a measuring cup, and the circular sample was placed on the measuring cup to prepare a measuring cup with a lid.

[0867] The measuring cup with a lid was placed in a constant temperature and humidity chamber at 65°C and 90% RH for 24 hours. The water vapor permeability (WVTR) of the circular sample (unit: g / (m 2 ·day)).

[0868] The above measurement was performed three times, and the average value of WVTR in the three measurements was calculated.

[0869] Moisture permeability was evaluated based on the WVTR reduction rate (%) of each example, with the WVTR of Comparative Example 1A set as 100%. A larger reduction rate indicates a lower moisture permeability compared to Comparative Example 1A, making the film more suitable as a protective film. In the following evaluation criteria, A or B is preferred, with A being more preferred.

[0870] In the above-mentioned measurements, the WVTR of a circular sample having a laminated structure of "a photosensitive layer / membrane filter having a total thickness of 40 μm after exposure" was measured in the aforementioned manner. However, since the WVTR of the membrane filter is significantly higher than the WVTR of the photosensitive layer after exposure, the above-mentioned measurements essentially measure the WVTR of the photosensitive layer itself after exposure.

[0871] A: The reduction rate of WVTR is more than 20%

[0872] B: WVTR reduction rate is 10% or more and less than 20%

[0873] C: WVTR reduction rate is 7.5% or more and less than 10%

[0874] D: WVTR reduction rate is 5% or more and less than 7.5%

[0875] E: WVTR reduction rate is less than 5%

[0876] Results

[0877] Table 2 below shows the types and amounts of polymer A and compound β in the photosensitive materials of each example or comparative example in the Example 1 series, as well as the test results.

[0878] The "Amount" column in the table shows the amounts (parts by mass) of polymer A and compound β added to the photosensitive material. The amounts (parts by mass) are the amounts of polymer A and compound β themselves (solid content) added to the photosensitive material.

[0879] The column "Molar ratio of carboxyl groups relative to polymer A (mol %)" in the table indicates the ratio (mol %) of the total number of structures (structure b0) (preferably a structure (structure b) capable of accepting electrons from the carboxyl groups of polymer A in a photoexcited state) possessed by compound β that reduce the amount of carboxyl groups in polymer A relative to the total number of carboxyl groups possessed by polymer A in the photosensitive material.

[0880] The column “ε365” indicates the molar absorption coefficient of compound β in acetonitrile for light with a wavelength of 365 nm (cm·mol / L). -1 ).

[0881] The column “ε365 / ε313” indicates the molar absorption coefficient of compound β with respect to light of wavelength 365 nm (cm·mol / L). -1 ) divided by the molar absorption coefficient of compound β for light with a wavelength of 313 nm ((cm·mol / L) -1 ) and the values ​​obtained. In addition, the molar absorption coefficients are all values ​​in acetonitrile.

[0882] The column "365 nm transmittance" indicates the transmittance of the photosensitive layer with respect to light having a wavelength of 365 nm.

[0883] The column “365 nm transmittance / 313 nm transmittance” shows a value obtained by dividing the transmittance of the photosensitive layer with respect to light having a wavelength of 365 nm by the transmittance of the photosensitive layer with respect to light having a wavelength of 313 nm.

[0884] [Table 2]

[0885]

[0886]

[0887] [Table 3]

[0888]

[0889] From the results shown in the above table, it was confirmed that the problems of the present invention can be solved by using the photosensitive material of the present invention.

[0890] Furthermore, it was confirmed that, from the viewpoint of achieving a more excellent effect of the present invention, in the photosensitive material, the total number of structures b0 (preferably structure b) possessed by compound β is preferably 3 mol% or more, more preferably 5 mol% or more, and further preferably 10 mol% or more relative to the total number of carboxyl groups possessed by polymer A (see comparison of the results of reference Examples 1-4, 1-8, 1-9, 1-10, and 1-11, etc.).

[0891] Furthermore, it was confirmed that the molar absorption coefficient of compound β with respect to light of wavelength 365 nm was 1×10 3 (cm·mol / L) -1 In the case of the following compounds (preferably having a molar absorption coefficient of 1×10 2 (cm·mol / L) -1 In the case of the following compounds), pattern forming properties are further improved (see comparison of the results of Examples 1-1 to 1-7, etc.).

[0892] Furthermore, it was confirmed that the compound β in the photosensitive layer of the transfer film of the present invention has a molar absorption coefficient (cm·mol / L) relative to light of 365 nm wavelength. -1 ) / molar absorption coefficient relative to light with a wavelength of 313 nm ((cm·mol / L) -1 In the case of a compound in which the ratio represented by ) is 3 or less, pattern forming properties are more excellent (see comparison of the results of Examples 1-1 to 1-7, etc.).

[0893] [Example 2 Series]

[0894] Preparation and Evaluation of Photosensitive Materials

[0895] The materials listed in Table 3 shown in the latter section were mixed and dissolved in a mixed solvent of propylene glycol monomethyl ether acetate / methyl ethyl ketone = 50 / 50 (mass ratio) so as to satisfy the mixing ratio listed in Table 3 and to prepare a photosensitive material having a solid content concentration of 25% by mass.

[0896] Regarding the photosensitive materials obtained in Example 2 (photosensitive materials of Examples 2-1 to 2-8), the carboxyl group consumption rate (mol %) was confirmed by IR measurement in the same manner as shown in Example 1, and it was found that the carboxyl group consumption rate was 20 mol % or more.

[0897] Furthermore, the carboxyl group consumption rate, the pattern forming properties of the photosensitive material, the relative dielectric constant, and the change in the relative dielectric constant before and after exposure, as well as the lamination suitability, pattern forming properties, relative dielectric constant, the change in the relative dielectric constant before and after exposure, and the moisture permeability of the transfer film were evaluated in the same manner as in Example 1. Furthermore, in the same manner as in Example 1, the carboxyl group consumption rate, the transmittance relative to 365 nm light, and the ratio of the transmittance relative to 365 nm light to the transmittance relative to 313 nm light of the photosensitive layer in the transfer film were also evaluated. Furthermore, the physical properties of ε365 / ε313 of the compound β contained in the photosensitive material and the photosensitive layer were evaluated in the same manner as in Example 1.

[0898] The relative dielectric constant or moisture permeability of Comparative Example 2A was used as a criterion for the reduction rate in the evaluation of the relative dielectric constant of the photosensitive material and the evaluation of the relative dielectric constant and moisture permeability of the transfer film.

[0899] Table 3 below shows the solid content composition of the photosensitive material of each example or comparative example in the Example 2 series and the test results.

[0900] In the table, the values ​​listed in the "Solids Content" column represent the content (parts by mass) of each solid component contained in the photosensitive material of each Example or Comparative Example. Furthermore, the values ​​in parentheses for Compound β represent the ratio (mol %) of the total number of structures (Structure b0) (preferably, structures (Structure b)) of Compound β that reduce the number of carboxyl groups in Polymer A (preferably, structures capable of accepting electrons from carboxyl groups in Polymer A in a photoexcited state) relative to the total number of carboxyl groups in Polymer A in the photosensitive material.

[0901] The value (ε365) in the brackets described in the component name of compound β represents the molar absorption coefficient (cm·mol / L) of compound β in acetonitrile with respect to light of wavelength 365 nm. -1 ).

[0902] The value in brackets (pKa in the ground state) included in the component name of compound β represents the pKa in the ground state of compound β. The measurement method is as described above.

[0903] In the evaluation of the photosensitive material and the evaluation of the transfer film, the column "ε365 / ε313" indicates the molar absorption coefficient (cm·mol / L) of compound β with respect to light of a wavelength of 365 nm. -1 ) divided by the molar absorption coefficient of compound β for light with a wavelength of 313 nm ((cm·mol / L) -1) and the values ​​obtained. In addition, the molar absorption coefficients are all values ​​in acetonitrile.

[0904] In addition, the column "365 nm transmittance" in the evaluation of the transfer film indicates the transmittance of the photosensitive layer with respect to light having a wavelength of 365 nm.

[0905] In the evaluation of the transfer film, the column "365 nm transmittance / 313 nm transmittance" indicates the value obtained by dividing the transmittance of the photosensitive layer to light of a wavelength of 365 nm by the transmittance of the photosensitive layer to light of a wavelength of 313 nm.

[0906] [Table 4]

[0907]

[0908] UC3910: ARUFON UC3910 (manufactured by TOAGOSEI CO., LTD.)

[0909] DPHA: dipentaerythritol hexaacrylate (A-DPH manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[0910] A-NOD-N: 1,9-nonanediol diacrylate (A-NOD-N manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[0911] DTMPT: ditrimethylolpropane tetraacrylate (KAYARAD T-1420(T) manufactured by Nippon Kayaku Co., Ltd.)

[0912] A-DCP: dicyclopentane dimethanol diacrylate (A-DCP manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[0913] TMPT: trimethylolpropane triacrylate (A-TMPT manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[0914] F551: MEGAFACE F551 (manufactured by DIC Corporation)

[0915] From the results in the above table, it was confirmed that even when the photosensitive material contains a polymerizable compound, the problem of the present invention can be solved by the photosensitive material of the present invention.

[0916] Furthermore, it was confirmed that the conditions under which the effects of the present invention are more excellent also follow the same tendency as that confirmed for Example 1.

[0917] [Example 3 Series]

[0918] Preparation and Evaluation of Photosensitive Materials

[0919] The materials listed in Table 4 shown later were mixed and dissolved in a mixed solvent of propylene glycol monomethyl ether acetate / methyl ethyl ketone = 50 / 50 (mass ratio) so that the blending amounts listed in Table 4 were satisfied and the solid content concentration of the finally obtained photosensitive material was 25% by mass, thereby preparing a photosensitive material.

[0920] When preparing the photosensitive material, as the "synthesis method of resin A" or "synthesis method of resin B", resin A or resin B is introduced into the photosensitive material using a solution of resin A or a solution of resin B obtained by the method described later.

[0921] Regarding the photosensitive materials of Example 3 (photosensitive materials of Examples 3-1 to 3-12) obtained, the results of the carboxyl group consumption rate (molar ratio) were confirmed by IR measurement in the same manner as shown in Example 1 (Evaluation of carboxyl group consumption rate (IR measurement)), and it was found that the carboxyl group consumption rates were all above 20 mol%.

[0922] In addition, the following test was conducted: a 1000 mJ / cm2 high-pressure mercury lamp was used in the (Evaluation of Carboxyl Group Consumption Rate (IR Measurement)) described in Example 1. 2 Before exposure, an ultra-high pressure mercury lamp was used to expose 100 mJ / cm 2 Then, a high pressure mercury lamp was used to expose 1000 mJ / cm 2 Even if 100mJ / cm 2 In the case of exposure, when any of the photosensitive materials of Example 3 (photosensitive materials of Examples 3-1 to 3-12) is used, 1000 mJ / cm 2 The carboxyl group consumption rate before and after exposure was also 20 mol% or more.

[0923] The obtained photosensitive materials of each Example or Comparative Example in Example 3 were evaluated for carboxyl group consumption rate, relative dielectric constant of the photosensitive material, and change in relative dielectric constant before and after exposure, as well as lamination suitability, relative dielectric constant, change in relative dielectric constant before and after exposure, and moisture permeability of the transfer film, in the same manner as in Example 1. Furthermore, the photosensitive layer in the transfer film was evaluated for carboxyl group consumption rate, transmittance at 365 nm, and the ratio of transmittance at 365 nm to transmittance at 313 nm, in the same manner as in Example 1. Furthermore, the physical properties of ε365 / ε313 of compound β contained in the photosensitive material and the photosensitive layer were evaluated in the same manner as in Example 1.

[0924] The relative dielectric constant or moisture permeability of Comparative Example 3A was used as a criterion for the reduction rate in the evaluation of the relative dielectric constant of the photosensitive material and the evaluation of the relative dielectric constant and moisture permeability of the transfer film.

[0925] Furthermore, the pattern forming properties of the photosensitive materials of each example or comparative example in Example 3 were evaluated. The specific procedure for evaluating the pattern forming properties was the same as that of Example 1 (Pattern Forming Properties Evaluation 1), except that the pattern forming method was changed as follows.

[0926] The photosensitive material of each example or comparative example was spin-coated on a silicon wafer, and the obtained coating film was then dried at 80° C. using a hot plate to obtain a photosensitive layer with a film thickness of 5 μm.

[0927] The obtained photosensitive layer was exposed to light using an ultra-high pressure mercury lamp through the same mask as in Example 1. The cumulative exposure dose measured by an illuminometer at 365 nm was 100 mJ / cm 2 .

[0928] The pattern-exposed photosensitive layer was then developed for 40 seconds using a 1 mass % sodium carbonate aqueous solution (liquid temperature: 32° C.) as a developer. After development, the layer was rinsed with pure water for 20 seconds and further air was blown in to remove moisture, thereby obtaining a pattern.

[0929] The obtained pattern was exposed to light using a high-pressure mercury lamp. The cumulative exposure dose measured by a 365 nm illuminometer was 1000 mJ / cm 2 .

[0930] The line and space patterns having a line and space width of 25 μm, 50 μm, or 250 μm produced in this manner were evaluated based on the evaluation criteria described in (Pattern Formability Evaluation 1) of Example 1.

[0931] Furthermore, pattern forming properties were evaluated for the transfer films of each example or comparative example in Example 3. The specific procedure for evaluating pattern forming properties was the same as that described above (Pattern Forming Property Evaluation 2) for Example 1, except that the pattern forming method was changed as follows.

[0932] The cover film was peeled off from the prepared transfer film and laminated onto a COP film (touch panel substrate) laminated with copper foil. The photosensitive layer of the transfer film was then transferred onto the surface of the copper foil, resulting in a laminate with a structure of "temporary support / photosensitive layer / copper foil / substrate (COP film)." Lamination conditions were as follows: a touch panel substrate temperature of 40°C, a rubber roller temperature (i.e., lamination temperature) of 110°C, a linear pressure of 3 N / cm, and a conveying speed of 2 m / min. The copper foil served as the wiring for the touch panel.

[0933] As a result, the lamination properties were good.

[0934] Next, a proximity exposure machine (Hitachi High-Tech Corporation) equipped with an ultra-high pressure mercury lamp was used, and the distance between the exposure mask surface and the surface of the temporary support was set to 125 μm. The ultra-high pressure mercury lamp was used at an exposure dose of 100 mJ / cm 2 The photosensitive layer of the laminate was pattern-exposed via a temporary support under the conditions of (i-ray).

[0935] The mask was a line and space pattern mask similar to that of Example 1. After exposure, the temporary support was peeled off from the laminate.

[0936] The photosensitive layer of the laminate from which the temporary support was peeled was then developed for 40 seconds using a 1% by mass sodium carbonate aqueous solution (liquid temperature: 32° C.) as a developer. After development, the laminate was washed with pure water for 20 seconds and air was blown in to remove moisture, thereby obtaining a pattern.

[0937] The obtained pattern was exposed to light using a high-pressure mercury lamp. The cumulative exposure dose measured by a 365 nm illuminometer was 1000 mJ / cm 2 .

[0938] The line and space patterns having a line and space width of 25 μm, 50 μm, or 250 μm produced in this manner were evaluated based on the evaluation criteria described in (Pattern Formability Evaluation 1) of Example 1.

[0939] <Evaluation of relative dielectric constant under double exposure conditions>

[0940] In Example 3, the relative dielectric constant was also evaluated under double exposure conditions. The relative dielectric constant evaluation under single exposure conditions refers to the evaluation of the relative dielectric constant under the same conditions as those described above (Relative Dielectric Constant Evaluation 2) in Example 1.

[0941] Regarding the photosensitive material of Example 3, a transfer film was produced in the same manner as described in Example 1 (Production of Transfer Film). The cover film was peeled from the obtained transfer film, and the transfer film was laminated on a 0.1 mm thick aluminum substrate under the same conditions as described above (Lamination Suitability Evaluation), resulting in a laminate having a laminate structure of "temporary support / photosensitive layer / aluminum substrate."

[0942] The first exposure was performed on the laminate using an ultra-high pressure mercury lamp and the entire surface of the photosensitive layer was exposed through a temporary support. In the first exposure, the cumulative exposure dose measured by a 365 nm illuminometer was 100 mJ / cm 2 In addition, since the first exposure is performed through the temporary support (polyethylene terephthalate), most of the light with a wavelength below 320nm is blocked. Therefore, it is believed that the material with a large molar absorption coefficient for light with a wavelength of 365nm (for example, 1×10 3 (cm·mol / L) -1 above) preferentially participate in the reaction.

[0943] Then, the temporary support was peeled off from the laminate, and the entire surface of the photosensitive layer was exposed using a high-pressure mercury lamp as the second exposure. In the second exposure, the cumulative exposure dose measured by a 365 nm illuminometer was 1000 mJ / cm 2 .

[0944] The relative dielectric constant of the photosensitive layer exposed in this manner was measured in the same manner as in the above (relative dielectric constant evaluation 2) described in Example 1.

[0945] However, as a reference of the relative dielectric constant, the relative dielectric constant of Comparative Example 3A under the double exposure condition was used.

[0946] Table 4 below shows the solid content composition of the photosensitive material of each example or comparative example in the Example 3 series and the test results.

[0947] In Table 4, the same entries as those in Table 3 have the same meanings as those described in Table 3.

[0948] [Table 5]

[0949]

[0950] Resin A: Resin with the following structure (acid value: 94.5 mgKOH / g)

[0951] [Chemical Formula 8]

[0952]

[0953] Synthesis method of resin A

[0954] 200 g of propylene glycol monomethyl ether and 50 g of propylene glycol monomethyl ether acetate were added to a flask and heated to 90° C. under a nitrogen stream. A solution of 192.9 g of cyclohexyl methacrylate, 4.6 g of methyl methacrylate, and 89.3 g of methacrylic acid dissolved in 60 g of propylene glycol monomethyl ether acetate, and a solution of 9.2 g of polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) dissolved in 114.8 g of propylene glycol monomethyl ether acetate were simultaneously added dropwise to the liquid over 3 hours. After the dropwise addition was completed, a solution of 2 g of V-601 dissolved in 10 g of propylene glycol monomethyl ether acetate was added three times at 1 hour intervals. The mixture was then allowed to react for a further 3 hours. The mixture was diluted with 168.7 g of propylene glycol monomethyl ether acetate. Under air flow, the reaction solution was heated to 100°C, and 1.5 g of tetraethylammonium bromide and 0.67 g of p-methoxyphenol were added. 63.4 g of glycidyl methacrylate (BLEMMER GH manufactured by NOF CORPORATION) was added dropwise thereto over 20 minutes. The mixture was reacted at 100°C for 6 hours to obtain a solution of resin A. The solid content concentration of the obtained solution was 36.2%. The weight average molecular weight converted to standard polystyrene in GPC was 27,000, the dispersity was 2.9, and the acid value of the polymer was 94.5 mgKOH / g. The amount of residual monomers measured using a gas chromatograph was less than 0.1% by mass relative to the polymer solid content in any monomer.

[0955] Resin B: Resin with the following structure (acid value: 94.5 mgKOH / g)

[0956] [Chemical Formula 9]

[0957]

[0958] Synthesis method of resin B

[0959] 82.4 g of propylene glycol monomethyl ether was placed in a flask and heated to 90° C. under a nitrogen stream. To this liquid, a solution in which 38.4 g of styrene, 30.1 g of dicyclopentanyl methacrylate, and 34.0 g of methacrylic acid were dissolved in 20 g of propylene glycol monomethyl ether, and a solution in which 5.4 g of polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) was dissolved in 43.6 g of propylene glycol monomethyl ether acetate were simultaneously added dropwise over 3 hours. After the dropwise addition was completed, 0.75 g of V-601 was added three times every hour. Then, the reaction was allowed to react for a further 3 hours. Thereafter, the mixture was diluted with 58.4 g of propylene glycol monomethyl ether acetate and 11.7 g of propylene glycol monomethyl ether. Under an air stream, the reaction solution was heated to 100° C., and 0.53 g of tetraethylammonium bromide and 0.26 g of p-methoxyphenol were added. 25.5 g of glycidyl methacrylate (BLEMMER GH manufactured by NOF CORPORATION) was added dropwise thereto over 20 minutes. The mixture was reacted at 100°C for 7 hours to obtain a solution of Resin B. The solid content concentration of the obtained solution was 36.2%. The weight-average molecular weight in terms of standard polystyrene in GPC was 17,000, the dispersity was 2.4, and the acid value of the polymer was 94.5 mgKOH / g. The amount of residual monomer measured using a gas chromatograph was less than 0.1% by mass relative to the polymer solid content in any monomer.

[0960] DPHA: dipentaerythritol hexaacrylate (A-DPH manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[0961] A-NOD-N: 1,9-nonanediol diacrylate (A-NOD-N manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[0962] DTMPT: ditrimethylolpropane tetraacrylate (KAYARAD T-1420(T) manufactured by Nippon Kayaku Co., Ltd.)

[0963] A-DCP: dicyclopentane dimethanol diacrylate (A-DCP manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[0964] TMPT: trimethylolpropane triacrylate (A-TMPT manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[0965] F551: MEGAFACE F551 (manufactured by DIC Corporation)

[0966] OXE-02: Irgacure OXE02 (manufactured by BASF, oxime ester compound). Molar absorption coefficient in acetonitrile for light at a wavelength of 365 nm: 2700 (cm·mol / L). -1

[0967] Omn907: Omnirad 907 (manufactured by IGM Resins BV, aminoacetophenone compound) with a molar absorption coefficient of 120 (cm·mol / L) in acetonitrile for light at a wavelength of 365 nm. -1

[0968] As shown in the table, it was confirmed that the photosensitive material according to the present invention can solve the problems of the present invention even when the photosensitive material contains a photopolymerization initiator.

[0969] Furthermore, it was confirmed that the conditions under which the effects of the present invention are more excellent also follow the same tendency as that confirmed for Example 1.

[0970] [Evaluation under Double Exposure Conditions of a Layer Having a Photosensitive Layer and a Second Resin Layer Formed Using the Photosensitive Material of Example 3]

[0971] <Production of transfer film>

[0972] (Formation of Photosensitive Layer)

[0973] On a polyethylene terephthalate film (manufactured by Toray Industries, Inc., 16KS40) (temporary support) having a thickness of 16 μm, a photosensitive material liquid of each embodiment shown in Example 3 was adjusted and applied to a thickness of 5 μm after drying using a slit nozzle, and then dried at 100°C for 2 minutes to form a photosensitive layer.

[0974] (Formation of Second Resin Layer)

[0975] Next, a second resin layer coating liquid having the following formulation 201 was prepared and applied onto the photosensitive layer to a thickness of 70 nm after drying. The coating was then dried at 80°C for 1 minute and then at 110°C for 1 minute, forming a second resin layer directly in contact with the photosensitive layer. The second resin layer had a thickness of 70 nm and a refractive index of 1.68.

[0976] In addition, formulation 201 is prepared using an acidic resin and an aqueous ammonia solution, and the acidic resin is neutralized by the aqueous ammonia solution. In other words, the second resin layer coating liquid is an aqueous resin composition containing an ammonium salt of the acidic resin.

[0977] Second resin layer coating liquid: Formulation 201 (water-based resin composition)

[0978] Acrylic resin (resin having an acid group, copolymerized resin of methacrylic acid / allyl methacrylate, weight average molecular weight 25,000, composition ratio (molar ratio) = 40 / 60, solid content 99.8%): 0.29 parts

[0979] ARONIX TO-2349 (monomer having a carboxyl group, manufactured by TOAGOSEI CO., LTD.): 0.04 parts

[0980] Nanouse OZ-S30M (ZrO2 particles, solid content 30.5%, methanol 69.5%, refractive index 2.2, average particle size: approximately 12 nm, manufactured by NISSAN CHEMICAL INDUSTRIES, LTD.): 4.80 parts

[0981] BT120 (benzotriazole, manufactured by JOHOKU CHEMICAL CO., LTD.): 0.03 parts

[0982] MEGAFACE F444 (fluorinated surfactant, manufactured by DIC Corporation): 0.01 part

[0983] Aqueous ammonia solution (2.5% by mass): 7.80 parts

[0984] Distilled water: 24.80 parts

[0985] Methanol: 76.10 parts

[0986] (Formation of Pattern)

[0987] A 16 μm thick polyethylene terephthalate film (16KS40, manufactured by Toray Industries, Inc.) (cover film) was pressure-bonded to the second resin layer of the laminate obtained in the above manner, in which a photosensitive layer was sequentially provided on a temporary support and a second resin layer was disposed in direct contact therewith. Thus, a transfer film (photosensitive transfer material) having a photosensitive layer and a second resin layer formed using the photosensitive materials of each Example 3 series was prepared.

[0988] The cover film was peeled off from the transfer film produced above and laminated onto a PET film (touch panel substrate) laminated with copper foil from GEOMATEC Co., Ltd. The photosensitive layer of the transfer film was transferred onto the surface of the copper foil, resulting in a laminate with a structure of "temporary support / photosensitive layer / second resin layer / copper foil / substrate (PET film)." Lamination conditions were as follows: touch panel substrate temperature of 40°C, rubber roller temperature (i.e., lamination temperature) of 110°C, linear pressure of 3 N / cm, and conveying speed of 2 m / min. The copper foil served as a film for the touch panel wiring.

[0989] The lamination properties were good and comparable to those of the transfer films of Example 3 which did not have the second resin layer.

[0990] Next, a proximity exposure machine (Hitachi High-Tech Corporation) equipped with an ultra-high pressure mercury lamp was used. The distance between the exposure mask (a quartz exposure mask having a pattern for forming a protective layer) and the surface of the temporary support was set to 125 μm. The ultra-high pressure mercury lamp was used to expose the film at an exposure dose of 100 mJ / cm 2 The photosensitive layer of the laminate was pattern-exposed via a temporary support under the conditions of (i-ray).

[0991] During exposure, exposure was performed through a mask having a line size of 50 μm and a line:space ratio of 1:1, or a mask having a line size of 250 μm and a line:space ratio of 1:1.

[0992] After the exposure, the temporary support was peeled off from the laminate.

[0993] Next, a 1% by mass aqueous solution of sodium carbonate (liquid temperature: 32° C.) was used as a developer to develop the photosensitive layer of the laminate from which the temporary support was peeled off for 40 seconds. After development, the laminate was washed with pure water for 20 seconds, and air was blown in to remove moisture to obtain a pattern. The obtained pattern was fully exposed using a high-pressure mercury lamp. The cumulative exposure measured by a 365nm illuminometer was 1000mJ / cm 2 .

[0994] The results of evaluating the line and space patterns with a line and space width of 50 μm or 250 μm produced in this manner in the same manner as described above (Pattern Formability Evaluation 1) showed that the evaluation results were equally good as those obtained when the pattern was formed and evaluated in the same manner as the transfer films of Example 3 that did not have a second resin layer.

[0995] That is, the photosensitive material of the present invention including the polymerizable compound and the photopolymerization initiator has good pattern forming properties even under two-stage exposure conditions.

[0996] A PET film having an ITO coating assumed to be a transparent electrode for a touch panel was used instead of a PET film laminated with copper foil, and the same evaluation conditions as the evaluation under double exposure conditions of a layer having a photosensitive layer and a second resin layer formed using the photosensitive material of Example 3 were performed. The results showed good lamination properties and pattern forming properties, just like the case of using a PET film laminated with copper foil.

[0997] [Example 4 Series]

[0998] The following Table 5 shows the structure of the polymer A used in Example 4. In addition, the polymer A used was a polymer synthesized by a known method.

[0999] Hereinafter, a method for synthesizing the polymer of Compound No. 1 will be described as a representative example.

[1000] (Synthesis of Polymer of Compound No. 1)

[1001] PGMEA (60 parts) and PGME (240 parts) were placed in a 2000 mL flask, and the resulting liquid was heated to 90° C. while stirring at a stirring speed of 250 rpm (round per minute; the same shall apply hereinafter).

[1002] As preparation of the dropping solution (1), styrene (47.7 parts), methyl methacrylate (1.3 parts) and methacrylic acid (51 parts) were mixed, and the mixture was diluted with PGMEA (60 parts) to obtain the dropping solution (1).

[1003] As preparation of the dropping solution (2), V-601 (dimethyl 2,2′-azobis(2-methylpropionate)) (9.637 parts) was dissolved in PGMEA (136.56 g) to obtain the dropping solution (2).

[1004] The dropwise addition liquid (1) and the dropwise addition liquid (2) were simultaneously added dropwise to the 2000 mL flask (specifically, a 2000 mL flask containing the liquid heated to 90°C) over 3 hours. After the dropwise addition was completed, V-601 (2.401 g) was added to the flask three times at 1-hour intervals. The mixture was then stirred at 90°C for an additional 3 hours.

[1005] The solution (reaction solution) obtained in the flask was then diluted with PGMEA (178 parts). Tetraethylammonium bromide (1.8 parts) and hydroquinone monomethyl ether (0.8 parts) were then added to the reaction solution. The temperature of the reaction solution was then raised to 100°C.

[1006] Next, glycidyl methacrylate was added dropwise to the reaction solution over 1 hour in an amount corresponding to the composition of Compound No. 1 in Table 5. The reaction solution was reacted at 100° C. for 6 hours to obtain a polymer solution (solid content concentration: 36.3% by mass).

[1007] The weight average molecular weight of the polymer A shown in Table 5 is within the range of 10,000 to 50,000 as shown in Table 5.

[1008] In addition, the numerical values ​​of the structural units in Table 5 represent mass ratios.

[1009] In the Polymer A column of Table 5, the abbreviations of the monomers forming the structural units of the polymer are as follows. GMA-MAA represents a structural unit obtained by adding glycidyl methacrylate to a structural unit derived from methacrylic acid, and GMA-AA represents a structural unit obtained by adding glycidyl methacrylate to a structural unit derived from acrylic acid.

[1010] St:Styrene

[1011] CHMA: Cyclohexyl methacrylate

[1012] CHA: Cyclohexyl acrylate

[1013] MMA: Methyl Methacrylate

[1014] EA: Ethyl acrylate

[1015] BzMA: benzyl methacrylate

[1016] BzA: benzyl acrylate

[1017] HEMA: 2-Hydroxyethyl Methacrylate

[1018] HEA: 2-Hydroxyethyl Acrylate

[1019] MAA: Methacrylic acid

[1020] AA: Acrylic acid

[1021] [Table 6]

[1022]

[1023] Preparation and Evaluation of Photosensitive Materials

[1024] The materials listed in Table 6 shown in the latter section were mixed and dissolved in a mixed solvent of propylene glycol monomethyl ether acetate / methyl ethyl ketone = 50 / 50 (mass ratio) so that the mixing amounts listed in Table 6 were satisfied and the solid content concentration of the finally obtained photosensitive material was 25% by mass, thereby preparing a photosensitive material.

[1025] In Table 6 below, the examples and comparative examples are represented by the head number + the sequence number. That is, Example 4-1-1 corresponds to Example 4-1 and the sequence number 1. Furthermore, Comparative Example 4A-1 corresponds to Example 4A and the sequence number 1.

[1026] Furthermore, the carboxyl group consumption rate, the pattern forming properties of the photosensitive material, the relative dielectric constant, and the change in the relative dielectric constant before and after exposure, as well as the lamination suitability, pattern forming properties, relative dielectric constant, the change in the relative dielectric constant before and after exposure, and the moisture permeability of the transfer film were evaluated in the same manner as in Example 1. Furthermore, the carboxyl group consumption rate, the transmittance at 365 nm, and the ratio of the transmittance at 365 nm to the transmittance at 313 nm of the photosensitive layer in the transfer film were also evaluated in the same manner as in Example 1. Furthermore, the physical properties of ε365 / ε313 of the compound β contained in the photosensitive material and the photosensitive layer were evaluated in the same manner as in Example 1.

[1027] The basis for the reduction rate in the evaluation of the relative dielectric constant of the photosensitive material and the evaluation of the relative dielectric constant and moisture permeability of the transfer film was the relative dielectric constant or moisture permeability of the comparative example with the same serial number. For example, in the case of Example 4-1-1, since the serial number was 1, the comparative example 4A-1 with the same serial number met the standard. Furthermore, in the case of Example 4-27-51, since the serial number was 51, the comparative example 4A-51 with the same serial number met the standard.

[1028] Table 6 below shows the solid content composition of the photosensitive material of each example or comparative example in the Example 4 series and the test results.

[1029] In the table, the "Compound No." in the "Polymer A" column corresponds to the "Compound No." described in Table 5 above.

[1030] In the table, the values ​​listed in the "parts by mass" column represent the solid content of each component (parts by mass). In addition, the above-mentioned amounts (parts by mass) are the amounts of "polymer A" and "compound β" themselves (solid content) added to the photosensitive material.

[1031] In addition, the value of "Molar ratio of carboxyl groups relative to polymer A (mol %)" of compound β in the table is expressed as follows: in the photosensitive material, the ratio (mol %) of the total number of structures (structure b0) (preferably a structure (structure b) capable of accepting electrons from carboxyl groups contained in polymer A in a photoexcited state) possessed by compound β to the total number of carboxyl groups possessed by polymer A.

[1032] In the evaluation of the photosensitive material and the evaluation of the transfer film, the column "ε365 / ε313" indicates the molar absorption coefficient (cm·mol / L) of compound β with respect to light of a wavelength of 365 nm. -1 ) divided by the molar absorption coefficient of compound β for light with a wavelength of 313 nm ((cm·mol / L) -1 ) and the values ​​obtained. In addition, the molar absorption coefficients are all values ​​in acetonitrile.

[1033] In addition, the column "365 nm transmittance" in the evaluation of the transfer film indicates the transmittance of the photosensitive layer with respect to light having a wavelength of 365 nm.

[1034] In the evaluation of the transfer film, the column "365 nm transmittance / 313 nm transmittance" indicates the value obtained by dividing the transmittance of the photosensitive layer to light of a wavelength of 365 nm by the transmittance of the photosensitive layer to light of a wavelength of 313 nm.

[1035] In Table 6, the types of compound β used for preparation of the photosensitive material are indicated by symbols.

[1036] The correspondence between the type and symbol of compound β is shown below. The determination method of "pKa in the ground state" described below for each compound β is as described above. "ε365" represents the molar absorption coefficient (cm·mol / L) of compound β in acetonitrile for light with a wavelength of 365 nm. -1 ).

[1037]

[1038]

[1039]

[1040]

[1041]

[1042]

[1043]

[1044]

[1045]

[1046]

[1047]

[1048]

[1049]

[1050]

[1051]

[1052]

[1053]

[1054]

[1055]

[1056]

[1057]

[1058]

[1059]

[1060]

[1061]

[1062]

[1063]

[1064]

[1065]

[1066]

[1067]

[1068]

[1069] From the results in the above table, it was confirmed that the transfer film of the present invention can solve the problems of the present invention.

[1070] Furthermore, it was confirmed that the conditions under which the effects of the present invention are more excellent also follow the same tendency as that confirmed for Example 1.

[1071] [Example 5 Series]

[1072] Preparation and Evaluation of Photosensitive Materials

[1073] The materials listed in Table 7 shown later were mixed and dissolved in a mixed solvent of propylene glycol monomethyl ether acetate / methyl ethyl ketone = 50 / 50 (mass ratio) so that the solid content concentration of the finally obtained photosensitive material would be 25 mass %, thereby preparing a photosensitive material.

[1074] The obtained photosensitive materials of each Example or Comparative Example in Example 5 were evaluated for carboxyl group consumption rate, pattern forming properties of the photosensitive material, relative dielectric constant, and change in relative dielectric constant before and after exposure, as well as the lamination suitability, pattern forming properties, relative dielectric constant, change in relative dielectric constant before and after exposure, and moisture permeability of the transfer film, in the same manner as in Example 1. Furthermore, the carboxyl group consumption rate, transmittance at 365 nm, and the ratio of transmittance at 365 nm to transmittance at 313 nm of the photosensitive layer in the transfer film were also evaluated in the same manner as in Example 1.

[1075] The relative dielectric constant or moisture permeability of Comparative Example 5A was used as a criterion for the reduction rate in the evaluation of the relative dielectric constant of the photosensitive material and the evaluation of the relative dielectric constant and moisture permeability of the transfer film.

[1076] Table 7 below shows the solid content composition of the photosensitive material of each example or comparative example in the Example 5 series and the test results.

[1077] In addition, the solid content in the photosensitive material of each example shown in Example 5 is a composition in which the polymer A is 100% by mass. In addition, the polymer A used in each example shown in Example 5 corresponds to the polymer Ab.

[1078] In the table, the column "x / y / z" indicates the mass ratio of each structural unit constituting polymer A.

[1079] The weight average molecular weights of the polymers A shown in Table 7 are all 10,000 to 50,000 as shown in Table 7.

[1080] In addition, the column "365 nm transmittance" in the evaluation of the transfer film indicates the transmittance of the photosensitive layer with respect to light having a wavelength of 365 nm.

[1081] In the evaluation of the transfer film, the column "365 nm transmittance / 313 nm transmittance" indicates the value obtained by dividing the transmittance of the photosensitive layer to light of a wavelength of 365 nm by the transmittance of the photosensitive layer to light of a wavelength of 313 nm.

[1082] In addition, the description of St / AA in the table|surface represents a styrene / acrylic acid copolymer (composition ratio: repeating unit based on styrene / repeating unit based on acrylic acid=80 / 20 (mass ratio)).

[1083]

[1084] From the results in the above table, it was confirmed that the transfer film of the present invention can solve the problems of the present invention.

[1085] [Example 6 Series]

[1086] Preparation and Evaluation of Photosensitive Materials

[1087] The materials listed in Table 8 shown in the latter section were mixed and dissolved in a mixed solvent of propylene glycol monomethyl ether acetate / methyl ethyl ketone = 50 / 50 (mass ratio) so that the mixing amounts listed in Table 8 were satisfied and the solid content concentration of the finally obtained photosensitive material was 25% by mass, thereby preparing a photosensitive material.

[1088] Furthermore, the carboxyl group consumption rate, pattern forming properties of the photosensitive material, relative dielectric constant, and relative dielectric constant change before and after exposure, as well as the lamination suitability, pattern forming properties, relative dielectric constant, relative dielectric constant change before and after exposure, and moisture permeability of the transfer film were evaluated in the same manner as in Example 1. Furthermore, the carboxyl group consumption rate, transmittance at 365 nm, and the ratio of transmittance at 365 nm to transmittance at 313 nm of the photosensitive layer in the transfer film were also evaluated in the same manner as in Example 1. Furthermore, the physical properties of ε365 / ε313 of the compound β contained in the photosensitive material and the photosensitive layer were evaluated in the same manner as in Example 1.

[1089] The relative dielectric constant or moisture permeability of Comparative Example 6A was used as a criterion for the reduction rate in the evaluation of the relative dielectric constant of the photosensitive material and the evaluation of the relative dielectric constant and moisture permeability of the transfer film.

[1090] Table 8 below shows the solid content composition of the photosensitive material of each example or comparative example in the Example 6 series and the test results.

[1091] In the table, the values ​​listed in the "Solids Content" column represent the content (parts by mass) of each solid component contained in the photosensitive material of each Example or Comparative Example. Furthermore, the values ​​in parentheses for Compound β represent the ratio (mol %) of the total number of structures (Structure b0) (preferably, structures (Structure b) capable of accepting electrons from carboxyl groups contained in Polymer A in a photoexcited state) contained in Compound β relative to the total number of carboxyl groups contained in Polymer A in the photosensitive material.

[1092] In addition, the measurement method of "pKa of compound β in the ground state" in the table is as described above.

[1093] In addition, the column "ε365 of compound β" in the table shows the molar absorption coefficient (cm·mol / L) of compound β in acetonitrile with respect to light of wavelength 365 nm. -1 ).

[1094] In the evaluation of the photosensitive material and the evaluation of the transfer film, the column "ε365 / ε313" indicates the molar absorption coefficient (cm·mol / L) of compound β with respect to light of a wavelength of 365 nm. -1 ) divided by the molar absorption coefficient of compound β for light of wavelength 365 nm ((cm·mol / L) -1 ) and the values ​​obtained. In addition, the molar absorption coefficients are all values ​​in acetonitrile.

[1095] In addition, the column "365 nm transmittance" in the evaluation of the transfer film indicates the transmittance of the photosensitive layer with respect to light having a wavelength of 365 nm.

[1096] In the evaluation of the transfer film, the column "365 nm transmittance / 313 nm transmittance" indicates the value obtained by dividing the transmittance of the photosensitive layer to light of a wavelength of 365 nm by the transmittance of the photosensitive layer to light of a wavelength of 313 nm.

[1097]

[1098]

[1099]

[1100]

[1101]

[1102]

[1103]

[1104]

[1105]

[1106]

[1107]

[1108] (Polymer A)

[1109] Polymers 1 to 4 corresponding to polymer A were synthesized by the same method as in Example 4. The abbreviations of monomers constituting each structural unit of the polymer are as described above.

[1110] Polymer 1: St / MAA / MMA / gMA-MAA=47.7 / 19.0 / 1.3 / 32.0 (mass ratio)

[1111] Polymer 2: CHMA / MAA / BzMA = 49 / 19 / 32 (mass ratio)

[1112] Polymer 3: St / AA / AA-GMA = 53.5 / 14.5 / 32 (mass ratio)

[1113] Polymer 4: CHA / AA / HEA = 53.5 / 14.5 / 32 (mass ratio)

[1114] In addition, as shown in Table 8, the weight average molecular weights of the polymers A are all within the range of 10,000 to 50,000.

[1115] (Polymerizable compound)

[1116] DPHA: dipentaerythritol hexaacrylate (A-DPH manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[1117] A-NOD-N: 1,9-nonanediol diacrylate (A-NOD-N manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[1118] DTMPT: ditrimethylolpropane tetraacrylate (KAYARAD T-1420(T) manufactured by Nippon Kayaku Co., Ltd.)

[1119] A-DCP: dicyclopentane dimethanol diacrylate (A-DCP manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[1120] TMPT: trimethylolpropane triacrylate (A-TMPT manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[1121] SR601: Ethoxylated (4) bisphenol A diacrylate (SR601 manufactured by TOMOE ENGINEERING CO., LTD.)

[1122] KRM8904: 9-functional aliphatic acrylic urethane (KRM8904 manufactured by DAICEL-ALLNEX LTD.)

[1123] KRM8452: 10-functional aliphatic acrylic urethane (KRM8452 manufactured by DAICEL-ALLNEX LTD.)

[1124] (Surfactant)

[1125] F551: MEGAFACE F551 (manufactured by DIC Corporation)

[1126] R41: MEGAFACE R-41 (manufactured by DIC Corporation)

[1127] 710FL: TERGENT 710FL (manufactured by Neos Corporation)

[1128] From the results in the above table, it was confirmed that the problems of the present invention can be solved by the transfer film of the present invention even when the photosensitive material contains a polymerizable compound.

[1129] [Example 7 Series]

[1130] Preparation and Evaluation of Photosensitive Materials

[1131] The materials listed in Table 9 shown in the latter section were mixed and dissolved in a mixed solvent of propylene glycol monomethyl ether acetate / methyl ethyl ketone = 50 / 50 (mass ratio) so as to satisfy the mixing ratio listed in Table 9 and to make the solid content concentration of the finally obtained photosensitive material be 25% by mass, thereby preparing a photosensitive material.

[1132] Furthermore, the carboxyl group consumption rate, the pattern forming properties of the photosensitive material, the relative dielectric constant, and the change in the relative dielectric constant before and after exposure, as well as the lamination suitability of the transfer film, the pattern forming properties, the relative dielectric constant, the change in the relative dielectric constant before and after exposure, the moisture permeability, and the change in the relative dielectric constant after two exposures of the photosensitive material of each example or comparative example in Example 7 were evaluated in the same manner as in Example 1. Furthermore, the carboxyl group consumption rate, the transmittance relative to 365 nm light, and the ratio of the transmittance relative to 313 nm light to the transmittance relative to 313 nm light of the photosensitive layer in the transfer film were also evaluated in the same manner as in Example 3. Furthermore, the physical properties of ε365 / ε313 of the compound β contained in the photosensitive material and the photosensitive layer were evaluated in the same manner as in Example 1.

[1133] The relative dielectric constant or moisture permeability of Comparative Example 7A was used as a criterion for the reduction rate in the evaluation of the relative dielectric constant of the photosensitive material and the evaluation of the relative dielectric constant and moisture permeability of the transfer film.

[1134] Table 9 below shows the solid content composition of the photosensitive material of each example or comparative example in the Example 7 series and the test results.

[1135] In the table, the values ​​listed in the "Solids Content" column represent the content (parts by mass) of each solid component contained in the photosensitive material of each Example or Comparative Example. Furthermore, the values ​​in parentheses for Compound β represent the ratio (mol %) of the total number of structures (Structure b0) (preferably, structures (Structure b) capable of accepting electrons from carboxyl groups contained in Polymer A in a photoexcited state) contained in Compound β relative to the total number of carboxyl groups contained in Polymer A in the photosensitive material.

[1136] In addition, the measurement method of "pKa of compound β in the ground state" in the table is as described above.

[1137] In addition, the column "ε365 of compound β" in the table shows the molar absorption coefficient (cm·mol / L) of compound β in acetonitrile with respect to light of wavelength 365 nm. -1 ).

[1138] In the evaluation of the photosensitive material and the evaluation of the transfer film, the column "ε365 / ε313" indicates the molar absorption coefficient (cm·mol / L) of compound β with respect to light of a wavelength of 365 nm. -1 ) divided by the molar absorption coefficient of compound β for light with a wavelength of 313 nm ((cm·mol / L) -1) and the values ​​obtained. In addition, the molar absorption coefficients are all values ​​in acetonitrile.

[1139] In addition, the column "365 nm transmittance" in the evaluation of the transfer film indicates the transmittance of the photosensitive layer with respect to light having a wavelength of 365 nm.

[1140] In the evaluation of the transfer film, the column "365 nm transmittance / 313 nm transmittance" indicates the value obtained by dividing the transmittance of the photosensitive layer to light of a wavelength of 365 nm by the transmittance of the photosensitive layer to light of a wavelength of 313 nm.

[1141]

[1142]

[1143]

[1144]

[1145]

[1146]

[1147]

[1148]

[1149]

[1150]

[1151]

[1152]

[1153]

[1154]

[1155] (Polymer A)

[1156] Polymers 1 to 4 corresponding to polymer A were synthesized by the same method as in Example 4. The abbreviations of monomers constituting each structural unit of the polymer are as described above.

[1157] Polymer 1: St / MAA / MMA / gMA-MAA=47.7 / 19.0 / 1.3 / 32.0 (mass ratio)

[1158] Polymer 2: CHMA / MAA / BzMA = 49 / 19 / 32 (mass ratio)

[1159] Polymer 3: St / AA / AA-GMA = 53.5 / 14.5 / 32 (mass ratio)

[1160] Polymer 4: CHA / AA / HEA = 53.5 / 14.5 / 32 (mass ratio)

[1161] In addition, the weight average molecular weight of the polymer A shown in Table 9 is within the range of 10,000 to 50,000 as shown in Table 9.

[1162] (Polymerizable compound)

[1163] DPHA: dipentaerythritol hexaacrylate (A-DPH manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[1164] A-NOD-N: 1,9-nonanediol diacrylate (A-NOD-N manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[1165] DTMPT: ditrimethylolpropane tetraacrylate (KAYARAD T-1420(T) manufactured by Nippon Kayaku Co., Ltd.)

[1166] A-DCP: dicyclopentane dimethanol diacrylate (A-DCP manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[1167] TMPT: trimethylolpropane triacrylate (A-TMPT manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[1168] SR601: Ethoxylated (4) bisphenol A diacrylate (SR601 manufactured by TOMOE ENGINEERING CO., LTD.)

[1169] KRM8904: 9-functional aliphatic acrylic urethane (KRM8904 manufactured by DAICEL-ALLNEX LTD.)

[1170] KRM8452: 10-functional aliphatic acrylic urethane (KRM8452 manufactured by DAICEL-ALLNEX LTD.)

[1171] (Photopolymerization initiator)

[1172] Omn379: Omnirad 379 (manufactured by IGM Resins BV, an alkylbenzophenone compound)

[1173] Oxe02: Irgacure OXE02 (manufactured by BASF, oxime ester compound)

[1174] Api307: (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropane-1-one (manufactured by Shenzhen UV-Chem Tech LTD)

[1175] (Surfactant)

[1176] F551: MEGAFACE F551 (manufactured by DIC Corporation)

[1177] R41: MEGAFACE R-41 (manufactured by DIC Corporation)

[1178] 710FL: TERGENT 710FL (manufactured by Neos Corporation)

[1179] [Examples 201 to 218, Comparative Example 201: Evaluation of Physical Properties of Compound β]

[1180] The compound β used in Examples 1 to 7 was evaluated for its volatilization resistance (residual rate in the photosensitive layer after the coating process) during the coating process for forming the photosensitive layer by the following procedure.

[1181] Preparation of photosensitive materials

[1182] In the photosensitive material of Example 1-1 of the above-mentioned Example 1 series, except that compound β was changed to the compound exemplified below and the amount of compound β was set to 0.2 equivalents relative to the molar amount of the carboxyl group of polymer A, the photosensitive materials of Examples 201 to 218 were prepared in the same manner.

[1183] Furthermore, a photosensitive material of Comparative Example 201 was prepared in the same manner as in the photosensitive material of Example 1-1 of the above-mentioned Example 1 series, except that 5,6,7,8-tetrahydroquinoline was not added.

[1184] <Evaluation of photosensitive materials>

[1185] (Production of Photosensitive Layer)

[1186] The photosensitive materials of the examples and comparative examples were spin-coated on a glass (Eagle XG manufactured by Corning Incorporated Co., Ltd.) 10×10 cm 2 Then, the obtained coating film was dried at 80° C. using a hot plate to obtain a photosensitive layer having a film thickness of 5 μm.

[1187] The obtained photosensitive layer was evaluated as follows.

[1188] (Measurement of Residual Rate of Compound β)

[1189] First, the following two types of samples were prepared.

[1190] (1) Sample obtained by diluting the photosensitive material 2-fold with deuterated acetone (Sample A)

[1191] (2) About 5 mg of the photosensitive layer obtained above was cut off and dissolved in deuterated acetone to obtain a sample (sample B).

[1192] Next, the AVANCE III manufactured by Bruker was used to measure the 1 The residual rate (%) of compound β was calculated based on the peak surface area ratio of styrene to compound β using H-NMR (lock solvent: deuterated acetone, pulse program: zg30, accumulation time 32 times) and the following formula (H).

[1193] Formula (H): Residual rate = (content of compound β in sample A - content of compound β in sample B) / content of compound β in sample A × 100 [%]

[1194] Next, evaluation was performed based on the following evaluation criteria. The results are shown in Table 10. In addition, Table 10 shown below also shows the molecular weight of compound β.

[1195] (Evaluation Criteria)

[1196] A residual rate is more than 85%

[1197] The B residual rate is 60% or more and less than 85%

[1198] The C residual rate is 20% or more and less than 60%

[1199] D residual rate is less than 20%

[1200] [Table 64]

[1201]

[1202] The results in Table 10 clearly show that when the molecular weight of compound β is 120 or greater (preferably 130 or greater, more preferably 180 or greater), the volatility during the coating process is low (the residual rate of compound β in the photosensitive layer after the coating process is high).

[1203] <Evaluation of transfer film>

[1204] (Production of transfer film)

[1205] On a polyethylene terephthalate film (manufactured by Toray Industries, Inc., 16KS40 (16QS62)) (temporary support) having a thickness of 16 μm, the photosensitive material of each embodiment and comparative example was adjusted and coated using a slit nozzle to have a thickness of 5 μm after drying, and then dried at 100°C for 2 minutes to form a photosensitive layer.

[1206] A 16 μm-thick polyethylene terephthalate film (16KS40 (16QS62) manufactured by Toray Industries, Inc.) (cover film) was pressure-bonded to the obtained photosensitive layer to prepare transfer films of Examples and Comparative Examples.

[1207] The cover film was peeled off from the transfer film prepared above and laminated onto a glass (Eagle XG manufactured by Corning Incorporated Co., Ltd.) 10×10 cm 2 The photosensitive layer of the transfer film was transferred onto the glass surface. Lamination conditions were: a touch panel substrate temperature of 40°C, a rubber roller temperature (i.e., lamination temperature) of 110°C, a linear pressure of 3 N / cm, and a conveying speed of 2 m / min.

[1208] About 5 mg of the photosensitive layer of the obtained glass with a photosensitive layer was cut out and dissolved in deuterated acetone to prepare a sample (sample C).

[1209] In the above (Determination of the residual rate of compound β), except for changing sample B to sample C, the volatility of compound β in the coating process (the residual rate of compound β in the photosensitive layer after the coating process) was determined by the same method, and the results were the same as the results shown in the above Table 10.

[1210] [Example 1001 (Fabrication and Evaluation of Device)]

[1211] <Production of Transparent Laminate>

[1212] A substrate was prepared in which an ITO transparent electrode pattern and copper routing wiring were formed on a cycloolefin transparent film.

[1213] Using the transfer film of Example 1-1 of the Example 1 series, with the protective film removed, an ITO transparent electrode pattern and copper routing wiring were laminated to the position covering the transfer film. Lamination was performed using a vacuum laminator manufactured by MCK Corporation under the following conditions: a cycloolefin transparent film temperature of 40°C, a rubber roller temperature of 100°C, a linear pressure of 3 N / cm, and a conveyor speed of 2 m / min.

[1214] Then, after peeling off the temporary support, pattern exposure was performed using an exposure mask (a quartz exposure mask having a pattern for forming an overcoat layer) and a high-pressure mercury lamp. As exposure conditions, the cumulative exposure dose measured by an illuminometer at 365 nm was 1000 mJ / cm 2 .

[1215] After the exposure, the photosensitive layer of the laminate from which the temporary support was peeled was developed for 40 seconds using a 1 mass % sodium carbonate aqueous solution (liquid temperature: 32° C.) as a developer.

[1216] Ultrapure water was then sprayed from an ultrahigh-pressure cleaning nozzle onto the developed transparent film substrate to remove any residue. Air was then blown in to remove moisture from the transparent film substrate, resulting in a transparent laminated structure consisting of an ITO transparent electrode pattern, copper routing wiring, and a cured film laminated in this order.

[1217] A touch panel was fabricated using the produced transparent laminate by a known method, and the produced touch panel was bonded to a liquid crystal display element produced by the method described in paragraphs 0097 to 0119 of Japanese Patent Application Laid-Open No. 2009-47936 to produce a liquid crystal display device including the touch panel.

[1218] It was confirmed that the obtained liquid crystal display devices equipped with a touch panel all had excellent display characteristics and operated normally.

[1219] [Example 1002 (Fabrication and Evaluation of Device)]

[1220] A liquid crystal display device having a touch panel is prepared by the same method as Example 1001, except that the above-mentioned transfer film is changed to a transfer film other than Example 1-1 of the above-mentioned Example 1 series and any one of the transfer films of the above-mentioned Example 2 series, Example 4 series, Example 5 series and Example 6 series.

[1221] It was confirmed that the obtained liquid crystal display devices equipped with a touch panel all had excellent display characteristics and operated normally.

[1222] [Example 1003 (Fabrication and Evaluation of Device)]

[1223] <Production of Transparent Laminate>

[1224] A substrate was prepared in which an ITO transparent electrode pattern and copper routing wiring were formed on a cycloolefin transparent film.

[1225] Using the transfer film of Example 3, from which the protective film had been removed, an ITO transparent electrode pattern and copper routing wiring were laminated to the position covering the transfer film. Lamination was performed using a vacuum laminator manufactured by MCK Corporation under the following conditions: a cycloolefin transparent film temperature of 40°C, a rubber roller temperature of 100°C, a linear pressure of 3 N / cm, and a conveyor speed of 2 m / min.

[1226] The resulting temporary support of the substrate with the photosensitive layer was then attached to an exposure mask (a quartz exposure mask having a pattern for forming an overcoat layer). Pattern exposure was performed through the temporary support using a proximity exposure machine (manufactured by Hitachi High-Tech Corporation) equipped with an ultrahigh-pressure mercury lamp, with a filter that cuts wavelengths of 350 nm or less. The exposure conditions were a cumulative exposure dose of 80 mJ / cm² as measured by an illuminometer at 365 nm. 2 .

[1227] After exposure, the temporary support was peeled off, and then the photosensitive layer of the laminate from which the temporary support was peeled off was developed for 40 seconds using a 1 mass % sodium carbonate aqueous solution (liquid temperature: 32° C.) as a developer.

[1228] Then, ultrapure water was sprayed from an ultrahigh pressure cleaning nozzle onto the transparent film substrate after the development process to remove the residue. Then, air was blown in to remove moisture from the transparent film substrate.

[1229] Next, the formed pattern was subjected to a second exposure using a high-pressure mercury lamp. In the second exposure using the high-pressure mercury lamp, the cumulative exposure dose measured by a 365 nm illuminometer was 1000 mJ / cm 2 .

[1230] Through the above-described procedure, a transparent laminated body was formed in which an ITO transparent electrode pattern, a copper routing wiring, and a cured film were sequentially laminated on a transparent film substrate.

[1231] A touch panel was fabricated using the produced transparent laminate by a known method, and the produced touch panel was bonded to a liquid crystal display element produced by the method described in paragraphs 0097 to 0119 of Japanese Patent Application Laid-Open No. 2009-47936 to produce a liquid crystal display device including the touch panel.

[1232] It was confirmed that the obtained liquid crystal display devices equipped with a touch panel all had excellent display characteristics and operated normally.

[1233] [Example 1004 (Fabrication and Evaluation of Device)]

[1234] A liquid crystal display device including a touch panel was produced by the same method as in Example 1003, except that the transfer film was replaced with the transfer film of the Example 7 series.

[1235] It was confirmed that the obtained liquid crystal display devices equipped with a touch panel all had excellent display characteristics and operated normally.

[1236] Explanation of symbols

[1237] 12 - Temporary support, 14 - Photosensitive layer, 16 - Cover film, 100 - Transfer film.

Claims

1. A photosensitive material that meets the following requirement W01: W01: Contains polymer Ab0, which is polymer A having carboxyl groups and further has a structure b0 in which the carboxyl groups of polymer A are decarboxylated by exposure to light, thereby reducing the amount of the carboxyl groups.

2. The photosensitive material according to claim 1, wherein The solubility of the polymer A in the developer changes in the exposed portion.

3. The photosensitive material according to claim 1 or 2, wherein The structure b0 is a heteroaromatic ring.

4. The photosensitive material according to claim 3, wherein The heteroaromatic ring is a polycyclic heteroaromatic ring.

5. The photosensitive material according to claim 4, wherein The heteroaromatic ring has 1 to 4 nitrogen atoms as ring member atoms.

6. The photosensitive material according to claim 4, wherein The heteroaromatic ring is a heteroaromatic ring formed by condensing 2 to 5 rings and has 1 to 4 nitrogen atoms as ring member atoms.

7. The photosensitive material according to claim 6, wherein The heteroaromatic ring has 5 to 15 ring member atoms.

8. The photosensitive material according to claim 6, wherein The heteroaromatic ring is a heteroaromatic ring obtained by condensing two or three rings.

9. The photosensitive material according to claim 6, wherein The polymer A has a repeating unit having the structure b0.

10. The photosensitive material according to claim 3, wherein The polymer A has a repeating unit having a carboxyl group.

11. The photosensitive material according to claim 10, wherein The polymer A has a repeating unit represented by the following general formula (A): In the general formula (A), R A1 represents a hydrogen atom, a halogen atom or an alkyl group, A 1 represents a single bond or a divalent linking group.

12. The photosensitive material according to claim 9, wherein The polymer A has a repeating unit represented by the following general formula (A): In the general formula (A), R A1 represents a hydrogen atom, a halogen atom or an alkyl group, A 1 represents a single bond or a divalent linking group.

13. The photosensitive material according to claim 12, wherein The content of the structure b0 in the polymer A is 1% by mass to 40% by mass relative to the total mass of the polymer A. The content of the repeating unit having a carboxyl group in the polymer A is 10 mol% to 65 mol% based on the polymer A.

14. The photosensitive material according to claim 3, wherein The polymer A has a repeating unit having a polymerizable group.

15. The photosensitive material according to claim 3, wherein The polymer includes a repeating unit having an aromatic ring. The photosensitive material according to claim 1 or 2, further comprising a polymerizable compound. 17 . The photosensitive material according to claim 1 , further comprising a photopolymerization initiator.

18. The photosensitive material according to claim 17, wherein The photopolymerization initiator is one or more selected from oxime ester compounds and aminoacetophenone compounds.

19. A pattern forming method, comprising: a step of forming a photosensitive layer on a substrate using the photosensitive material according to claim 17 or 18; exposing the photosensitive layer to a pattern; a step of developing the exposed photosensitive layer using an alkaline developer to form a patterned photosensitive layer; and a step of exposing the patterned photosensitive layer to light.

20. A pattern forming method comprising: Step X1 of forming a photosensitive layer on a substrate using the photosensitive material according to claim 1 or 2, Step X2 of pattern-exposing the photosensitive layer, and Step X3 of developing the pattern-exposed photosensitive layer using a developer. 21 . A transfer film comprising a temporary support and a photosensitive layer formed using the photosensitive material according to claim 1 .

22. The transfer film according to claim 21, wherein The transmittance of the photosensitive layer at 365 nm is greater than 65%.

23. The transfer film according to claim 21 or 22, wherein A ratio of the transmittance of the photosensitive layer at 365 nm to the transmittance of the photosensitive layer at 313 nm is 1.5 or more.

24. The transfer film according to claim 21 or 22, wherein The content of the carboxyl group in the photosensitive layer is reduced at a reduction rate of 5 mol % or more by irradiation with actinic rays or radiation.

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